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Sample records for naphthenic acid solvent

  1. Investigation of aggregation in solvent extraction of lanthanides by acidic extractants (organophosphorus and naphthenic acid)

    Science.gov (United States)

    Zhou, N.; Wu, J.; Yu, Z.; Neuman, R.D.; Wang, D.; Xu, G.

    1997-01-01

    Three acidic extractants (I) di(2-ethylhexyl) phosphoric acid (HDEHP), (II) 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEHPEHE) and (III) naphthenic acid were employed in preparing the samples for the characterization of the coordination structure of lanthanide-extractant complexes and the physicochemical nature of aggregates formed in the organic diluent of the solvent extraction systems. Photo correlation spectroscopy (PCS) results on the aggregates formed by the partially saponified HDEHP in n-heptane showed that the hydrodynamic radius of the aggregates was comparable to the molecular dimensions of HDEHP. The addition of 2-octanol into the diluent, by which the mixed solvent was formed, increased the dimensions of the corresponding aggregates. Aggregates formed from the lanthanide ions and HDEHP in the organic phase of the extraction systems were found very unstable. In the case of naphthenic acid, PCS data showed the formation of w/o microemulsion from the saponified naphthenic acid in the mixed solvent. The extraction of lanthanides by the saponified naphthenic acid in the mixed solvent under the given experimental conditions was a process of destruction of the w/o microemulsion. A possible mechanism of the breakdown of the w/o microemulsion droplets is discussed.

  2. Investigation of aggregation in solvent extraction of lanthanides by acidic extractants (organo-phosphorus and naphthenic acid)

    Institute of Scientific and Technical Information of China (English)

    周乃扶; 吴瑾光; 俞致健; 王笃金; 徐光宪

    1997-01-01

    Three acidic extractants (Ⅰ) di(2-ethylhexyl) phosphoric acid (HDEHP),(Ⅱ) 2-ethylhexyl phos-phonic acid mono-2-ethylhexyl ester (KEHPEHE) and (Ⅲ) naphthenic acid were employed in preparing the samples for the characterization of the coordination structure of lanthanlde-extractant complexes and the physicochemical nature of aggregates formed in the organic diluent of the solvent extraction systems.Photo correlation spectroscopy (PCS) re-suits on the aggregates formed by the partially saponified HDEHP in n -heptane showed that the hydrodynamic radius of the aggregates was comparable to the molecular dimensions of HDEHP.The addition of 2-octanol into the diluent,by which the mixed solvent was formed,increased the dimensions of the corresponding aggregates.Aggregates formed from the ianthamde ions and HDEHP in the organic phase of the extraction systems were found very unstable.In the case of naphthenic acid,PCS data showed the formation of w/o microemulsion from the saponified naphthenic acid in the mix

  3. IMPROVED PROCESSES TO REMOVE NAPHTHENIC ACIDS

    Energy Technology Data Exchange (ETDEWEB)

    Aihua Zhang; Qisheng Ma; Kangshi Wang, William A. Goddard, Yongchun Tang

    2005-05-05

    In the second year of this project, we continued our effort to develop low temperature decarboxylation catalysts and investigate the behavior of these catalysts at different reaction conditions. We conducted a large number of dynamic measurements with crude oil and model compounds to obtain the information at different reaction stages, which was scheduled as the Task2 in our work plan. We developed a novel adsorption method to remove naphthenic acid from crude oil using naturally occurring materials such as clays. Our results show promise as an industrial application. The theoretical modeling proposed several possible reaction pathways and predicted the reactivity depending on the catalysts employed. From all of these studies, we obtained more comprehensive understanding about catalytic decarboxylation and oil upgrading based on the naphthenic acid removal concept.

  4. Improved Processes to Remove Naphthenic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Aihua Zhang; Qisheng Ma; Kangshi Wang; Yongchun Tang; William A. Goddard

    2005-12-09

    In the past three years, we followed the work plan as we suggested in the proposal and made every efforts to fulfill the project objectives. Based on our large amount of creative and productive work, including both of experimental and theoretic aspects, we received important technical breakthrough on naphthenic acid removal process and obtained deep insight on catalytic decarboxylation chemistry. In detail, we established an integrated methodology to serve for all of the experimental and theoretical work. Our experimental investigation results in discovery of four type effective catalysts to the reaction of decarboxylation of model carboxylic acid compounds. The adsorption experiment revealed the effectiveness of several solid materials to naphthenic acid adsorption and acidity reduction of crude oil, which can be either natural minerals or synthesized materials. The test with crude oil also received promising results, which can be potentially developed into a practical process for oil industry. The theoretical work predicted several possible catalytic decarboxylation mechanisms that would govern the decarboxylation pathways depending on the type of catalysts being used. The calculation for reaction activation energy was in good agreement with our experimental measurements.

  5. Coal is a potential source of naphthenic acids in groundwater.

    Science.gov (United States)

    Scott, Angela C; Whittal, Randy M; Fedorak, Phillip M

    2009-03-15

    Naphthenic acids, with the general formula C(n)H(2n+Z)O(2), are found in conventional petroleums and oil sands ores. These acids are toxic to aquatic life, so their discharge from petroleum processing into receiving waters must be avoided. In a previous study, naphthenic acids were putatively identified in groundwaters from two domestic wells that were distant from petroleum sources. However, coal deposits were near these wells. In this study, waters from the two wells were extracted and analyzed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to unequivocally confirm the presence of naphthenic acids and other organic acids. In addition, distilled water was percolated through three crushed coal samples and the leachates were shown to contain a variety of organic acids, including naphthenic acids. These results clearly demonstrate that coal is a source of naphthenic acids and that the naphthenic acids can leach into groundwaters. Thus, the presence of naphthenic acids in waters cannot be solely attributed to petroleum or petroleum industry activities.

  6. Interfacial (o/w) properties of naphthetic acids and metal naphthenates, naphtenic acid characterization and metal naphthenate inhibition

    Energy Technology Data Exchange (ETDEWEB)

    Brandal, Oeystein

    2005-07-01

    Deposition of metal naphthenates in process facilities is becoming a huge problem for petroleum companies producing highly acidic crudes. In this thesis, the main focus has been towards the oil-water (o/w) interfacial properties of naphthenic acids and their ability to react with different divalent cations across the interface to form metal naphthenates. The pendant drop technique was utilized to determine dynamic interfacial tensions (IFT) between model oil containing naphthenic acid, synthetic as well as indigenous acid mixtures, and pH adjusted water upon addition of different divalent cations. Changes in IFT caused by the divalent cations were correlated to reaction mechanisms by considering two reaction steps with subsequent binding of acid monomers to the divalent cation. The results were discussed in light of degree of cation hydration and naphthenic acid conformation, which affect the interfacial conditions and thus the rate of formation of 2:1 complexes of acid and cations. Moreover, addition of non-ionic oil-soluble surfactants used as basis compounds in naphthenate inhibitors was found to hinder a completion of the reaction through interfacial dilution of the acid monomers. Formation and stability of metal naphthenate films at o/w interfaces were studied by means of Langmuir technique with a trough designed for liquid-liquid systems. The effects of different naphthenic acids, divalent cations, and pH of the subphase were investigated. The results were correlated to acid structure, cation hydration, and degree of dissociation, which all affect the film stability against compression. Naphthenic acids acquired from a metal naphthenate deposit were characterized by different spectroscopic techniques. The sample was found to consist of a narrow family of 4-protic naphthenic acids with molecular weights around 1230 g/mol. These acids were found to be very o/w interfacially active compared to normal crude acids, and to form Langmuir monolayers with stability

  7. Microwave-assisted preparation of naphthenic acid esters

    Directory of Open Access Journals (Sweden)

    VERA CIRIN-NOVTA

    2006-12-01

    Full Text Available The synthesis of esters of natural petroleum acids of the naphthenic type assisted with microwave irradiation under the conditions of acid catalysis was carried out with various alcohols: methanol, ethanol, n-butanol and tert-butyl alcohol. Microwave dielectric heating of the reaction mixture in an unmodified microwave oven with activation of the naphthenic acids with sulfuric and p-toluenesulfonic acid afforded the esters of the naphthenic acids. Depending on the catalyst and the steric and nucleophilic properties of the alcohols, the yield of naphthenic esters ranged from 31.25 % to 88.90 %. As a consequence of microwave dielectric heating, the esterification time was reduced from 6–10 h to 5 min.

  8. Model development for naphthenic acids ozonation process.

    Science.gov (United States)

    Al Jibouri, Ali Kamel H; Wu, Jiangning

    2015-02-01

    Naphthenic acids (NAs) are toxic constituents of oil sands process-affected water (OSPW) which is generated during the extraction of bitumen from oil sands. NAs consist mainly of carboxylic acids which are generally biorefractory. For the treatment of OSPW, ozonation is a very beneficial method. It can significantly reduce the concentration of NAs and it can also convert NAs from biorefractory to biodegradable. In this study, a factorial design (2(4)) was used for the ozonation of OSPW to study the influences of the operating parameters (ozone concentration, oxygen/ozone flow rate, pH, and mixing) on the removal of a model NAs in a semi-batch reactor. It was found that ozone concentration had the most significant effect on the NAs concentration compared to other parameters. An empirical model was developed to correlate the concentration of NAs with ozone concentration, oxygen/ozone flow rate, and pH. In addition, a theoretical analysis was conducted to gain the insight into the relationship between the removal of NAs and the operating parameters.

  9. Characterization of Magnetite Scale Formed in Naphthenic Acid Corrosion

    Science.gov (United States)

    Jin, Peng; Robbins, Winston; Bota, Gheorghe; Nesic, Srdjan

    2017-02-01

    Naphthenic acid corrosion (NAC) is one of the major concerns for corrosion engineers in refineries. Traditionally, the iron sulfide (FeS) scale, formed when sulfur compounds in crudes corrode the metal, is expected to be protective and limit the NAC. Nevertheless, no relationship has been found between protectiveness and the characteristics of FeS scale. In this study, lab scale tests with model sulfur compounds and naphthenic acids replicated corrosive processes of refineries with real crude fractions behavior. The morphology and chemical composition of scales were analyzed with scanning electron microscopy and transmission electron microscopy. These high-resolution microscopy techniques revealed the presence of an iron oxide (Fe3O4 or magnetite) scale and discrete particulates on metal surfaces under FeS scales, especially on a low chrome steel. The presence of the iron oxide was correlated with the naphthenic acid activity during the experiments. It is postulated that the formation of the magnetite scale resulted from the decomposition of iron naphthenates at high temperatures. It is further postulated that a nano-particulate form of magnetite may be providing corrosion resistance.

  10. Characterization of Magnetite Scale Formed in Naphthenic Acid Corrosion

    Science.gov (United States)

    Jin, Peng; Robbins, Winston; Bota, Gheorghe; Nesic, Srdjan

    2016-10-01

    Naphthenic acid corrosion (NAC) is one of the major concerns for corrosion engineers in refineries. Traditionally, the iron sulfide (FeS) scale, formed when sulfur compounds in crudes corrode the metal, is expected to be protective and limit the NAC. Nevertheless, no relationship has been found between protectiveness and the characteristics of FeS scale. In this study, lab scale tests with model sulfur compounds and naphthenic acids replicated corrosive processes of refineries with real crude fractions behavior. The morphology and chemical composition of scales were analyzed with scanning electron microscopy and transmission electron microscopy. These high-resolution microscopy techniques revealed the presence of an iron oxide (Fe3O4 or magnetite) scale and discrete particulates on metal surfaces under FeS scales, especially on a low chrome steel. The presence of the iron oxide was correlated with the naphthenic acid activity during the experiments. It is postulated that the formation of the magnetite scale resulted from the decomposition of iron naphthenates at high temperatures. It is further postulated that a nano-particulate form of magnetite may be providing corrosion resistance.

  11. Ozonation of oil sands process water removes naphthenic acids and toxicity.

    Science.gov (United States)

    Scott, Angela C; Zubot, Warren; MacKinnon, Michael D; Smith, Daniel W; Fedorak, Phillip M

    2008-03-01

    Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): or = 22).

  12. Mitigation of naphthenate related production upsets in high TAN (Total Acid Number) crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Ostojic, Nik [Maersk Oil, Copenhagen (Denmark); Vijn, Pieter; Reiners, Robert [Champion Technologies Europe BV, Delden (Netherlands)

    2012-07-01

    This paper describes a strategy for prediction, evaluation and mitigation of calcium naphthenate related production problems. Developing fields with acidic crude in the North Sea, West Africa, Bohai Bay (China) and Brazil is becoming more common in recent years. The high acid crude contains a considerable amount of naphthenic acids, typically having a Total Acid Number (TAN) higher than 0.5 mg KOH/g. Formation of either hard type 'calcium naphthenate precipitates' or soft type 'sodium carboxylate/emulsions' during crude oil production can lead to severe flow assurance and separation problems. In severe cases this may lead to production shutdowns to clean-up the equipment. A number of different naphthenate mitigation approaches have been published but no one particular approach is considered to be the most efficient as it depends significantly on the particular field conditions. Initially, this problem was addressed by deploying large volumes of (usually organic) acid, but more recently high efficiency low dose naphthenate inhibitors have been introduced. For predicting naphthenate scaling potential, methods were developed to determine the concentration of 1230 Dalton naphthenic tetra acid (ARN acids) in either deposit or crude oil and this information can be used to locate and potentially isolate the problem to a certain reservoir. Also, methods were developed to design suitable low dose naphthenate inhibitors. As these inhibitors are field tested, monitoring is required to ensure the product is performing most efficiently. In cases of tight emulsions however, this is less difficult as the oil dehydration and water quality is affected instantly. Methods were developed to allow monitoring of the calcium naphthenate deposition in field trails, thus allow trending and evaluation of the chemicals performance. After detailed analyses and discussions of the developed methods, a North Sea case history is presented reviewing several years of treating

  13. Role of naphthenic acids in stabilizing water-in-diluted model oil emulsions.

    Science.gov (United States)

    Gao, Song; Moran, Kevin; Xu, Zhenghe; Masliyah, Jacob

    2010-06-17

    The need for alkaline conditions in oil sands processing is, in part, to produce natural surfactants from bitumen. Previous studies have shown that the produced surfactants are primarily carboxylic salts of naphthenic acids with the possibility of sulfonic salts as well. The role of these natural surfactants, particularly those in the naphthenate class, is to provide a physicochemical basis for several subprocesses in bitumen extraction. In this study, it was found that the content of indigenous naphthenic acids in bitumen can destabilize, to some extent, the water-in-oil emulsion by lowering the interfacial tension, reducing the rigidity and promoting the coalescence of water droplets.

  14. Synergy effect of naphthenic acid corrosion and sulfur corrosion in crude oil distillation unit

    Science.gov (United States)

    Huang, B. S.; Yin, W. F.; Sang, D. H.; Jiang, Z. Y.

    2012-10-01

    The synergy effect of naphthenic acid corrosion and sulfur corrosion at high temperature in crude oil distillation unit was studied using Q235 carbon-manganese steel and 316 stainless steel. The corrosion of Q235 and 316 in corrosion media containing sulfur and/or naphthenic acid at 280 °C was investigated by weight loss, scanning electron microscope (SEM), EDS and X-ray diffractometer (XRD) analysis. The results showed that in corrosion media containing only sulfur, the corrosion rate of Q235 and 316 first increased and then decreased with the increase of sulfur content. In corrosion media containing naphthenic acid and sulfur, with the variations of acid value or sulfur content, the synergy effect of naphthenic acid corrosion and sulfur corrosion has a great influence on the corrosion rate of Q235 and 316. It was indicated that the sulfur accelerated naphthenic acid corrosion below a certain sulfur content but prevented naphthenic acid corrosion above that. The corrosion products on two steels after exposure to corrosion media were investigated. The stable Cr5S8 phases detected in the corrosion products film of 316 were considered as the reason why 316 has greater corrosion resistance to that of Q235.

  15. Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples.

    Science.gov (United States)

    Scott, Angela C; Young, Rozlyn F; Fedorak, Phillip M

    2008-11-01

    The extraction of bitumen from the oil sands in Canada releases toxic naphthenic acids into the process-affected waters. The development of an ideal analytical method for quantifying naphthenic acids (general formula C(n)H(2n+Z)O(2)) has been impeded by the complexity of these mixtures and the challenges of differentiating naphthenic acids from other naturally-occurring organic acids. The oil sands industry standard FTIR method was compared with a newly-developed GC-MS method. Naphthenic acids concentrations were measured in extracts of surface and ground waters from locations within the vicinity of and away from the oil sands deposits and in extracts of process-affected waters. In all but one case, FTIR measurements of naphthenic acids concentrations were greater than those determined by GC-MS. The detection limit of the GC-MS method was 0.01 mg L(-1) compared to 1 mg L(-1) for the FTIR method. The results indicated that the GC-MS method is more selective for naphthenic acids, and that the FTIR method overestimates their concentrations.

  16. A New Method for Determination of Naphthenic Acids in Crude Oil

    Institute of Scientific and Technical Information of China (English)

    Lü Zhenbo; Zhai Yuchun; Zhao Shanlin; Zhuang Lihong

    2004-01-01

    The petroleum acids in crude oil were separated by extraction with column chromatogram and anion exchange resin. The separation effect and the related composition and structure of petroleum acids were obtained by using IR (Infra-Red) spectra techniques. The separated petroleum acids can under special conditions react with methanol to form corresponding esters, which can be analyzed by CI (chemical ionization)-MS (mass spectrometry). The characteristic ion peaks m/z (M+15)+ of naphthenic acid esters combined with z-series formula CnH2n+zO2 of naphthenic acids can be used to classify naphthenic acids into fatty acids, mono-cyclic, bi-cyclic, tri-cyclic, and higher polycyclic acids. The analytical results can give the molecular weight and the carbon number distribution of petroleum acids contained in crude oil. The results of study indicate that this method is simple, rapid and easy in operation.

  17. Immunotoxic effects of oil sands-derived naphthenic acids to rainbow trout

    Energy Technology Data Exchange (ETDEWEB)

    MacDonald, Gillian Z.; Hogan, Natacha S. [Canadian Rivers Institute, Department of Biology, University of Prince Edward Island, 550 University Avenue, Charlottetown, PEI (Canada); Koellner, Bernd [Friedrich Loeffler Institute, Federal Research Institute of Animal Health, Institute of Immunology, Greifswald (Germany); Thorpe, Karen L.; Phalen, Laura J. [Canadian Rivers Institute, Department of Biology, University of Prince Edward Island, 550 University Avenue, Charlottetown, PEI (Canada); Wagner, Brian D. [Department of Chemistry, University of Prince Edward Island, Charlottetown (Canada); Heuvel, Michael R. van den, E-mail: mheuvel@upei.ca [Canadian Rivers Institute, Department of Biology, University of Prince Edward Island, 550 University Avenue, Charlottetown, PEI (Canada)

    2013-01-15

    Naphthenic acids are the major organic constituents in waters impacted by oil sands. To investigate their immunotoxicity, rainbow trout (Oncorhynchus mykiss) were injected with naphthenic acids extracted from aged oil sands tailings water. In two experiments, rainbow trout were injected intraperitoneally with 0, 10, or 100 mg/kg of naphthenic acids, and sampled after 5 or 21 d. Half of the fish from the 21 d exposure were co-exposed to inactivated Aeromonas salmonicida (A.s.) to induce an immune response. A positive control experiment was conducted using an intraperitoneal injection of 100 mg/kg of benzo[a]pyrene, a known immune suppressing compound. T-lymphocytes, B-lymphocytes, thrombocytes, and myeloid cells were counted in blood and lymphatic tissue using flow cytometry. In the 5 d exposure, there was a reduction in blood leucocytes and spleen thrombocytes at the 100 mg/kg dose. However, at 21 d, leucocyte populations showed no effects of exposure with the exception that spleen thrombocyte populations increase at the 100 mg/kg dose. In the 21 d exposure, B- and T-lymphocytes in blood showed a significant Dose Multiplication-Sign A.s. interaction, indicating stimulated blood cell proliferation due to naphthenic acids alone as well as due to A.s. Naphthenic acid injections did not result in elevated bile fluorescent metabolites or elevated hepatic EROD activity. In contrast to naphthenic acids exposures, as similar dose of benzo[a]pyrene caused a significant decrease in B- and T-lymphocyte absolute counts in blood and relative B-lymphocyte counts in spleen. Results suggest that the naphthenic acids may act via a generally toxic mechanism rather than by specific toxic effects on immune cells.

  18. Biodegradation of naphthenic acid surrogates by axenic cultures.

    Science.gov (United States)

    Yue, Siqing; Ramsay, Bruce A; Ramsay, Juliana A

    2015-07-01

    This is the first study to report that bacteria from the genera Ochrobactrum, Brevundimonas and Bacillus can be isolated by growth on naphthenic acids (NAs) extracted from oil sands process water (OSPW). These pure cultures were screened for their ability to use a range of aliphatic, cyclic and aromatic NA surrogates in 96-well microtiter plates using water-soluble tetrazolium redox dyes (Biolog Redox Dye H) as the indicator of metabolic activity. Of the three cultures, Ochrobactrum showed most metabolic activity on the widest range of NA surrogates. Brevundomonas and especially Ochrobactrum had higher metabolic activity on polycyclic aromatic compounds than other classes of NA surrogates. Bacillus also oxidized a wide range of NA surrogates but not as well as Ochrobactrum. Using this method to characterize NA utilisation, one can identify which NAs or NA classes in OSPW are more readily degraded. Since aromatic NAs have been shown to have an estrogenic effect and polycyclic monoaromatic compounds have been suggested to pose the greatest environmental threat among the NAs, these bacterial genera may play an important role in detoxification of OSPW. Furthermore, this study demonstrates that bacteria belonging to the genera Ochrobactrum and Bacillus can also degrade surrogates of tricyclic NAs.

  19. Response of Chlamydomonas reinhardtii to naphthenic acid exposure

    Energy Technology Data Exchange (ETDEWEB)

    Goff, K.; Wilson, K. [Saskatchewan Univ., Saskatoon, SK (Canada); Headley, J. [Environment Canada, Ottawa, ON (Canada)

    2010-07-01

    This study examined the feasibility of using a model organism for the algal bioremediation of oil sands process water (OSPW), a highly toxic mixture of sediments, bitumen, ions, and organic and inorganic compounds. Naphthenic acids (NAs) are a contaminant class of particular concern. Bioremediation techniques may mitigate toxicity of OSPW in general, and NAs in particular. Although most studies on the biodegradation of NAs focus on the role of bacteria, fungi, and emergent macrophytes, studies have indicated that algae may also play a key role through direct degradation, biosequestration, or photosynthetic aeration of waters to promote other biological reactions. Chlamydomonas frigida is of particular interest, but no cultures are currently available. Therefore, this study used C. reinhardtii, a well-characterized model organism, to begin analysis of potential algal bioremediation of OSPW. Cultures of C. reinhardtii were grown heterotrophically in nutrient media spiked with a dilution series of NAs. Culture densities were measured to compile growth curves over time, changes in rate of growth, and survivability. Negative ion electrospray mass spectrometry was used to determine the concentration of NAs in solution in relation to growth rate and culture density. The study determined the tolerance of C. reinhardtii to NAs. A mechanism for this tolerance was then proposed.

  20. Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst (Ⅰ) Mechanism of Catalytic Decarboxylation

    Institute of Scientific and Technical Information of China (English)

    Fu Xiaoqin; Dai Zhenyu; Tian Songbai; Hou Suandi; Wang Xieqing

    2008-01-01

    In this paper, the charge distribution, the chemical bond order and the reactive performance of carboxylic acid model compounds on acidic catalyst were investigated by using molecular simulation technology. The simulation results showed that the bond order of C-O was higher than that of C-C,and C-C bond connected to the carbon atom in the carboxyl radical had the lowest bond order. The charge distributions of model naphthenic acids were similar in characteristics that the negative charges were concentrated on carboxyls. According to the simulation results, the mechanisms of catalytic decarboxylation over acidic solid catalyst were proposed, and a new route was put forward regarding removal of the naphthenic acid from crude oil through catalytic decarboxylation.

  1. Measuring naphthenic acid corrosion potential with the Fe powder test

    Directory of Open Access Journals (Sweden)

    Hau, J. L.

    2003-12-01

    Full Text Available Results are presented of experiments performed using a new method to measure the naphthenic acid corrosion potential. The method consists of adding pure iron powder into a small autoclave containing the crude or oil sample. The test is then performed at a given temperature for one hour, after which the oil sample is filtered and the remaining liquid is sent for iron content determination (ppm. The tests are run at 7 different temperature levels, 3 more are run as repeated tests. A best-fitted curve is drawn through these 10 experimental points and the maximum point is thus determined. This becomes the main outcome of the test and it is used to give a measure of the naphthenic acid corrosion potential. The same general trends as observed in the past using the neutralization number or TAN (Total Acid Number is obtained. However, this new test seems capable oí detecting anomalous cases where oil samples having larger values of TAN exhibit less corrosivity than others having much lower values of TAN or where they show completely different corrosivity despite having similar or the same TAN.

    Se presentan los resultados de experimentos realizados con un nuevo método para medir el potencial de corrosión por ácidos nafténicos. El método consiste en añadir hierro puro en polvo a una muestra de crudo o aceite, en un autoclave pequeño. El ensayo se realiza a una temperatura dada durante una hora; luego se filtra la muestra de aceite y el líquido filtrado se envía para medir la concentración de hierro disuelto (ppm. El ensayo se reitera para siete temperaturas diferentes y se repiten tres más para determinar su reproducibilidad. Con estos 10 puntos experimentales se dibuja la mejor curva de ajuste y se determina un máximo de hierro disuelto. Este máximo se convierte en el resultado principal del ensayo y se usa para dar una medida del potencial de corrosión por ácidos nafténicos. Se obtienen las mismas tendencias generales observadas

  2. Mass spectrometry of oil sands naphthenic acids : degradation in OSPW and wetland plants

    Energy Technology Data Exchange (ETDEWEB)

    Headley, J. [Environment Canada, Saskatoon, SK (Canada). Water Science and Technology Directorate

    2009-07-01

    This presentation discussed mass spectrometry of oil sands naphthenic acids and the degradation in OSPW and wetland plants. It presented background information on the Athabasca oil sands and naphthenic acids which involve a mixture of alkanes and cycloalkane carboxylic acids with aliphatic side chains. The presentation also discussed mass spectrometry with electrospray operating in negative ion modes. Loop injection, external standard methods and solid phase extraction were reviewed along with improved analysis by removing background ions. Other topics that were presented included hydroponic test systems and wetland plant toxicity, growth and transpiration. It was concluded that dissipation included species containing oxygen, ozone, O{sub 4}, and O{sub 5}. tabs., figs.

  3. Studies of Heterogeneous Hydrothermal Stripping from Iron-loaded Naphthenic Acid-Alcohol-Kerosen

    Institute of Scientific and Technical Information of China (English)

    王兴尧; 康晓红; 谢慧琴; 卢立柱

    2003-01-01

    The technique of hydrothermal stripping from mixed aqueous-organic systems is a promising method for synthesizing oxide ceramic powders for high-performance applications. Some factors influencing heterogeneous hydrothermal stripping with water from iron-loaded organic phase of naphthenic acid-isooctyl alcohol-kerosene, such as initial concentrations of iron and naphthenic acid, concentration of Fe2O3 "seed", temperature and time, were investigated. Based on the experimental results, the rate equation was established. Nano-ferric oxide powders were obtained by the technique of hydrothermal stripping from the iron-loaded organic phase. The results suggest that the heterogeneous hydrothermal stripping proceeds in 3 steps: adsorption of naphthenic acid dimers and naphthenic complex of iron onto the surface of "seed", hydrolysis of adsorbed complex of iron, and condensation of hydrolyzed complex. The process activation energy is 115 kJ/mol and the heterogeneous hydrothermal stripping is controlled by a chemical reaction(the hydrolysis of naphthenic complex of iron).

  4. Biodegradation of a surrogate naphthenic acid under denitrifying conditions.

    Science.gov (United States)

    Gunawan, Yetty; Nemati, Mehdi; Dalai, Ajay

    2014-03-15

    Extraction of bitumen from the shallow oil sands generates extremely large volumes of waters contaminated by naphthenic acid which pose severe environmental and ecological risks. Aerobic biodegradation of NA in properly designed bioreactors has been investigated in our earlier works. In the present work, anoxic biodegradation of trans-4-methyl-1-cyclohexane carboxylic acid (trans-4MCHCA) coupled to denitrification was investigated as a potential ex situ approach for the treatment of oil sand process waters in bioreactors whereby excessive aeration cost could be eliminated, or as an in situ alternative for the treatment of these waters in anoxic stabilization ponds amended with nitrate. Using batch and continuous reactors (CSTR and biofilm), effects of NA concentration (100-750mgL(-1)), NA loading rate (up to 2607.9mgL(-1)h(-1)) and temperature (10-35°C) on biodegradation and denitrification processes were evaluated. In the batch system biodegradation of trans-4MCHCA coupled to denitrification occurred even at the highest concentration of 750mgL(-1). Consistent with the patterns reported for aerobic biodegradation, increase in initial concentration of NA led to higher biodegradation and denitrification rates and the optimum temperature was determined as 23-24°C. In the CSTR, NA removal and nitrate reduction rates passed through a maximum due to increases in NA loading rate. NA loading rate of 157.8mgL(-1)h(-1) at which maximum anoxic NA and nitrate removal rates (105.3mgL(-1)h(-1) and 144.5mgL(-1)h(-1), respectively) occurred was much higher than those reported for the aerobic alternative (NA loading and removal rates: 14.2 and 9.6mgL(-1)h(-1), respectively). In the anoxic biofilm reactor removal rates of NA and nitrate were dependent on NA loading rate in a linear fashion for the entire range of applied loading rates. The highest loading and removal rates for NA were 2607.9 and 2028.1mgL(-1)h(-1), respectively which were at least twofold higher than the values

  5. Naphthenic acid characterization and distribution in crude oils; Caracterizacao e distribuicao de acidos naftenicos em petroleos

    Energy Technology Data Exchange (ETDEWEB)

    Guimaraes, Regina C.L.; Gomes, Alexandre de O. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil)

    2008-07-01

    Naphthenic acid corrosion was observed for the first time during the distillation process of some kind of crude oils in 1920. Recent reports about naphthenic acid corrosion have been found in China, India, Venezuela, Eastern Europe, Russia and the USA. In Brazil, heavy and acid crude oil processing is rising. Some brazilian crude oils have TAN around 3,0 mg KOH/g. The presence of relatively high levels of naphthenic acids in crude oils is a bane of petroleum refiners; and more recently, of producers as well, who have reported problems during production with calcium and sodium naphthenate . Essentially, these acids which are found to greater or lesser extent in virtually all crude oils are corrosive and tend to cause equipment failures, lead to high maintenance costs and may pose environmental disposal problems. In order to give these information to PETROBRAS, The Research and Development Center of PETROBRAS (CENPES) has been working in house and with brazilian universities developing analytical technicians to know better molecular structures and distribution of these acids compounds in crude oils. This work presents the actual methods and some results from these developments. (author)

  6. Genome Sequence Analysis of the Naphthenic Acid Degrading and Metal Resistant Bacterium Cupriavidus gilardii CR3.

    Directory of Open Access Journals (Sweden)

    Xiaoyu Wang

    Full Text Available Cupriavidus sp. are generally heavy metal tolerant bacteria with the ability to degrade a variety of aromatic hydrocarbon compounds, although the degradation pathways and substrate versatilities remain largely unknown. Here we studied the bacterium Cupriavidus gilardii strain CR3, which was isolated from a natural asphalt deposit, and which was shown to utilize naphthenic acids as a sole carbon source. Genome sequencing of C. gilardii CR3 was carried out to elucidate possible mechanisms for the naphthenic acid biodegradation. The genome of C. gilardii CR3 was composed of two circular chromosomes chr1 and chr2 of respectively 3,539,530 bp and 2,039,213 bp in size. The genome for strain CR3 encoded 4,502 putative protein-coding genes, 59 tRNA genes, and many other non-coding genes. Many genes were associated with xenobiotic biodegradation and metal resistance functions. Pathway prediction for degradation of cyclohexanecarboxylic acid, a representative naphthenic acid, suggested that naphthenic acid undergoes initial ring-cleavage, after which the ring fission products can be degraded via several plausible degradation pathways including a mechanism similar to that used for fatty acid oxidation. The final metabolic products of these pathways are unstable or volatile compounds that were not toxic to CR3. Strain CR3 was also shown to have tolerance to at least 10 heavy metals, which was mainly achieved by self-detoxification through ion efflux, metal-complexation and metal-reduction, and a powerful DNA self-repair mechanism. Our genomic analysis suggests that CR3 is well adapted to survive the harsh environment in natural asphalts containing naphthenic acids and high concentrations of heavy metals.

  7. Simple Method to Determine the Partition Coefficient of Naphthenic Acid in Oil/Water

    DEFF Research Database (Denmark)

    Bitsch-Larsen, Anders; Andersen, Simon Ivar

    2008-01-01

    The partition coefficient for technical grade naphthenic acid in water/n-decane at 295 K has been determined (K-wo = 2.1 center dot 10(-4)) using a simple experimental technique with large extraction volumes (0.09 m(3) of water). Furthermore, nonequilibrium values at different pH values are prese...

  8. Measurement of naphthenic acids in the receiving waters around an offshore oil platform by passive sampling.

    Science.gov (United States)

    Harman, Christopher; Langford, Katherine; Sundt, Rolf C; Brooks, Steven

    2014-09-01

    Polar organic chemical integrative samplers (POCIS) were deployed in the vicinity of an offshore oil installation and analyzed for naphthenic acids (NAs). The POCIS accumulated a range of mono- to tetracyclic NAs, with different degrees of alkylation, with monocyclic acids being the most abundant. Currently, POCIS or similar polar samplers may be the only way to measure exposure to NAs from offshore discharges in situ. In addition, they may be a valuable tool for monitoring similar organic acids in general. © 2014 SETAC.

  9. Tracking Catalytic Esterification of Naphthenic Acids in Crude Oil by ESI FT-ICR MS

    Institute of Scientific and Technical Information of China (English)

    Li Xiaohui; Wu Bencheng; Zhu Jianhua; Tao Xiujuan

    2016-01-01

    The catalytic esterification reaction was used to decrease total acid number (TAN) of crude oil by converting naphthenic acids to naphthenic acid esters in the presence of Zn-Al hydrotalcite used as the catalyst and glycol used as the reactant. The crude oil and its corresponding esterified oil were characterized by the negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Six acidic class species, O2, O1, N1, N2, N1O1 and N1O2 were assigned in the negative-ion spectrum both in the crude oil and its esterified oil. Among the identified acidic compounds, the O2 class was dominant. The relative abundance of O2 class species was much higher than other acidic class species in crude oil, while it was significantly decreased after esterification. The most abundant O2 class species had a car-bon number of 30-34 and a double-bond equivalence (DBE) value of 5 before and after esterification. It could be concluded that the naphthenic acids in crude oil can be esterified to lower its TAN value, and each of them seems to exhibit identical esterification efficiency approximately due to the similar DBE versus the -carbon number distribution before and after es-terification.

  10. Influence of containing of asphaltenes and naphthenic acids over organic deposition inhibitor performance

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Geiza E.; Mansur, Claudia R.E.; Pires, Renata V.; Passos, Leonardo B.; Lucas, Elizabete F. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas; Alvares, Dellyo R.S.; Gonzalez, Gaspar [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2004-07-01

    Organic deposition is a serious problem confronted by the petroleum industry in Brazil and worldwide. Among the main petroleum components that may cause deposition problems are waxes and asphaltenes. This work aims at evaluating the influence of petroleum fractions (asphaltenes and naphthenic acids) on the organic deposition phenomenon as well as on organic deposition inhibitors performance. The influence of the organic fractions was evaluated by their ability to change wax crystals, to lower the pour point and to alter the initial wax appearance temperature. The efficiency of the additives was tested by pour point measurements. The results show that asphaltenes seem to act as organic deposition inhibitors, while naphthenic acids do not significantly change the system. Moreover, employing both of them produces no synergic effect. Among polymeric inhibitors, all of the chemically modified EVA copolymer presented better results than the non-modified commercial EVA copolymer. The best result was observed for EVA28C{sub 16}. (author)

  11. The influence of naphthenic acids and their fractions onto cell membrane permeability

    Directory of Open Access Journals (Sweden)

    Pavlović Ksenija

    2015-01-01

    Full Text Available The influence of naphthenic acids (NAs mixture and their narrow fractions (called NA pH 4, pH 8 and pH 10 onto permeability of beetroot cell membrane is examined. The results showed that the effect depends on treatment duration, concentration and NAs structure. Longer treatment of plant cell membranes with sodium naphthenate (Na-naph resulted in the increase of membrane permeability (e.g. 4-hour treatment with Na-naph (C=100 μmol L-1 increased membrane permeability about 3 times, while prolongation of treatment to 24 hour resulted in the 18 times increasing of the effect. NAs in the concentration range from 0.1 to 10 μmol L-1 does not change membrane permeability, while membrane permeability is increasing linearly with concentration increasing from 10-100 μmol L-1. The strongest effect expressed fraction pH 8, where bi- and tricyclic carboxylic acids are the most abundant. These structures are predominant in the total NAs mixture as well. Thereby could be explained their closest, but a little bit weaker effect, comparing to NAs present in fraction pH 8. The effect of NAs onto beetroot cell membrane is between the effects of anionic (SDS and LS and non-ionic surfactants (Triton X-100. [Projekat Ministarstva nauke Republike Srbije, br. 172006. i br. TR31036

  12. Photocatalytic degradation of commercially sourced naphthenic acids by TiO2-graphene composite nanomaterial.

    Science.gov (United States)

    Liu, Juncheng; Wang, Lin; Tang, Jingchun; Ma, Jianli

    2016-04-01

    Naphthenic acids (NAs) are a major contributor to the toxicity in oil sands process-affected water (OSPW), which is produced by hot water extraction of bitumen. NAs are extremely difficult to be degraded due to its complex ring and side chain structure. Photocatalysis is recognized as a promising technology in the removal of refractory organic pollutants. In this work, TiO2-graphene (P25-GR) composites were synthesized by means of solvothermal method. The results showed that P25-GR composite exhibited better photocatalytic activity than pure P25. The removal efficiency of naphthenic acids in acid solution was higher than that in neutral and alkaline solutions. It was the first report ever known on the photodegradation of NAs based on graphene, and this process achieved a higher removal rate than other photocatalysis degradation of NAs in a shorter reaction time. LC/MS analysis showed that macromolecular NAs (carbon number 17-22, z value -2) were easy to be degraded than the micromolecular ones (carbon number 11-16, z value -2). Furthermore, the reactive oxygen species that play the main role in the photocatalysis system were studied. It was found that holes and ·OH were the main reactive species in the UV/P25-GR photocatalysis system. Given the high removal efficiency of refractory organic pollutants and the short degradation time, photodegradation based on composite catalysts has a broad and practical prospect. The study on the photodegradation of commercially sourced NAs may provide a guidance for the degradation of OSPW NAs by this method. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Mechanistic investigation of industrial wastewater naphthenic acids removal using granular activated carbon (GAC) biofilm based processes.

    Science.gov (United States)

    Islam, Md Shahinoor; Zhang, Yanyan; McPhedran, Kerry N; Liu, Yang; Gamal El-Din, Mohamed

    2016-01-15

    Naphthenic acids (NAs) found in oil sands process-affected waters (OSPW) have known environmental toxicity and are resistant to conventional wastewater treatments. The granular activated carbon (GAC) biofilm treatment process has been shown to effectively treat OSPW NAs via combined adsorption/biodegradation processes despite the lack of research investigating their individual contributions. Presently, the NAs removals due to the individual processes of adsorption and biodegradation in OSPW bioreactors were determined using sodium azide to inhibit biodegradation. For raw OSPW, after 28 days biodegradation and adsorption contributed 14% and 63% of NA removal, respectively. For ozonated OSPW, biodegradation removed 18% of NAs while adsorption reduced NAs by 73%. Microbial community 454-pyrosequencing of bioreactor matrices indicated the importance of biodegradation given the diverse carbon degrading families including Acidobacteriaceae, Ectothiorhodospiraceae, and Comamonadaceae. Overall, results highlight the ability to determine specific processes of NAs removals in the combined treatment process in the presence of diverse bacteria metabolic groups found in GAC bioreactors.

  14. Limitation of fluorescence spectrophotometry in the measurement of naphthenic acids in oil sands process water.

    Science.gov (United States)

    Lu, Weibing; Ewanchuk, Andrea; Perez-Estrada, Leonidas; Sego, Dave; Ulrich, Ania

    2013-01-01

    Fluorescence spectrophotometry has been proposed as a quick screening technique for the measurement of naphthenic acids (NAs). To evaluate the feasibility of this application, the fluorescence emission spectra of NAs extracted from three oil sands process water sources were compared with that of commercial NAs. The NAs resulting from the bitumen extraction process cannot be differentiated because of the similarity of the fluorescence spectra. Separation of the fluorescent species in NAs using high performance liquid chromatography with fluorescence detector proved unsuccessful. The acidic fraction of NAs is fluorescent but the basic fraction of NAs is not fluorescent, implying that aromatic acids in NAs give rise to the fluorescent signals. The concentrations of NAs in oil sands process water were measured by Fourier transform infrared spectroscopy (FTIR), fluorescence spectrophotometry and ultra high performance liquid chromatography-time of flight/mass spectrometry (UPLC-TOF/MS). Commercial Merichem and Kodak NAs are the best standards to use when measuring NAs concentration with FTIR and fluorescence spectrophotometry. In addition, the NAs concentrations measured by fluorescence spectrophotometry are about 30 times higher than those measured by FTIR and UPLC-TOF/MS. The findings in this study underscore the limitation of fluorescence spectrophotometry in the measurement of NAs.

  15. Solar photocatalytic degradation of naphthenic acids in oil sands process-affected water.

    Science.gov (United States)

    Leshuk, Tim; Wong, Timothy; Linley, Stuart; Peru, Kerry M; Headley, John V; Gu, Frank

    2016-02-01

    Bitumen mining in the Canadian oil sands creates large volumes of oil sands process-affected water (OSPW), the toxicity of which is due in part to naphthenic acids (NAs) and other acid extractable organics (AEO). The objective of this work was to evaluate the potential of solar photocatalysis over TiO2 to remove AEO from OSPW. One day of photocatalytic treatment under natural sunlight (25 MJ/m(2) over ∼14 h daylight) eradicated AEO from raw OSPW, and acute toxicity of the OSPW toward Vibrio fischeri was eliminated. Nearly complete mineralization of organic carbon was achieved within 1-7 day equivalents of sunlight exposure, and degradation was shown to proceed through a superoxide-mediated oxidation pathway. High resolution mass spectrometry (HRMS) analysis of oxidized intermediate compounds indicated preferential degradation of the heavier and more cyclic NAs (higher number of double bond equivalents), which are the most environmentally persistent fractions. The photocatalyst was shown to be recyclable for multiple uses, and thus solar photocatalysis may be a promising "green" advanced oxidation process (AOP) for OSPW treatment.

  16. Determination of dissolved naphthenic acids in natural waters by using negative-ion electrospray mass spectrometry.

    Science.gov (United States)

    Headley, John V; Peru, Kerry M; McMartin, Dena W; Winkler, Marcus

    2002-01-01

    Naphthenic acids (NAs) have been implicated as some of the most toxic substances in oil sands leachates and identified as priority substances impacting on aquatic environments. As a group of compounds, NAs are not well characterized and comprise a large group of saturated aliphatic and alicyclic carboxylic acids found in hydrocarbon deposits (petroleum, oil sands bitumen, and crude oils). Described is an analytical method using negative-ion electrospray ionization mass spectrometry (ES/MS) of extracts. Preconcentration was achieved by using a solid-phase extraction procedure utilizing a crosslinked polystyrene-based polymer with acetonitrile elution. Recovery of the Fluka Chemicals NA mixture was highly pH-dependent, with 100% recovery at pH 3.0, but only 66 and 51% recoveries at pHs 7 and 9, respectively. The dissolved phase of the NA was very dependent on sample pH. It is thus critical to measure the pH and determine the appropriate mass profiles to identify NAs in natural waters. The ES/MS analytical procedure proved to be a fast and sensitive method for the recovery and detection of NAs in natural waters, with a detection limit of 0.01 mg/L.

  17. Harnessing oil sands microbial communities for use in ex situ naphthenic acid bioremediation.

    Science.gov (United States)

    Demeter, Marc A; Lemire, Joe; George, Iain; Yue, Gordon; Ceri, Howard; Turner, Raymond J

    2014-02-01

    The caustic hot water extraction process used to release bitumen from the Alberta oil sands generates large volumes of tailings waste, or oil sands process water (OSPW). OSPW contains several components of environmental concern including diluents, polyaromatic hydrocarbons, heavy metals, and naphthenic acids (NAs); the latter are of particular concern as they are acutely toxic to aquatic organisms and mammals. Studies have demonstrated that the naturally occurring OSPW bacteria are capable of metabolizing the NAs. However, this in situ process takes place over hundreds of years, and is incomplete, leaving a recalcitrant fraction of NAs intact. In this study we explore options for recovering and harnessing the naturally occurring OSPW bacteria for potential future use in an aerobic ex situ OSPW treatment system. Here we evaluate our recovered microbes on their ability to degrade two model NAs, cyclohexane carboxylic acid and cyclohexane acetic acid. Using OSPW as a source for a bacterial inoculum, we were able to compare single and multispecies OSPW cultures, grown as either a biofilm, or as a planktonic suspension. Furthermore, we examined the effect of available nutrients on the ability of these cultures to degrade NAs. All biofilms were grown using the Calgary Biofilm Device. GC-MS, and GC-FID reveal that multispecies biofilm and planktonic cultures are each capable of degrading both NAs; a trait not observed for single species cultures. Moreover, complementary carbon sources have a tangible effect on the ability of the cultures to initiate the degradation of the NAs. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Removal of naphthenic acids using adsorption process and the effect of the addition of salt.

    Science.gov (United States)

    Azad, Fakhry Seyedeyn; Abedi, Jalal; Iranmanesh, Sobhan

    2013-01-01

    In this study, various types of adsorbents were examined for the removal of Naphthenic acids (NAs) in the preliminary stage of this study. Among them, activated carbon and nickel (Ni) based alumina (Ni-Al2O3) possess relatively high adsorption capacity of NAs. The removal of NAs was evaluated comparing the total organic carbon (TOC) of the solution before and after the adsorption process. The effect of Ni loading was investigated using Ni-Al2O4 with various nickel loadings. The highest adsorption capacity (20 mg of TOC/1 mg of adsorbent) was belong to Ni-Al2O4 with 10.7% Ni loading. By the addition of salt (1500 ppm NaCl) to NAs solutions having concentrations from of 15 to 38 ppm, it was observed that the adsorption decreased dramatically (up to 80%) depending on the concentration of TOC. The kinetics of the adsorption of TOC on Ni-based alumina was also investigated. The decrease of TOC was more that 40% in the first half hour, indicating that adsorption was very rapid in the beginning. The adsorption increased slightly for up to 5 h and then leveled off when the TOC reached to 50% of initial TOC concentration. However, when sodium chloride (NaCl) was added to the solution, the adsorption decreased to almost 9% within the first half hour, reaching to almost 5% after 3 h. These phenomena suggest that the effectiveness of adsorbents may be improved by decreasing the total dissolved salts in tailings pond wastewater.

  19. Naphthenic acids degradation and toxicity mitigation in tailings wastewater systems and aquatic environments: a review.

    Science.gov (United States)

    Kannel, Prakash R; Gan, Thian Y

    2012-01-01

    Naphthenic acids, NAs (classical formula C(n)H(2n+z)O(2), where n is the carbon numbers, z represents zero or negative even integers), found in oil sands process waters (OSPWs), are toxic to aquatic environments depending upon several factors such as pH, salinity, molecular size and chemical structure of NAs. Among various available methods, biodegradation seems to be generally the most cost-effective method for decreasing concentrations of NAs (n ≤ 21) and reducing their associated toxicity in OSPW, however the mechanism by which the biodegradation of NAs occurs are poorly understood. Ozonation is superior over biodegradation in decreasing higher molecular weight alkyl branched NAs (preferentially, n ≥ 22, -6 ≥ z ≥ -12) as well as enabling accelerated biodegradation and reducing toxicity. Photolysis (UV at 254 nm) is effective in cleaving higher molecular weight NAs into smaller fragments that will be easier for microorganisms to degrade, whereas photocatalysis can metabolize selective NAs (0 ≥ z ≥ -6) efficiently and minimize their associated toxicity. Phytoremediation is applicable for metabolizing specific NAs (O(2), O(3), O(4), and O(5) species) and minimizing their associated toxicities. Petroleum coke (PC) adsorption is effective in reducing the more structurally complex NAs (preferentially 12 ≥ n ≥ 18 and z = -10, -12) and their toxicity in OSPWs, depending upon the PC content, pH and temperature. Several factors have influence on the degradation of NAs in OSPWs and aquatic environments, which include molecular mass and chemical structure of NAs, sediment structure, temperature, pH, dissolved oxygen, nutrients, and bacteria types.

  20. Competitive Adsorption of Naphthenic Acids and Polyaromatic Molecules at a Toluene-Water Interface.

    Science.gov (United States)

    Teklebrhan, Robel B; Jian, Cuiying; Choi, Phillip; Xu, Zhenghe; Sjöblom, Johan

    2016-12-22

    The early-stage competitive co-adsorption of interfacially active naphthenic acids (NAs) and polyaromatic (PA) molecules to a toluene-water interface from the bulk toluene phase was studied using molecular dynamics (MD) simulation. The NA molecules studied had the same polar functional group but different cycloaliphatic nonpolar tails, and a perylene bisimide (PBI)-based molecule was used as a representative PA compound. The results from our simulations suggest that the size and structural features of NA molecules greatly influence the interfacial activity of PA molecules and partitioning of NA molecules at the toluene-water interface. At low concentrations of PA (∼2.3 wt %) and NA (∼0.4 wt %) molecules, NA molecules containing large cycloaliphatic rings (e.g., four rings) or with a very long aliphatic tail (e.g., carbon chain length of 14) were observed to impede the migration of PA molecules to the interface, whereas small NA molecules containing two cycloaliphatic rings had little effect on the adsorption of PA molecules at the toluene-water interface. At high NA concentrations, the adsorption of PA molecules (∼5.75-17.25 wt %) was greatly hindered by the presence of small NA molecules (∼1.6-4.8 wt %) due to the solvation of PA nanoaggregates in the bulk. Adsorption mechanisms of PA and NA molecules at toluene-water interfaces were clarified through a detailed analysis on the interactions among different species in the system. The results obtained from this work provide insights into designing appropriate chemical demulsifiers or co-demulsifiers for breaking water-in-oil emulsions of great industrial applications.

  1. Effects of environmental conditions on aerobic degradation of a commercial naphthenic acid.

    Science.gov (United States)

    Kinley, Ciera M; Gaspari, Daniel P; McQueen, Andrew D; Rodgers, John H; Castle, James W; Friesen, Vanessa; Haakensen, Monique

    2016-10-01

    Naphthenic acids (NAs) are problematic constituents in energy-derived waters, and aerobic degradation may provide a strategy for mitigating risks to aquatic organisms. The overall objective of this study was to determine the influence of concentrations of N (as ammonia) and P (as phosphate), and DO, as well as pH and temperatures on degradation of a commercial NA in bench-scale reactors. Commercial NAs provided replicable compounds necessary to compare influences of environmental conditions on degradation. NAs were quantified using high performance liquid chromatography. Microbial diversity and relative abundance were measured in treatments as explanatory parameters for potential effects of environmental conditions on microbial populations to support analytically measured NA degradation. Environmental conditions that positively influenced degradation rates of Fluka NAs included nutrients (C:N 10:1-500:1, C:P 100:1-5000:1), DO (4.76-8.43 mg L(-1)), pH (6-8), and temperature (5-25 °C). Approximately 50% removal of 61 ± 8 mg L(-1) was achieved in less than 2 d after NA introduction, achieving the method detection limit (5 mg L(-1)) by day 6 of the experiment in treatments with a C:N:P ratio of 100:10:1, DO > 8 mg L(-1), pH ∼8-9, and temperatures >23 °C. Microbial diversity was lowest in lower temperature treatments (6-16 °C), which may have resulted in observed slower NA degradation. Based on results from this study, when macro- and micronutrients were available, DO, pH, and temperature (within environmentally relevant ranges) influenced rates of aerobic degradation of Fluka NAs. This study could serve as a model for systematically evaluating environmental factors that influence NA degradation in field scenarios.

  2. Culturing oil sands microbes as mixed species communities enhances ex situ model naphthenic acid degradation.

    Science.gov (United States)

    Demeter, Marc A; Lemire, Joseph A; Yue, Gordon; Ceri, Howard; Turner, Raymond J

    2015-01-01

    Oil sands surface mining for bitumen results in the formation of oil sands process water (OSPW), containing acutely toxic naphthenic acids (NAs). Potential exists for OSPW toxicity to be mitigated by aerobic degradation of the NAs by microorganisms indigenous to the oil sands tailings ponds, the success of which is dependent on the methods used to exploit the metabolisms of the environmental microbial community. Having hypothesized that the xenobiotic tolerant biofilm mode-of-life may represent a feasible way to harness environmental microbes for ex situ treatment of OSPW NAs, we aerobically grew OSPW microbes as single and mixed species biofilm and planktonic cultures under various conditions for the purpose of assaying their ability to tolerate and degrade NAs. The NAs evaluated were a diverse mixture of eight commercially available model compounds. Confocal microscopy confirmed the ability of mixed and single species OSPW cultures to grow as biofilms in the presence of the NAs evaluated. qPCR enumeration demonstrated that the addition of supplemental nutrients at concentrations of 1 g L(-1) resulted in a more numerous population than 0.001 g L(-1) supplementation by approximately 1 order of magnitude. GC-FID analysis revealed that mixed species cultures (regardless of the mode of growth) are the most effective at degrading the NAs tested. All constituent NAs evaluated were degraded below detectable limits with the exception of 1-adamantane carboxylic acid (ACA); subsequent experimentation with ACA as the sole NA also failed to exhibit degradation of this compound. Single species cultures degraded select few NA compounds. The degradation trends highlighted many structure-persistence relationships among the eight NAs tested, demonstrating the effect of side chain configuration and alkyl branching on compound recalcitrance. Of all the isolates, the Rhodococcus spp. degraded the greatest number of NA compounds, although still less than the mixed species cultures

  3. Bio-physicochemical effects of gamma irradiation treatment for naphthenic acids in oil sands fluid fine tailings

    Energy Technology Data Exchange (ETDEWEB)

    Boudens, Ryan; Reid, Thomas; VanMensel, Danielle; Sabari Prakasanm, M.R. [Great Lakes Institute for Environmental Research, University of Windsor, Windsor, ON (Canada); Ciborowski, Jan J.H. [Biological Sciences, University of Windsor, Windsor, ON (Canada); Weisener, Christopher G., E-mail: weisener@uwindsor.ca [Great Lakes Institute for Environmental Research, University of Windsor, Windsor, ON (Canada)

    2016-01-01

    Naphthenic acids (NAs) are persistent compounds that are components of most petroleum, including those found in the Athabasca oil sands. Their presence in freshly processed tailings is of significant environmental concern due to their toxicity to aquatic organisms. Gamma irradiation (GI) was used to reduce the toxicity and concentration of NAs in oil sands process water (OSPW) and fluid fine tailings (FFT). This investigation systematically studied the impact of GI on the biogeochemical development and progressive reduction of toxicity using laboratory incubations of fresh and aged tailings under anoxic and oxic conditions. GI reduced NA concentrations in OSPW by up to 97% in OSPW and in FFT by 85%. The GI-treated FFT exhibited increased rates of biogeochemical change, dependent on the age of the tailings source. Dissolved oxygen (DO) flux was enhanced in GI-treated FFT from fresh and aged source materials, whereas hydrogen sulfide (HS{sup −}) flux was stimulated only in the fresh FFT. Acute toxicity to Vibrio fischeri was immediately reduced following GI treatment of fresh OSPW. GI treatment followed by 4-week incubation reduced toxicity of aged OSPW to V. fischeri. - Highlights: • Gamma irradiation substantially reduced concentrations of ecotoxic naphthenic acids • Acute toxicity was reduced in gamma irradiated process water • Gamma irradiated tailings exhibited increased rates of microbial respiration.

  4. Processing and Utilization of Naphthenic Base Heavy Crude Oil (continued)

    Institute of Scientific and Technical Information of China (English)

    Wang Xianqing; Men Cungui

    1995-01-01

    @@ Strategy of the Comprehensive Utilization of Naphthenic Base Heavy Crude The further study on the properties and characteristics of the naphthenic base heavy crude shows that the utilization of naphthenic acid, production of low freezing point lube stocks and a series of asphalts are important future trends for comprehensive utilization of these resources.

  5. 炼油厂含盐废水中环烷酸的鉴定与分析%Analysis of Naphthenic Acids in Brine Wastewater from Refineries

    Institute of Scientific and Technical Information of China (English)

    李凌波; 郭宏山; 周艳红; 马荣华

    2012-01-01

    分别用快速化学定性法、GC-MS法、电喷雾(ESI)-MS法和FTIR法研究了加工高酸原油含盐废水及其处理过程废水中环烷酸的快速鉴定、来源、分子识别及含量.实验结果表明,利用在酸性和碱性条件下均产生沉淀的现象可快速鉴定炼油厂含盐废水中的环烷酸;GC-MS法可确定环烷酸主要来自含酸原油电脱盐过程,是影响含酸原油加工废水达标排放的主要组分;ESI-MS法能有效鉴定废水中环烷酸的类型及相对分子质量分布,某炼油厂含盐废水生化处理出水中检出碳数为5~41、相对分子质量为102~ 596、环数为0~6的环烷酸,其中C18环烷酸的含量最高;FTIR法测定某炼油厂气浮和生化处理后,环烷酸的总去除率为93.3%.%Naphthenic acids in brine wastewater from refineries processing acidic crude oil were analyzed by means of chemical analysis, GC-MS, electrospray ionization tandem MS and FTIR. The results showed that the naphthenic acids could be rapidly identified by chemical deposition under acidic and basic conditions. The naphthenic acids were found to derive mainly from crude oil desalter effluent by GC-MS, and were main components to prevent brine wastewater treatment effluent from reaching the discharge standards. The structures and relative molecular mass distributions of the naphthenic acids can be determined by anion electrospray ionization tandem MS. The naphthenic acids in biologically treated brine wastewater from a refinery were identified with the results of the relative molecular mass 102-596, the carbon number 5-41 and the ring number 0-6, in which the content of C18 naphthenic acids was the highest. The naphthenic acid concentration in crude oil desalter effluent from a refinery could be removed 93.3% by gas floatation and biochemical treatment.

  6. PILOT PLANT TEST OF REMOVING NAPHTHENIC ACID FROM 4th VACUUM CUT OF KARAMAY HEAVY CRUDE VIA MICROREACTOR%克拉玛依稠油减四线馏分微反应器脱酸中试研究

    Institute of Scientific and Technical Information of China (English)

    刘江华; 甄新平; 熊良铨; 海日古力

    2012-01-01

    以克拉玛依稠油减四线馏分油为原料,在200 kg/h微通道反应器上进行脱酸新工艺中试试验研究.试验结果表明:与同时运行的工业装置相比,微反应器脱酸工艺的一级脱酸率大于85%,高于工业装置的两级脱酸效果;该工艺能够大幅度降低剂油比,降低装置回收溶剂的能耗,而且简化了脱酸工艺,为从重质原油馏分油中抽出大分子石油酸提供了一项新技术.%Pilot plant tests of removing naphthenic acid from the 4th vacuum side cut of Karamay heavy crud were carried out on a 200 kg/h microchannel reactor. Test results showed that the acid removal rate of this single stage microreactor process was more than 85% , which was better than that of the industrial two-stage extraction process with the same feedstock. Besides, this new process simplified the acid removal process, its solvent to oil ratio and energy consumption were much lower. It offers a new choice to remove large naphthenic acid molecules from heavy crude fractions effectively.

  7. Degradation and aquatic toxicity of naphthenic acids in oil sands process-affected waters using simulated wetlands.

    Science.gov (United States)

    Toor, Navdeep S; Franz, Eric D; Fedorak, Phillip M; MacKinnon, Michael D; Liber, Karsten

    2013-01-01

    Oil sands process-affected waters (OSPWs) produced during the extraction of bitumen at the Athabasca Oil Sands (AOS) located in northeastern Alberta, Canada, are toxic to many aquatic organisms. Much of this toxicity is related to a group of dissolved organic acids known as naphthenic acids (NAs). Naphthenic acids are a natural component of bitumen and are released into process water during the separation of bitumen from the oil sand ore by a caustic hot water extraction process. Using laboratory microcosms as an analogue of a proposed constructed wetland reclamation strategy for OSPW, we evaluated the effectiveness of these microcosms in degrading NAs and reducing the aquatic toxicity of OSPW over a 52-week test period. Experimental manipulations included two sources of OSPW (one from Syncrude Canada Ltd. and one from Suncor Energy Inc.), two different hydraulic retention times (HRTs; 40 and 400 d), and increased nutrient availability (added nitrate and phosphate). Microcosms with a longer HRT (for both OSPWs) showed higher reductions in total NAs concentrations (64-74% NAs reduction, p100% v/v) independent of HRT. However, EC20s from separate Microtox® bioassays were relatively unchanged when comparing the input and microcosm waters at both HRTs over the 52-week study period (p>0.05), indicating that some sub-lethal toxicity persisted under these experimental conditions. The present study demonstrated that given sufficiently long HRTs, simulated wetland microcosms containing OSPW significantly reduced total NAs concentrations and acute toxicity, but left behind a persistent component of the NAs mixture that appeared to be associated with residual chronic toxicity.

  8. Investigating salt and naphthenic acids interactions in the toxicity of oil sands process water to freshwater invertebrates

    Energy Technology Data Exchange (ETDEWEB)

    Turcotte, D.; Kautzman, M.; Wojnarowicz, P.; Cutter, J.; Bird, E.; Liber, K. [Saskatchewan Univ., Regina, SK (Canada)

    2010-07-01

    The hot water extraction process used to produce bitumens from oil sands produces a large volume of oil sands process water (OSPW) that contain elevated concentrations of naphthenic acids (NA) and salts. Many oil sands reclamation projects are proposing the use of OSPW as part of reconstructed wetlands projects. This study investigated the toxicity of OSPW to freshwater invertebrates. The toxic interactions between NA and salinity on freshwater invertebrates were assessed. Bioassays with laboratory-cultured Ceriodaphnia dubia were conducted to determine the toxicity of OSPW from selected water bodies. The study showed that while the concentrations of NAs and salinity were elevated in OSPW waters that caused toxic responses, the concentrations of salinity ions varied greatly among the OSPW samples. Results of the study suggested that ion composition may be a factor in toxicity. Interactions between NAs and salinity were then assessed by performing bioassays with mixtures representing major ion combinations in OSPW.

  9. In vitro evaluation of the toxic effects and endocrine disrupting potential of oil sands processed water and naphthenic acids

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, X.; Wiseman, S.; Higley, E.; Jones, P.D.; Hecker, M.; Giesy, J.P. [Saskatchewan Univ., Saskatoon, SK (Canada); Gamel El Din, M.; Martin, J.W. [Alberta Univ., Edmonton, AB (Canada)

    2009-07-01

    Naphthenic acids (NAs) are the primary toxic constituents of oil sands process-affected waters (OSPW). This presentation reported on a series of in vitro studies that were initiated to evaluate potential endocrine modulating effects of OSPW and their constituent NAs. The H295R steroidogenesis bioassay was used to examine the impact of OSPW and NA on 52 steroidogenesis. In particular, dose-response and time course studies were conducted to evaluate the impact of OSPW and NAs on testosterone and estradiol production. Aromatase activity and transcript abundance of the key 11 steroidogenic enzymes were also quantified to complement analysis of hormone levels. The MVLN trans-activation assay was used to test the estrogenicity/anti-estrogenicity of OSPW and NAs. In vitro cell viability and apoptosis (live-dead) caused by OSPW and NAs was quantified by the MTS reduction and caspase-3/7 activity in H295R and MVLN cells.

  10. Naphthenic Acid Corrosion in Petroleum Refineries. A Review La corrosion naphténique en raffinerie. Synthèse bibliographique

    Directory of Open Access Journals (Sweden)

    Jayaraman A.

    2006-11-01

    Full Text Available The problem of naphthenic acid corrosion is specific to certain crudes from India, Romania, Russia, Texas, Venezuela, Congo, Nigeria, etc. The nature of corrosion due to naphthenic acids is in the form of sharp-edged streamlined grooves. Detailed laboratory studies and some field data indicate that naphthenic acid corrosion increases beyond a specific neutralization number of crude, when the process temperature is between 220 and 400°C and when fluid velocities are high. The different factors responsible for naphthenic corrosion as well as the ways of fighting it are reviewed. Among them are predistillation, the blending of crudes, neutralization, the selection of construction materials and especially the mastery of fluid flow. La corrosion naphténique est spécifique à certains bruts de l'Inde, de la Roumanie, de l'URSS, du Texas, du Venezuela, du Congo, du Nigeria, etc. L'aspect de la corrosion due aux acides naphténiques est caractéristique, cratères et sillons à arètes vives. Des études de laboratoire et surtout l'expérience en raffinerie montrent que la corrosion naphténique, au-dessus d'un indice d'acide spécifique et dans un domaine de température de l'ordre de 220 à 400°C, croît avec la vitesse des fluides. Les différents facteurs responsables de la corrosion naphténique ainsi que les moyens de la combattre sont passés en revue. Parmi eux, la prédistillation, le mélange de bruts, la neutralisation, la sélection des matériaux de construction et surtout la maîtrise de l'écoulement des fluides.

  11. Potential of capillary electrophoresis mass spectrometry for the characterization and monitoring of amine-derivatized naphthenic acids from oil sands process-affected water.

    Science.gov (United States)

    MacLennan, Matthew S; Tie, Cai; Kovalchik, Kevin; Peru, Kerry M; Zhang, Xinxiang; Headley, John V; Chen, David D Y

    2016-11-01

    Capillary electrophoresis coupled to mass spectrometry (CE-MS) was used for the analysis of naphthenic acid fraction compounds (NAFCs) of oil sands process-affected water (OSPW). A standard mixture of amine-derivatized naphthenic acids is injected directly onto the CE column and analyzed by CE-MS in less than 15min. Time of flight MS analysis (TOFMS), optimized for high molecular weight ions, showed NAFCs between 250 and 800m/z. With a quadrupole mass analyzer, only low-molecular weight NAFCs (between 100 and 450m/z) are visible under our experimental conditions. Derivatization of NAFCs consisted of two-step amidation reactions mediated by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), or mediated by a mixture of EDC and N-hydroxysuccinimide, in dimethyl sulfoxide, dichloromethane or ethyl acetate. The optimum background electrolyte composition was determined to be 30% (V/V) methanol in water and 2% (V/V) formic acid. NAFCs extracted from OSPW in the Athabasca oil sands region were used to demonstrate the feasibility of CE-MS for the analysis of NAFCs in environmental samples, showing that the labeled naphthenic acids are in the mass range of 350 to 1500m/z. Copyright © 2016. Published by Elsevier B.V.

  12. Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish.

    Science.gov (United States)

    Scarlett, A G; Reinardy, H C; Henry, T B; West, C E; Frank, R A; Hewitt, L M; Rowland, S J

    2013-09-01

    The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic. In the present study we therefore assayed the acute toxicity to larval fish, of a whole acidified OSPW extract and an esterifiable naphthenic acids fraction, de-esterified with alkali: both fractions were toxic (LC50 ∼5-8mgL(-1)). We then fractionated the acids by argentation solid phase extraction of the esters and examined the acute toxicity of two fractions: a de-esterified alicyclic acids fraction, which contained, for example, adamantane and diamantane carboxylic acids, and an aromatic acids fraction. The alicyclic acids were toxic (LC50 13mgL(-1)) but the higher molecular weight aromatic acids fraction was somewhat more toxic, at least on a weight per volume basis (LC50 8mgL(-1); P<0.05) (for comparison, the monoaromatic dehydroabietic acid had a LC50 of ∼1mgL(-1)). These results show how toxic naphthenic acids of OSPW are to these larval fish and that on a weight per volume basis, the aromatic acids are at least as toxic as the 'classical' alicyclic acids. The environmental fates and other toxic effects, if any, of the fractions remain to be established. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Shifts in root-associated microbial communities of Typha latifolia growing in naphthenic acids and relationship to plant health.

    Science.gov (United States)

    Phillips, Lori A; Armstrong, Sarah A; Headley, John V; Greer, Charles W; Germida, James J

    2010-01-01

    Naphthenic acids (NAs) are a complex mixture of organic acid compounds released during the extraction of crude oil from oil sands operations. The accumulation of toxic NAs in tailings pond water (TPW) is of significant environmental concern, and phytoremediation using constructed wetlands is one remediation option being assessed. Since root-associated microorganisms are an important factor during phytoremediation of organic compounds, this study investigated the impact of NAs on the microbial communities associated with the macrophyte Typha latifolia (cattail). Denaturing gradient gel electrophoresis revealed that the impact of NAs on microbial communities was niche dependent, with endophytic communities being the most stable and bulk water communities being the least stable. The type of NA used was significant to microbial response, with commercial NAs causing greater adverse changes than TPW NAs. In general, plant beneficial bacteria such as diazotrophs were favoured in cattails grown in TPW NAs, while potentially deleterious bacteria such as denitrifying Dechlorospirillum species increased in commercial NA treatments. These findings suggest that NAs may affect plant health by impacting root-associated microbial communities. A better understanding of these impacts may allow researchers to optimize those microbial communities that support plant health, and thus further optimize wetland treatment systems.

  14. Modified biopolymers as sorbents for the removal of naphthenic acids from oil sands process affected water (OSPW).

    Science.gov (United States)

    Arshad, Muhammad; Khosa, M A; Siddique, Tariq; Ullah, Aman

    2016-11-01

    Oil sands operations consume large volumes of water in bitumen extraction process and produce tailings that express pore water to the surface of tailings ponds known as oil sands process-affected water (OSPW). The OSPW is toxic and cannot be released into the environment without treatment. In addition to metals, dissolved solids, dissolved gases, hydrocarbons and polyaromatic compounds etc., OSPW also contains a complex mixture of dissolved organic acids, referred to as naphthenic acids (NAs). The NAs are highly toxic and react with metals to develop highly corrosive functionalities which cause corrosion in the oil sands processing and refining processes. We have chemically modified keratin biopolymer using polyhedral oligomeric silsesquioxanes (POSS) nanocages and goethite dopant to unfold keratinous structure for improving functionality. The untreated neat keratin and two modified sorbents were characterized to investigate structural, morphological, dimensional and thermal properties. These sorbents were then tested for the removal of NAs from OSPW. The NAs were selectively extracted and quantified before and after sorption process. The biosorption capacity (Q), rejection percentage (R%) and isotherm models were studied to investigate NAs removal efficiency of POSS modified keratin biopolymer (PMKB) and goethite modified keratin biopolymer (GMKB) from aliquots of OSPW.

  15. Photocatalytic degradation kinetics of naphthenic acids in oil sands process-affected water: Multifactorial determination of significant factors.

    Science.gov (United States)

    Leshuk, Tim; de Oliveira Livera, Diogo; Peru, Kerry M; Headley, John V; Vijayaraghavan, Sucharita; Wong, Timothy; Gu, Frank

    2016-12-01

    Oil sands process-affected water (OSPW) is generated as a byproduct of bitumen extraction in Canada's oil sands. Due to the water's toxicity, associated with dissolved acid extractable organics (AEO), especially naphthenic acids (NAs), along with base-neutral organics, OSPW may require treatment to enable safe discharge to the environment. Heterogeneous photocatalysis is a promising advanced oxidation process (AOP) for OSPW remediation, however, predicting treatment efficacy can be challenging due to the unique water chemistry of OSPW from different tailings ponds. The objective of this work was to study various factors affecting the kinetics of photocatalytic AEO degradation in OSPW. The rate of photocatalytic treatment varied significantly in two different OSPW sources, which could not be accounted for by differences in AEO composition, as studied by high resolution mass spectrometry (HRMS). The effects of inorganic water constituents were investigated using factorial and response surface experiments, which revealed that hydroxyl (HO) radical scavenging by iron (Fe(3+)) and bicarbonate (HCO3(-)) inhibited the NA degradation rate. The effects of NA concentration and temperature on the treatment kinetics were also evaluated in terms of Langmuir-Hinshelwood and Arrhenius models; pH and temperature were identified as weak factors, while dissolved oxygen (DO) was critical to the photo-oxidation reaction. Accounting for all of these variables, a general empirical kinetic expression is proposed, enabling prediction of photocatalytic treatment performance in diverse sources of OSPW.

  16. Isolation and estimation of the 'aromatic' naphthenic acid content of an oil sands process-affected water extract.

    Science.gov (United States)

    Jones, David; West, Charles E; Scarlett, Alan G; Frank, Richard A; Rowland, Steven J

    2012-07-20

    The naphthenic acids of oil sands process-affected water (OSPW) are said to be important toxicants. The major acids are stated to have alicyclic structures and recently, numerous of these have been identified, but some evidence suggests 'aromatic' acids are also present. The proportions of such acids have not been reported because they exist in so-called supercomplex mixtures with the alicyclic species. Their contribution to the toxicity of OSPW, if any, is therefore unknown. Here we report the use of multidimensional comprehensive gas chromatography-mass spectrometry (GC×GC-MS) with polar first dimension and non-polar second dimension GC columns and argentation solid phase extraction, to separate methyl esters of the acids of an OSPW supercomplex, into distinct fractions. A major fraction (ca 70%) was shown to contain acids (methyl esters) previously identified as alicyclic species. Authentic adamantane acid methyl esters were shown to chromatograph in this fraction. This fraction was isolated by argentation solid phase extraction (SPE) by elution with hexane. GC-MS and GC×GC-MS confirmed this to be the major fraction in the original supercomplex containing alicyclic acids (methyl esters). A second fraction shown to contain monoaromatic acids (methyl esters) by GC×GC-MS was unexpectedly abundant (ca 30% relative to the acyclic acids). The naphtheno-aromatic dehydroabietic acid was confirmed by co-injection with an authentic compound and several acids previously tentatively identified as naphtheno-monoaromatics were present. This fraction was isolated by argentation SPE by elution with more polar 5% diethyl ether in hexane. GC-MS and GC×GC-MS confirmed that the fraction represented a significant proportion of the original supercomplex. A further fraction, eluting from the argentation SPE column with more 5% diethyl ether in hexane in the same retention volume as authentic methyl naphthoate, contained, in addition to some of the second fraction, a third, much

  17. Remotion of naphthenic acidity through adsorption with transition metal-perovskita; Remocao de acidez naftenica por adsorcao utilizando perovsquita com metais de transicao

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Andressa Mendes [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil); Santos, Jean Heliton Lopes dos [Companhia Brasileira de Petroleo Ipiranga, Rio de Janeiro, RJ (Brazil); Souza, Aleksandros El Aurens Meira de; Barbosa, Celmy Maria Bezerra de Menezes [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Engenharia Quimica

    2008-07-01

    Some existent oxygenated compounds in the petroleum are main responsible for the acidity and corrodibility of petroleum derivates. Naphthenic acids are most present molecules, and there already are some quantity of phenols and fat acids. The aim of this work was to evaluate the kinetic behavior of naphthenic acid removal, using a new adsorbent material based on perovskite forms (LaZnO{sub 3}). Two model mixtures were used to carry out the research: the first one was 4-tertbuthylbenzoic acid soluble in n-dodecane and the other one was dodecanoic acid also in n dodecane. For the 4-tertbuthylbenzoic analysis, the adsorption reached the equilibrium at 180 min, with the adsorption capacity of q{sub ads} = 0,25 g{sub acid}/g{sub adsorbent}, and a q{sub ads,max} = 0,55 g{sub acid}/g{sub adsorbent} at equilibrium. For the analysis of the dodecanoic acid removal, the adsorption occurred at first minutes, reaching the equilibrium at 250 min, with the adsorption capacity of q{sub ads} = 0,87 g{sub acid}/g{sub adsorbent}, and a q{sub ads,max} = 0,62 g{sub acid}/g{sub adsorbent} at equilibrium. (author)

  18. Are there toxic interactions between salinity and naphthenic acids in the toxicity of oil sands process water to freshwater invertebrates?

    Energy Technology Data Exchange (ETDEWEB)

    Turcotte, D.; Pasloski, A.; Lanser, B.; Alm, K.; Liber, K. [Saskatchewan Univ., Saskatoon, SK (Canada)

    2009-07-01

    Large volumes of water are used to extract oil from the oil sands in the Athabasca deposit. The resulting oil sands process water (OSPW) has been proposed for use in future reclamation landscapes. Therefore, it is necessary to evaluate the toxicity of OSPW to freshwater invertebrates in order to develop environmentally acceptable OSPW reclamation plans. The OSPW generally contains high concentrations of salts and naphthenic acids (NAs), but low levels of other contaminants such as PAHs and metals. This study investigated the combined toxic effect of NAs and salinity on freshwater invertebrates. Laboratory cultured Ceriodaphnia dubia were used initially to determine the toxicity of OSPW from selected water bodies. The pond waters that generated a toxic response had elevated levels of NAs and salinity, but the concentrations of salinity ions varied considerably among ponds. Results suggested that ion composition may be a factor in toxicity. Subsequent bioassays were performed with single salts and with mixtures representing major ion combinations present in the OSPW, such as carbonate, sulphate, chloride and sodium. The interaction between NAs and salinity was evaluated by exposing Ceriodaphnia dubia and Daphnia pulex to mixtures of NAs extracted from OSPW and relevant major ions chosen according to the salt toxicity test results.

  19. Toxic effects of oil sand naphthenic acids on the biomass accumulation of 21 potential phytoplankton remediation candidates.

    Science.gov (United States)

    Woodworth, Adam P J; Frank, Richard A; McConkey, Brendan J; Müller, Kirsten M

    2012-12-01

    The oil sands of northern Alberta, Canada contain an estimated 170 billion barrels of crude oil. Extraction processes produce large amounts of liquid tailings known as oil sand process affected water (OSPW) that are toxic to aquatic organisms. Naphthenic acids (NAs), and their sodium salts, represent a significant contributor to the toxicity of these waters. Due to the recalcitrant nature of these compounds, an effective mode of remediation has yet to be established. This study investigates the suitability of the use of phytoplankton for remediation efforts based on two criteria: the ability of phytoplankton strains to withstand the toxic effects of NAs, and their rate of biomass accumulation. A total of 21 phytoplankton strains were isolated from waters containing NAs, cultured, and maintained under unialgal conditions. These strains were then exposed to NAs in concentrations ranging from 0mg L(-1) to 1000mg L(-1) over a 14 day period. Inhibition of growth was observed at 30mg L(-1) NA (one strain), 100mg L(-1) NA (one strain), 300mg L(-1) NA (six strains), and 1000mg L(-1) NA (six strains). Five strains failed to show any growth inhibition at any test concentration and two strains could not be analysed due to poor growth during the test period. Strains were then ranked based on their suitability for use in remediation efforts.

  20. Naphthenic acids speciation and removal during petroleum-coke adsorption and ozonation of oil sands process-affected water.

    Science.gov (United States)

    Gamal El-Din, Mohamed; Fu, Hongjing; Wang, Nan; Chelme-Ayala, Pamela; Pérez-Estrada, Leonidas; Drzewicz, Przemysław; Martin, Jonathan W; Zubot, Warren; Smith, Daniel W

    2011-11-01

    The Athabasca Oil Sands industry produces large volumes of oil sands process-affected water (OSPW) as a result of bitumen extraction and upgrading processes. Constituents of OSPW include chloride, naphthenic acids (NAs), aromatic hydrocarbons, and trace heavy metals, among other inorganic and organic compounds. To address the environmental issues associated with the recycling and/or safe return of OSPW into the environment, water treatment technologies are required. This study examined, for the first time, the impacts of pretreatment steps, including filtration and petroleum-coke adsorption, on ozonation requirements and performance. The effect of the initial OSPW pH on treatment performance, and the evolution of ozonation and its impact on OSPW toxicity and biodegradability were also examined. The degradation of more than 76% of total acid-extractable organics was achieved using a semi-batch ozonation system at a utilized ozone dose of 150 mg/L. With a utilized ozone dose of 100 mg/L, the treated OSPW became more biodegradable and showed no toxicity towards Vibrio fischeri. Changes in the NA profiles in terms of carbon number and number of rings were observed after ozonation. The filtration of the OSPW did not improve the ozonation performance. Petroleum-coke adsorption was found to be effective in reducing total acid-extractable organics by a 91%, NA content by an 84%, and OSPW toxicity from 4.3 to 1.1 toxicity units. The results of this study indicate that the combination of petroleum-coke adsorption and ozonation is a promising treatment approach to treat OSPW.

  1. Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst Ⅱ. Experimental results of catalytic decarboxylation over acidic catalysts

    Institute of Scientific and Technical Information of China (English)

    Fu Xiaoqin; Tian Songbai; Hou Shuandi; Longjun; Wang Xieqing

    2008-01-01

    The energy barriers of thermal decarboxylation reactions of petroleum acids and catalytic decarboxylation reactions of Br(o)nsted acid and Lewis acid were analyzed using molecular simulation technology.Compared with thermal decarboxylation reactions of petroleum acids, the decarboxylation reactions by acid catalysts were easier to occur. The decarboxylaton effect by Lewis acid was better than Br(o)nsted acid. The mechanisms of catalytic decarboxylation over acid catalyst were also verified by experiments on a fixed bed and a fluidized bed, the experimental results showed that the rate of acid removal could reach up to 97% over the acidic catalyst at a temperature above 400℃.

  2. Thermodynamics Analysis on HDO Reaction of Naphthenic Acid Glycol Ester%环烷酸乙二醇酯的 HDO 热力学分析

    Institute of Scientific and Technical Information of China (English)

    陈伟东; 马锐; 朱建华

    2016-01-01

    Taking naphthenic acid glycol ester as model compound, the possibility of the hydrogenation reaction of the model compound was analyzed by thermodynamics method. Due to the complexity of the structures of naphthenic acid glycol ester and bicycloalkane, their thermodynamic data could not be obtained from literatures directly. Therefore, the method of group contribution was applied to estimate the enthalpy and entropy of naphthenic acid glycol ester and bicycloalkane under the standard state. Meanwhile, the functional correlation between the heat capacity of these organic compounds and temperature was established. Furthermore, the enthalpy change, the Gibbs free energy change and equilibrium constant of the HDO reaction were calculated under the different reaction conditions. The results illustrate that the HDO reaction of the naphthenic acid glycol ester may occur and its equilibrium constant is very large, therefore it can be considered as an irreversible reaction. The method set up in this paper can also be used in the thermodynamic analysis of HDO reaction of other esters.%以选取的环烷酸乙二醇酯模型化合物为基础,利用热力学斱法分析其加氢脱氧反应収生的可能性。由于环烷酸乙二醇酯及双环环烷烃的结构复杂,无法直接获得其热力学数据,故采用基团贡献法估算了环烷酸乙二醇酯及双环环烷烃在298.15 K 标准状态下的生成焓、标准熵及热容随温度的变化关系,迚而得到不同温度条件下环烷酸乙二醇酯 HDO 的焓变、吉布斯自由能变及平衡常数。计算结果表明,环烷酸乙二醇酯的 HDO 反应在指定条件下为放热反应幵可自収迚行,且其平衡常数很大,可视为不可逆反应。该斱法也可用于其它酯类物质 HDO 的热力学分析。

  3. Diamondoid naphthenic acids cause in vivo genetic damage in gills and haemocytes of marine mussels.

    Science.gov (United States)

    Dissanayake, Awantha; Scarlett, Alan G; Jha, Awadhesh N

    2016-04-01

    Diamondoids are polycyclic saturated hydrocarbons that possess a cage-like carbon skeleton approaching that of diamond. These 'nano-diamonds' are used in a range of industries including nanotechnologies and biomedicine. Diamondoids were thought to be highly resistant to degradation, but their presumed degradation acid products have now been found in oil sands process-affected waters (OSPW) and numerous crude oils. Recently, a diamondoid-related structure, 3-noradamantane carboxylic acid, was reported to cause genetic damage in trout hepatocytes under in vitro conditions. This particular compound has never been reported in the environment but led us to hypothesise that other more environmentally relevant diamondoid acids could also be genotoxic. We carried out in vivo exposures (3 days, semi-static) of marine mussels to two environmentally relevant diamondoid acids, 1-adamantane carboxylic acid and 3,5-dimethyladamantane carboxylic acid plus 3-noradamantane carboxylic acid with genotoxic damage assessed using the Comet assay. An initial screening test confirmed that these acids displayed varying degrees of genotoxicity to haemocytes (increased DNA damage above that of controls) when exposed in vivo to a concentration of 30 μmol L(-1). In a further test focused on 1-adamantane carboxylic acid with varying concentrations (0.6, 6 and 30 μmol L(-1)), significant (P genetic damage was similar to that observed following exposure to a known genotoxin, benzo(a)pyrene (exposure concentration, 0.8 μmol L(-1)). These findings may have implications for a range of worldwide industries including oil extraction, nanotechnology and biomedicine.

  4. Characterization of commercial ceramic adsorbents and their application on naphthenic acids removal of petroleum distillates; Caracterizacao de adsorventes ceramicos comerciais e sua aplicacao na remocao de acidos naftenicos de destilados de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Silva, J.P.; Senna, L.F. de; Lago, D.C.B. do; Silva Junior, P.F. da; Figueiredo, M.A.G. de; Dias, E.G. [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil)], e-mail: julia_psi@yahoo.com.br; Chiaro, S.S.X. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2006-07-01

    One denominates 'naphthenic acids' to the mixture of carboxylic acids that is present in petroleum oil, and is directly responsible for its acidity and corrosiveness in liquid phase during the refine process. These acids are also presents in distilled fraction of petroleum, causing several problems in final products quality. A possible way to remove them from petroleum distilled fractions is the adsorption in porous materials. However, the published results indicate that ion exchange resins would be the best adsorbents for this process, which would probably increase its cost. In this work, two commercial adsorbents (clay and activated alumina) were characterized by a set of physical-chemistry techniques and evaluated concerning their capacity of removing naphthenic acids from a light petroleum fraction. It was also verified the influence of a previous thermal treatment to the adsorption in their physical-chemistry characteristics and its properties. (author)

  5. Novel naphthenate surfactants based on petroleum acids and nitrogenous bases as corrosion inhibitors for C1018-type mild steel in CO2-saturated brine

    Directory of Open Access Journals (Sweden)

    Hany M. Abd El-Lateef

    2015-06-01

    Full Text Available The efficiency of two natural naphthenate surfactants (Naphthenic-dimethylamine and Naphthenic-diethylamine complexes, as corrosion inhibitors for mild steel in CO2-saturated 1% NaCl solution, has been determined by linear polarization resistance corrosion rate and potentiodynamic polarization measurements. These compounds inhibit corrosion even at very low concentrations (25 ppm, and Naphthenic-diethylamine complex is the best inhibitor giving maximum inhibition efficiency (99.76 at 100 ppm. Polarization curves indicate that, the two investigated compounds are mixed inhibitors, affecting both cathodic and anodic corrosion currents. Adsorption of naphthenate surfactants on the mild steel surface is in good agreement with the Langmuir adsorption isotherm model, and the calculated Gibbs free energy values confirm the chemical nature of the adsorption. Energy dispersive X-ray fluorescence microscopy (EDRF and scanning electron microscope (SEM observations confirmed the existence of such an adsorbed film on the mild steel surface.

  6. Acids and bases solvent effects on acid-base strenght

    CERN Document Server

    Cox, Brian G

    2013-01-01

    Acids and bases are ubiquitous in chemistry. Our understanding of them, however, is dominated by their behaviour in water. Transfer to non-aqueous solvents leads to profound changes in acid-base strengths and to the rates and equilibria of many processes: for example, synthetic reactions involving acids, bases and nucleophiles; isolation of pharmaceutical actives through salt formation; formation of zwitter- ions in amino acids; and chromatographic separation of substrates. This book seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous solvents. The behaviour is related where possible to that in water, but correlations and contrasts between solvents are also presented.

  7. The effect of oil sands process-affected water and model naphthenic acids on photosynthesis and growth in Emiliania huxleyi and Chlorella vulgaris.

    Science.gov (United States)

    Beddow, Jessica; Johnson, Richard J; Lawson, Tracy; Breckels, Mark N; Webster, Richard J; Smith, Ben E; Rowland, Steven J; Whitby, Corinne

    2016-02-01

    Naphthenic acids (NAs) are among the most toxic organic pollutants present in oil sands process waters (OSPW) and enter marine and freshwater environments through natural and anthropogenic sources. We investigated the effects of the acid extractable organic (AEO) fraction of OSPW and individual surrogate NAs, on maximum photosynthetic efficiency of photosystem II (PSII) (FV/FM) and cell growth in Emiliania huxleyi and Chlorella vulgaris as representative marine and freshwater phytoplankton. Whilst FV/FM in E. huxleyi and C. vulgaris was not inhibited by AEO, exposure to two surrogate NAs: (4'-n-butylphenyl)-4-butanoic acid (n-BPBA) and (4'-tert-butylphenyl)-4-butanoic acid (tert-BPBA), caused complete inhibition of FV/FM in E. huxleyi (≥10 mg L(-1)n-BPBA; ≥50 mg L(-1)tert-BPBA) but not in C. vulgaris. Growth rates and cell abundances in E. huxleyi were also reduced when exposed to ≥10 mg L(-1)n- and tert-BPBA; however, higher concentrations of n- and tert-BPBA (100 mg L(-1)) were required to reduce cell growth in C. vulgaris. AEO at ≥10 mg L(-1) stimulated E. huxleyi growth rate (p ≤ 0.002), yet had no apparent effect on C. vulgaris. In conclusion, E. huxleyi was generally more sensitive to NAs than C. vulgaris. This report provides a better understanding of the physiological responses of phytoplankton to NAs which will enable improved monitoring of NA pollution in aquatic ecosystems in the future.

  8. Solvent extraction of metals with hydroxamic acids.

    Science.gov (United States)

    Vernon, F; Khorassani, J H

    1978-07-01

    Solvent extraction with hydroxamic acids has been investigated. with comparison of aliphatic and aromatic reagents for the extraction of iron, copper, cobalt and nickel. Caprylohydroxamic acid has been evaluated for use in extraction systems for titanium, vanadium, chromium, molybdenum and uranium, both in terms of acidity of aqueous phase and oxidation state of the metal. It has been established that caprylohydroxamic acid in 1-hexanol is a suitable extractant for the removal of titanium(IV), vanadium(V), chromium(VI), molybdenum(VI) and uranium(VI) from 6M hydrochloric acid.

  9. Prediction of naphthenic acid species degradation by kinetic and surrogate models during the ozonation of oil sands process-affected water.

    Science.gov (United States)

    Islam, Md Shahinoor; Moreira, Jesús; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

    2014-09-15

    Oil sands process-affected water (OSPW) is a complex mixture of organic and inorganic contaminants, and suspended solids, generated by the oil sands industry during the bitumen extraction process. OSPW contains a large number of structurally diverse organic compounds, and due to variability of the water quality of different OSPW matrices, there is a need to select a group of easily measured surrogate parameters for monitoring and treatment process control. In this study, kinetic and surrogate correlation models were developed to predict the degradation of naphthenic acids (NAs) species during the ozonation of OSPW. Additionally, the speciation and distribution of classical and oxidized NA species in raw and ozonated OSPW were also examined. The structure-reactivity of NA species indicated that the reactivity of individual NA species increased as the carbon and hydrogen deficiency numbers increased. The kinetic parameters obtained in this study allowed calculating the evolution of the concentrations of the acid-extractable fraction (AEF), chemical oxygen demand (COD), and NA distributions for a given ozonation process. High correlations between the AEF and COD and NA species were found, suggesting that AEF and COD can be used as surrogate parameters to predict the degradation of NAs during the ozonation of OSPW.

  10. Naphthenic Acid Mixtures from Oil Sands Process-Affected Water Enhance Differentiation of Mouse Embryonic Stem Cells and Affect Development of the Heart.

    Science.gov (United States)

    Mohseni, Paria; Hahn, Noah A; Frank, Richard A; Hewitt, L Mark; Hajibabaei, Mehrdad; Van Der Kraak, Glen

    2015-08-18

    Extraction of petrochemicals from the surface mining of oil sand deposits results in generation of large volumes of oil sands process-affected water (OSPW). Naphthenic acids (NA) are generally considered to be among the most toxic components of OSPW. Previous studies have shown that NAs are toxic to aquatic organisms, however knowledge of their effects on mammalian health and development is limited. In the present study, we evaluated the developmental effects of an NA extract prepared from fresh OSPW on differentiating mouse embryonic stem cells (ESC). We found that treatment of differentiating cells with the NA extract at noncytotoxic concentrations alters expression of various lineage specification markers and development of the heart. Notably, expression of cardiac specific markers such as Nkx2.5, Gata4, and Mef2c were significantly up-regulated. Moreover, exposure to the NA extract enhanced differentiation of embryoid bodies and resulted in the early appearance of spontaneously beating clusters. Interestingly, exposure of undifferentiated mouse ESCs to the NA extract did not change the expression level of pluripotency markers (i.e., Oct4, Nanog, and Sox2). Altogether, these data identify some of the molecular pathways affected by components within this NA extract during differentiation of mammalian cells.

  11. Fractionation of oil sands-process affected water using pH-dependent extractions: a study of dissociation constants for naphthenic acids species.

    Science.gov (United States)

    Huang, Rongfu; Sun, Nian; Chelme-Ayala, Pamela; McPhedran, Kerry N; Changalov, Mohamed; Gamal El-Din, Mohamed

    2015-05-01

    The fractionation of oil sands process-affected water (OSPW) via pH-dependent extractions was performed to quantitatively investigate naphthenic acids (NAs, CnH2n+ZO2) and oxidized NAs (Ox-NAs) species (CnH2n+ZO3 and CnH2n+ZO4) using ultra-performance liquid chromatography time-of-flight mass spectrometry (UPLC-TOFMS). A mathematical model was also developed to estimate the dissociation constant pKa for NAs species, considering the liquid-liquid extraction process and the aqueous layer acid-base equilibrium. This model provides estimated dissociation constants for compounds in water samples based on fractionation extraction and relative quantification. Overall, the sum of O2-, O3-, and O4-NAs species accounted for 33.6% of total extracted organic matter. Accumulative extracted masses at different pHs revealed that every oxygen atom added to NAs increases the pKa (i.e., O2-NAs

  12. Mixed solvent system for treating acidic gas

    Energy Technology Data Exchange (ETDEWEB)

    Capobianco, P.J.; Butwell, K.F.; Kossakowski, E.J.

    1987-11-10

    This invention discloses mixtures of alkyl dialcohol amines and mono alkyl ethers of polyethylene glycols which are useful in removing acidic gases from gaseous mixtures. The solvent mixtures contain between 1.5 N and 5.0 N methyl diethanolamine (MDEA), 10 to 40 percent water and the balance is methoxytriglycol (MTG). The overall heat of reaction of the solution is typically less than 500 BTU/lb CO/sub 2/, and remains as a single liquid phase during normal gas scrubber operating conditions.

  13. Solubilities of Isophthalic Acid in Acetic Acid + Water Solvent Mixtures

    Institute of Scientific and Technical Information of China (English)

    CHENG Youwei; HUO Lei; LI Xi

    2013-01-01

    The solubilities of isophthalic acid (1) in binary acetic acid (2) + water (3) solvent mixtures were determined in a pressurized vessel.The temperature range was from 373.2 to 473.2K and the range of the mole fraction of acetic acid in the solvent mixtures was from x2 =0 to 1.A new method to measure the solubility was developed,which solved the problem of sampling at high temperature.The experimental results indicated that within the temperature range studied,the solubilities of isophthalic acid in all mixtures showed an increasing trend with increasing temperature.The experimental solubilities were correlated by the Buchowski equation,and the calculate results showed good agreement with the experimental solubilities.Furthermore,the mixed solvent systems were found to exhibit a maximum solubility effect on the solubility,which may be attributed to the intermolecular association between the solute and the solvent mixture.The maximum solubility effect was well modeled by the modified Wilson equation.

  14. Naphthenic Acid Corrosion Resistance of Typical Refining and Chemical Materials%典型炼油化工材料耐环烷酸腐蚀性能综述

    Institute of Scientific and Technical Information of China (English)

    许述剑; 刘小辉

    2011-01-01

    从材料热力学、冶金学角度概括分析了碳钢、Cr5Mo、304和316L奥氏体不锈钢、渗铝钢和Ni-P化学镀表面改性材料等典型炼油化工材料耐环烷酸腐蚀的机理,以及介质酸值、流速、温度等因素对环烷酸腐蚀影响的动力学基础.%The corrosion mechanisms of some typical refining and chemical materials, including carbon steel, Cr5Mo, 304 and 316L stainless steels, aluminized steel and Ni-P chemical plating surface modification materials and so on, in naphthenic acid environments are summarized by thermodynamical and metallurgical analyses. The kinetic analyses of the major factors affecting the naphthenic acid corrosion, including the acid value of oil, operation temperature, fluid velocity and flow pattern, are also discussed.

  15. DILUTE SOLUTION BEHAVIOR OF CHITOSAN IN DIFFERENT ACID SOLVENTS

    Institute of Scientific and Technical Information of China (English)

    WANG Wei; WANG Lihua; QIN Wen

    1994-01-01

    Dilute solution behavior of chitosan was studied in formic acid, acetic acid,lactic acid and hydrochloric acid aqueous solution under different pH values. The reduced viscosities, ηsp/C,of chitosan solutions were dependent on the properties of acid and pH value of solvents. For a given chitosan concentration, ηsp/C decreased with the increase of acid concentration, or decreasing pH of solvent, indicating shielding effect of excessive acid similar to adding salt into solution. The stabilities of dilute chitosan solution in formic acid and lactic acid were better than that in acetic acid and hydrochloric acid.

  16. Study on Naphthenic Acid Sodium Wastewater Treatment by Flocculation Magnetic Separation Technology%絮凝磁分离技术处理环烷酸钠废水的研究

    Institute of Scientific and Technical Information of China (English)

    鲁风芹; 李兴盼; 孙文

    2011-01-01

    环烷酸钠是导致炼油废水不能达标排放的主要原因,文章采用絮凝磁分离技术处理环烷酸钠废水,研究各因素对实验结果的影响,确定最佳处理条件,并对实际废水进行了实验研究,结果表明该技术可有效去除炼油废水中的CODcr.%The naphthenic acid sodium is the main reason causing the refinery wastewater failed to meet the requirement of discharging. This paper adopts flocculation magnetic separation technology to treat naphthenic acid sodium wastewater through studying the influence of each factor on the experiment to determine the optimum conditions. Then the actual wastewater was treated. The resuhs show that this technology can remove the COD or of refinery wastewater effectively.

  17. Chemical fingerprinting of naphthenic acids at an oil sands end pit lake by comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC×GC/TOFMS)

    Science.gov (United States)

    Bowman, D. T.; Arriaga, D.; Morris, P.; Risacher, F.; Warren, L. A.; McCarry, B. E.; Slater, G.

    2016-12-01

    Naphthenic acids (NAs) are naturally occurring in Athabasca oil sands and accumulate in tailings as a result of water-based extraction processes. NAs contribute to the toxicity of tailings and oil sands process-affected water (OSPW). NAs exist as a complex mixture, so the development of an analytical technique to characterize them has been an on-going challenge. The monitoring of individual NAs and their associated isomers through multidimensional chromatography has the potential to provide greater insight into the behavior of NAs in the environment. For NAs whose proportions do not change during environmental processing, NA ratios may provide a means to develop fingerprints characteristic of specific sources. Alternatively, relative changes in the proportions of NAs may provide a tracer of their occurrence and extent of removal. As yet, only a few studies have begun to explore these possibilities. In this study, comprehensive two dimensional gas chromatography/time-of-flight mass spectrometry was used to monitor individual naphthenic acids in an end pit lake in Alberta, Canada. NA profiles from different depths and sampling locations were compared to evaluate the spatial variations at the site.

  18. Review on aggregation of acid extractants in solvent extraction of metal ions: remark on the general model

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The aggregation behavior of various acid extractants in the solvent extraction systems of metal ions is re-examined and explained according to knowledge obtained in recent work. The conclusions are as follows. (1) Complexes formed by the extractants and metal ions can form reversed micelles in organic diluents, depending on the microstructures of the complexes. The dimers of the acid extractant cannot percolate to the metal-extractant aggregates, and the acid-salt complexes are always formed in the aggregates. The reversed micelles or the W/O microemulsions formed by different species cannot be associated with each other to form a unified aggregate. (2) In solvent extraction systems, hydration of the extractants and metal ions can be considered as the driving force of forming reversed micelles. (3) Information of the first approach to the insight of the bicontinuous microemulsion of NaDEHP shows that various components in the aqueous phase behave confined and very similar to the typical AOT/n-heptane W/O microemulsions. (4) In the extraction of lanthanide ions by the W/O microemulsion of sodium naphthenate, the saponification is a process of forming reversed micelle or W/O microemulsion, while the extraction step is a process of destroying reversed micelles or W/O microemulsion droplets.

  19. 改性环烷酸萃取体系分离稀土和铝的优越性%Superiority Research on Rare Earth and Aluminium Separation in Modified Naphthenic Acid Extraction System

    Institute of Scientific and Technical Information of China (English)

    李剑虹; 张兴

    2011-01-01

    以不同皂化值的环烷酸和氯代环烷酸为铝和稀土混合料液的萃取体系,研究了不同酸度和铝浓度的稀土料液在萃取体系中铝和稀土的分配比及分离系数,发现2萃取体系中铝和稀土的优化分离条件均是料液铝浓度12.5 mmol/L、pH=0.10、萃取剂皂化值0.35,其中氯代环烷酸萃取体系铝和稀土的分离系数是环烷酸萃取体系的4.5倍以上,且氯代环烷酸萃取体系可以避免乳化现象的发生,因此,具有显著的优越性.%Distribution ratio and separation coefficient of aluminium, rare earth in naphthenic and chloronaphthenic acid systems with different extractant saponification value have been studied respectively in different acidity and aluminium concentration The results show that optimized process parameters are all MAl = 12.5 mmol/L, pH = 0.10 and 0.35 extractant saponidication value in the two extractant systems. Moreover, separation coefficient of aluminium, rare earth in chloronaphthenic acid is about 4. 5 times than naphthenic acid systems. Besides these, avoiding emulsion problem is also advantage of chloronaphthenic acid. So chloronaphthenie acid system has more superiorty.

  20. Naphthenic acids hydrates of gases: influence of the water/oil interface on the dispersing properties of an acidic crude oil; Acides naphteniques hydrates de gaz de l'interface eau/huile sur les proprietes dispersantes d'un brut acide

    Energy Technology Data Exchange (ETDEWEB)

    Arla, D.

    2006-01-15

    Nowadays, the development of offshore oil production under increasing water depths (high pressures and low temperatures) has led oil companies to focus on gas hydrates risks. Hydrates are crystals containing gas and water molecules which can plug offshore pipelines. It has been shown that some asphaltenic crude oils stabilize water-in-oil emulsions (W/O) during several months and exhibit very good anti-agglomerant properties avoiding hydrate plugs formation. In this work, we have studied the 'anti-hydrate' properties of a West African acidic crude oil called crude AH. This oil contains naphthenic acids, RCOOH hydrocarbons which are sensitive to both the pH and the salinity of the water phase.The emulsifying properties of the crude AH have firstly been explored. It has been shown that heavy resins and asphaltenes are the main compounds of the crude AH responsible for the long term stability of the W/O emulsions whereas the napthenates RCOO{sup -} lead to less stable W/O emulsions. Dealing with hydrates, the crude AH exhibits moderate anti-agglomerant properties due to the presence of heavy resins and asphaltenes. However, the naphthenates RCOO{sup -} drastically increase the formation of hydrate plugs. Moreover, it has been pointed out that hydrate particles agglomeration accelerates the kinetics of hydrate formation and enhances the water/oil separation. In order to explain these behaviours, a mechanism of agglomeration by 'sticking' between a hydrate particle and a water droplet has been proposed. Finally, we have developed a model which describes the physico-chemical equilibria of the naphthenic acids in the binary system water/crude AH, in order to transpose the results obtained in the laboratory to the real oil field conditions. (author)

  1. Comparison of solvent mixtures for pressurized solvent extraction of soil fatty acid biomarkers.

    Science.gov (United States)

    Jeannotte, Richard; Hamel, Chantal; Jabaji, Suha; Whalen, Joann K

    2008-10-19

    The extraction and transesterification of soil lipids into fatty acid methyl esters (FAMEs) is a useful technique for studying soil microbial communities. The objective of this study was to find the best solvent mixture to extract soil lipids with a pressurized solvent extractor system. Four solvent mixtures were selected for testing: chloroform:methanol:phosphate buffer (1:2:0.8, v/v/v), chloroform:methanol (1:2, v/v), hexane:2-propanol (3:2, v/v) and acetone. Soils were from agricultural fields and had a wide range of clay, organic matter and microbial biomass contents. Total lipid fatty acid methyl esters (TL-FAMEs) were the extractable soil lipids identified and quantified with gas chromatography and flame ionization detection. Concentrations of TL-FAMEs ranged from 57.3 to 542.2 nmole g(-1) soil (dry weight basis). The highest concentrations of TL-FAMEs were extracted with chloroform:methanol:buffer or chloroform:methanol mixtures than with the hexane:2-propanol or acetone solvents. The concentrations of TL-FAMEs in chemical groups, including saturated, branched, mono- and poly-unsaturated and hydroxy fatty acids were assessed, and biological groups (soil bacteria, mycorrhizal fungi, saprophytic fungi and higher plants) was distinguished. The extraction efficiency for the chemical and biological groups followed the general trend of: chloroform:methanol:buffer> or =chloroform:methanol>hexane:2-propanol=acetone. Discriminant analysis revealed differences in TL-FAME profiles based on the solvent mixture and the soil type. Although solvent mixtures containing chloroform and methanol were the most efficient for extracting lipids from the agricultural soils in this study, soil properties and the lipid groups to be studied should be considered when selecting a solvent mixture. According to our knowledge, this is the first report of soil lipid extraction with hexane:2-propanol or acetone in a pressurized solvent extraction system.

  2. A unique laboratory test rig reduces the need for offshore tests to combat calcium naphthenate deposition in oilfield process equipment.

    Energy Technology Data Exchange (ETDEWEB)

    Mediaas, Heidi; Grande, Knut; Hustad, Britt-Marie; Hoevik, Kim Reidar; Kummernes, Hege; Nergaard, Bjoern; Vindstad, Jens Emil

    2006-03-15

    Producing and refining high-TAN crude oils introduces a number of challenges, among which calcium naphthenate deposition in process facilities is the most serious production issue. Until recently, the only option for studying chemicals and process parameters in order to prevent naphthenate deposition has been field tests. Statoil has now developed a small scale pilot plant where these experiments can be performed in the laboratory at Statoil's Research and Technology Center in Trondheim, Norway. The results from the pilot plant are in full agreement with the extensive naphthenate experience obtained from almost 9 years operation of the Heidrun oilfield. The design and operational procedures for this test facility are based on the recent discovery by Statoil and ConocoPhillips of the ARN acid. The ARN acid is a prerequisite for calcium naphthenate deposition. The new continuous flow pilot plant, the Naphthenate Rig, is used to develop new environmental friendly naphthenate inhibitors and to optimize process operating conditions. Since it operates on real crudes the need for field tests in qualifying new naphthenate inhibitors is reduced. To the best of our knowledge, the rig is the first of its kind in the world. (Author)

  3. Solvent

    OpenAIRE

    Hamida Y. Mostafa; Ebaa A. El-Shamy; Amal S. Farag; Nadia G. Kandile

    2013-01-01

    Neat ethylacetoacetate (EAA) and its mixtures with a co-solvent and an anti-solvent have been studied for refining of heavy wax distillate fraction to produce substantially non-carcinogenic base oil. The co-solvent and anti-solvent used are dipropylene glycol (DPG) and ethylene glycol (EG) respectively. The solubility characteristics of the main solvent and its mixed solvent systems were studied. Selection of the optimum solvent mixture and extraction variables has been studied. The effect of...

  4. Biochemical changes in cuttings of Robinia pseudoacacia after treatment with naphthenate

    Directory of Open Access Journals (Sweden)

    SLAVKO KEVRESAN

    2007-10-01

    Full Text Available Naphthenic acids were isolated from gas oil fractions (distillation interval 168–290 °C of Vojvodina crude oil “Velebit”, characterized and their biological ac­tivity evaluated by the biochemical changes in cuttings of Robinia pseudoacacia after treatment with naphthenate. The activities of IAA peroxidase, total peroxi­da­ses and amylase, as well as the contents of reducing sugars and total proteins, were determined in the basal parts of soft wood cuttings of black locust after treat­ment with sodium naphthenate or the sodium salt of 1-naphthaleneacetic acid (NAA, con­­centration 10-7 mol dm-3 for 3 or 6 h. High activities of IAA oxidase and amy­lase, together with a low activity of peroxidase (which is known as being stimula­tory for the initiation and activation of primordia were obtained after the three-hour treatment with sodium naphthenate. Six-hour treatment had an inhibitory effect on the examined biochemical markers. The effects of three- and six-hour treatments with NAA were between those of the corresponding treatment with naphthenic acids.

  5. 21 CFR 524.463 - Copper naphthenate.

    Science.gov (United States)

    2010-04-01

    ... and ponies for thrush caused by organisms susceptible to copper naphthenate. (3) Limitations. Use on horses and ponies only. Avoid contact around eyes. Do not contaminate feed. Do not use in horses...

  6. Difference between Chitosan Hydrogels via Alkaline and Acidic Solvent Systems

    Science.gov (United States)

    Nie, Jingyi; Wang, Zhengke; Hu, Qiaoling

    2016-10-01

    Chitosan (CS) has generated considerable interest for its desirable properties and wide applications. Hydrogel has been proven to be a major and vital form in the applications of CS materials. Among various types of CS hydrogels, physical cross-linked CS hydrogels are popular, because they avoided the potential toxicity and sacrifice of intrinsic properties caused by cross-linking or reinforcements. Alkaline solvent system and acidic solvent system are two important solvent systems for the preparation of physical cross-linked CS hydrogels, and also lay the foundations of CS hydrogel-based materials in many aspects. As members of physical cross-linked CS hydrogels, gel material via alkaline solvent system showed significant differences from that via acidic solvent system, but the reasons behind are still unexplored. In the present work, we studied the difference between CS hydrogel via alkaline system and acidic system, in terms of gelation process, hydrogel structure and mechanical property. In-situ/pseudo in-situ studies were carried out, including fluorescent imaging of gelation process, which provided dynamic visualization. Finally, the reasons behind the differences were explained, accompanied by the discussion about design strategy based on gelation behavior of the two systems.

  7. Third generation capture system: precipitating amino acid solvent systems

    NARCIS (Netherlands)

    Sanchez Fernandez, E.; Misiak, K.; Ham, L. van der; Goetheer, E.L.V.

    2013-01-01

    This work summarises the results of the design of novel separation processes for CO2 removal from flue gas based on precipitating amino acid solvents. The processes here described (DECAB, DECAB Plus and pH-swing) use a combination of enhanced CO2 absorption (based on the Le Chatelier’s principle) an

  8. Gas Stirring to Enhance Mass Transfer During Extraction of Copper by Naphthenic Acid%用气相搅动方法强化环烷酸萃取铜的质量传递

    Institute of Scientific and Technical Information of China (English)

    Olfat A Fadali

    2004-01-01

    The effect of nitrogen sparging on the mass transfer rate in the extraction of copper from aqueous solution by a kerosene solution of naphthenic acids was studied.Investigated variables: nitrogen flow rate, copper ion concentration, and extraction temperature. It was concluded that the mass transfer coefficient of copper extraction was related to the gas flow rate by the equation: K = aU. The effect of temperature on the mass transfer coefficient was found to obey Arrhenius equation with an activation energy of 2875 calories. The mass transfer coefficient was found to decrease with increasing copper ion concentration.%研究了氮注射对环烷酸萃取溶液中铜离子的质量转移速率的影响.研究的因素包括:氮流速、铜离子浓度及萃取温度.结果发现,铜离子萃取的质量转移速率与气体流速有关,并遵守如下方程:K=aU,温度对质量转移速率的影响遵循阿列纽斯方程,其活化能为2875卡路里;质量转移系数随溶液中铜离子浓度的增加而降低.

  9. Aromatic naphthenic acids in oil sands process-affected water, resolved by GCxGC-MS, only weakly induce the gene for vitellogenin production in zebrafish (Danio rerio) larvae.

    Science.gov (United States)

    Reinardy, Helena C; Scarlett, Alan G; Henry, Theodore B; West, Charles E; Hewitt, L Mark; Frank, Richard A; Rowland, Steven J

    2013-06-18

    Process waters from oil sands industries (OSPW) have been reported to exhibit estrogenic effects. Although the compounds responsible are unknown, some aromatic naphthenic acids (NA) have been implicated. The present study was designed to investigate whether aromatic NA might cause such effects. Here we demonstrate induction of vitellogenin genes (vtg) in fish, which is a common bioassay used to indicate effects consistent with exposure to exogenous estrogens. Solutions in water of 20-2000 μg L(-1) of an extract of a total OSPW NA concentrate did not induce expression of vtg in larval zebrafish, consistent with earlier studies which showed that much higher NA concentrations of undiluted OSPW were needed. Although 20-2000 μg L(-1) of an esterifiable NA subfraction of the OSPW NA concentrate did induce expression, this was of much lower magnitude to that induced by much lower concentrations of 17α-ethynyl estradiol, indicating that the effect of the total NAs was only weak. However, given the high NA concentrations and large volumes of OSPW extant in Canada, it is important to ascertain which of these esterifiable NA in the OSPW produce the effect. Up to 1000 μg L(-1) of an OSPW subfraction containing only alicyclic NA, and considered by most authors to be NA sensu stricto, did not produce induction; but, as predicted, 10-1000 μg L(-1) of an aromatic NA fraction did. Such effects by the aromatic acids are again consistent with those of only a weak estrogenic substance. These findings may help to focus studies of the most environmentally significant OSPW-related pollutants, if reproduced in a greater range of OSPW.

  10. Biological research for human being skin color and color transform - 4- ammonia methyl - naphthenic acid effect%人皮肤色泽受反式-4-氨甲基-环己烷甲酸作用的研究

    Institute of Scientific and Technical Information of China (English)

    张劲松; 方震(通讯作者); 于丽; 陈振鹤; 李长根; 林雪贞; 罗晓丹

    2013-01-01

    Objective :Exploring TRANS-methyl-cyclohexane carboxylic acid and the change regularity of the relationship between human skin color. Methods :September 2010 -2013 years June,, takes the person living specimen normal skin (in the fol owing palpebralis relaxation technique to plan to excise skin) to 18 cases of cases to carry on transform - 4- ammonia methyl - naphthenic acid injects partial y, groups the different drug concentration and dosage (supplement measurement), after being the scheduled dosage, left the surgery takes down by transform - 4- ammonia methyl - naphthenic acid function and right not by transform - 4- ammonia methyl - the skin specimen of naphthenic acid function, groups to freeze the preserve immediately. After accumulating the certain amount specimen, determines its skin color. Results :This group 18 cases of patients, transform - 4- ammonia methyl - after naphthenic acid partial injection, wil cause the partial skin color change.Conclusion :At present thinks transform - 4- ammonia methyl -naphthenic acid and human skin color change has the relevance, is not only related transform - 4- ammonia methyl - naphthenic acid change skin color provides clinical and experiment basis, can in the director daily life to the correct choice of related medicine.%  目的:探讨反式-4-氨甲基-环己烷甲酸与人类皮肤色泽改变相关性的规律性。方法:2010年9月~2013年6月,对18例病例取人活体正常皮肤(如下睑松弛术中计划切除皮肤)进行反式-4-氨甲基-环己烷甲酸局部注射,分组不同药物浓度、剂量(补充计量),达到预定剂量后[1],手术取下左侧受反式-4-氨甲基-环己烷甲酸作用的和右侧未受反式-4-氨甲基-环己烷甲酸作用的皮肤标本,立即分组冷冻储藏[2]。待积累一定数量标本后[3],对其皮肤色泽进行测定。结果:本组共18例患者,反式-4-氨甲基-环己烷甲酸局部注射后

  11. Effects of temperature and solvent concentration on the solvent crystallization of palm-based dihydroxystearic acid with isopropyl alcohol

    Institute of Scientific and Technical Information of China (English)

    Gregory F.L.Koay; Teong-Guan Chuah; Sumaiya Zainal-Abidin; Salmiah Ahmad; Thomas S.Y.Choong

    2012-01-01

    Palm-based dihydroxystearic acid of 69.55% purity was produced in a 500-kg-per-batch operation pilot plant and purified through solvent crystallization in a custom fabricated simultaneous batch crystallizer unit.The effects of temperature and solvent concentration on yield,particle size distribution and purity were studied.The purity was higher,while the yield and particle size were lower and smaller,respectively,at higher temperature and solvent concentration.The solvent crystallization process efficiency was rated at 66-69% when carried out with 70-80% isopropyl alcohol at 20 ℃.

  12. 两种钢在高温环烷酸中腐蚀行为的研究%Study on Corrosion Behaviors of Two Kinds of Steel in High Temperature Naphthenic Acid

    Institute of Scientific and Technical Information of China (English)

    杨瑞; 程丽华; 于湘; 战洪仁; 杨鑫莉; 余俊良; 王智

    2016-01-01

    采用高温高压反应釜,考察温度、酸值和转速对20#碳钢、304不锈钢腐蚀速率的影响。结果表明:在220~300℃随着温度的升高,20#碳钢腐蚀速率先增大后减小,在280℃达到最大值0.654 mm/a,304不锈钢材料腐蚀速率逐渐较小;随着酸值的增大,20#碳钢腐蚀速率不断上升,在酸值为8~10 mgKOH/g时增速最大,304不锈钢呈直线趋势逐渐减小;在转速为0.8~2 m/s的范围内,20#碳钢腐蚀速率由0.654 mm/a变化到0.56 mm/a,304不锈钢由0.0396 mm/a变化到0.0112 mm/a,说明在低转速范围内环烷酸腐蚀影响并不太明显。%Using high temperature and high pressure reaction kettle, influence of temperature, acid value and rotating speed on 20#carbon steel and SS304 stainless steel corrosion rates was investigated. The results show that: with the increase of temperature, 20# carbon steel corrosion rate first increases and then decreases, the maximum value is 0.654 mm/a at 280℃, and SS304 stainless steel corrosion rate decreases gradually; with the increase of acid value, 20# carbon steel corrosion rate rises,the largest growth appears in the value of 8~10 mgKOH/g, and SS304 stainless steel corrosion rate decreases gradually; when rotation rate is in the range of 0.8~2 m/s , 20# carbon steel corrosion rate changes from 0.654 mm/a to 0.56 mm/a, SS304 stainless steel corrosion rate changes from 0.039 6 mm/a to 0.011 2 mm/a ,which proves that influence of rotation rate in low speed range on the naphthenic acid corrosion is not obvious.

  13. A knowledge based advisory system for acid/base titrations in non-aqueous solvents

    NARCIS (Netherlands)

    Bos, M.; Linden, van der W.E.

    1996-01-01

    A computer program was developed that could advice on the choice of solvent and titrant for acid/base titrations in nonaqueous media. It is shown that the feasibility of a titration in a given solvent can be calculated from solvent properties and intrinsic acid/base properties of the sample componen

  14. 21 CFR 173.280 - Solvent extraction process for citric acid.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Solvent extraction process for citric acid. 173.280... extraction process for citric acid. A solvent extraction process for recovery of citric acid from conventional Aspergillus niger fermentation liquor may be safely used to produce food-grade citric acid...

  15. Evaluating the hydrophilic-lipophilic nature of asphaltenic oils and naphthenic amphiphiles using microemulsion models.

    Science.gov (United States)

    Kiran, Sumit K; Acosta, Edgar J; Moran, Kevin

    2009-08-01

    Asphaltenes and naphthenic acid derivatives, which are polar and surface-active species, are known to interfere with the recovery of heavy crude oil by promoting the formation of stable emulsions. In this study, previously established microemulsion phase behavior models were applied to quantify the hydrophilic-lipophilic nature of asphaltenic oils (bitumen, deasphalted bitumen, asphalt, naphthalene) and surface-active species found in heavy oils (naphthenic compounds and asphaltenes). For the test oils, the equivalent alkane carbon number (EACN) was determined by evaluating the "salinity shifts" of microemulsions formulated with a reference surfactant (sodium dihexyl sulfosuccinate--SDHS) and a reference oil (toluene) as a function of test oil volume fraction. Similarly, the characteristic curvature (C(C)) of surface-active species was determined by evaluating the salinity shifts as a function of the molar fraction of the surface-active species in mixture with SDHS. As a part of the oil phase, asphaltenes and asphaltene-like species are highly hydrophilic, which lead to low EACN values despite their large molecular weight. As a surface-active material, asphaltenes are hydrophobic species that lead to the formation of water-in-oil emulsions. Naphthenates, particularly sodium naphthenates, are highly hydrophilic compounds that lead to the formation of oil-in-water emulsions. These hydrophilic-lipophilic characterization parameters, and the methods used to determine them, can be used in the future to understand the phase behavior of complex oil-water systems.

  16. Water-enhanced solubility of carboxylic acids in organic solvents and its applications to extraction processes

    Energy Technology Data Exchange (ETDEWEB)

    Starr, J.N.; King, C.J.

    1991-11-01

    The solubilities of carboxylic acids in certain organic solvents increase remarkably with an increasing amount of water in the organic phase. This phenomenon leads to a novel extract regeneration process in which the co-extracted water is selectively removed from an extract, and the carboxylic acid precipitates. This approach is potentially advantageous compared to other regeneration processes because it removes a minor component of the extract in order to achieve a large recovery of acid from the extract. Carboxylic acids of interest include adipic acid, fumaric acid, and succinic acid because of their low to moderate solubilities in organic solvents. Solvents were screened for an increase in acid solubility with increased water concentration in the organic phase. Most Lewis-base solvents were found to exhibit this increased solubility phenomena. Solvents that have a carbonyl functional group showed a very large increase in acid solubility. 71 refs., 52 figs., 38 tabs.

  17. Naphthenic corrosion resistance, mechanical properties and microstructure evolution of experimental Cr-Mo steels with high Mo content

    Directory of Open Access Journals (Sweden)

    Lorena Braga Moura

    2012-04-01

    Full Text Available One method to face the effects of naphthenic acid corrosion in petroleun refining plants is to use alloys with good resistance to this kind of corrosion. For this purpose, molybdenum additions to chromium containing steels are specially recommended. In this work, experimental Fe-9Cr-xMo (x = 5, 7 and 9 wt. (% ingots were cast, forged and hot rolled before being tested in a naphthenic acid environment. Evolution of the mechanical properties with composition is presented. The precipitation and dissolution of phases were investigated with the help of Thermocalc and electron backscattered diffraction (EBSD.

  18. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

    Institute of Scientific and Technical Information of China (English)

    XUXin; ZHUTun

    2002-01-01

    Solvent extraction equiliria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester, di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent of the e/r value and hydration energy of the metal ions. The minor shift of the P→O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P→O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compunds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effects is explained by using IR spectra of the loaded organic phase.

  19. 2,5-PRODAN Derivatives as Highly Sensitive Sensors of Low Solvent Acidity

    Directory of Open Access Journals (Sweden)

    Alexandra H. Yoon

    2014-05-01

    Full Text Available Two 5-acyl-2-dimethylaminonaphthalene derivatives, one with a propionyl group and the other with a fused cyclohexanone ring, are investigated as sensors of H-bond-donating ability in protic solvents of low solvent acidity. Their fluorescence is highly quenched in protic solvents, and the quenching order of magnitude is linearly related to the H-bond-donating ability of the solvent as quantified by the solvent acidity (SA scale. As the solvent acidity increases from 0.15 to 0.40, the fluorescence for both is quenched by more than a factor of ten; thus, they are extremely sensitive sensors of the hydrogen-bond-donating ability in this weakly acidic range. Preferential solvation studies suggest that quenching occurs from a doubly H-bonded excited state.

  20. A knowledge based advisory system for acid/base titrations in non-aqueous solvents

    OpenAIRE

    1996-01-01

    A computer program was developed that could advice on the choice of solvent and titrant for acid/base titrations in nonaqueous media. It is shown that the feasibility of a titration in a given solvent can be calculated from solvent properties and intrinsic acid/base properties of the sample components. A consistent set of properties for various solvents and a large number of acidic and basic compounds was calculated from literature data with the use of a genetic algorithm. Test results show t...

  1. EFFECTS OF SOLVENT POLARITY ON FREE RADICAL COPOLY MERIZATION OF 5-HEXENOIC ACID AND ACRYLONITRILE

    Institute of Scientific and Technical Information of China (English)

    WANG Bing; XIE Shishan; CAO Mengjiun

    1987-01-01

    The effects of solvent polarity on free radical copolymerization of 5-hexenoic acid and acrylonitrile at 60℃ were studied. It was observed that as the polarity of solvents enhanced, both the copolymerization rate and the reactivity ratios r1, r2 increased, while the alternating tendency of monomer units in copolymer chain decreased. It is believed that the solvent polarity raises the reactivities of acrylonitrile monomer and its growing chain radical, but causes no distinct variation in those of 5-hexenoic acid.

  2. Controlling the assembly of CdS nanorods via solvent and acidity

    NARCIS (Netherlands)

    Koster, L. J. A.; Khodabakhsh, S.; Greenham, N. C.

    2014-01-01

    We report control over the phase behavior of CdS nanorods via the solvent and acidity. CdS nanorods were synthesized using alkane phosphonic acid ligands, which were replaced after synthesis by a series of aromatic ligands. Change of ligand enabled us to cast films from different solvents. By replac

  3. Solvent-Controlled Chemoselectivity in the Photolytic Release of Hydroxamic Acids and Carboxamides from Solid Support.

    Science.gov (United States)

    Qvortrup, Katrine; Petersen, Rico G; Dohn, Asmus O; Møller, Klaus B; Nielsen, Thomas E

    2017-06-16

    The synthetic utility and theoretical basis of a photolabile hydroxylamine-linker are presented. The developed protocols enable the efficient synthesis and chemoselective photolytic release of either hydroxamates or carboxamides from solid support. The bidetachable mode of the linker unit is uniquely dependent on the solvent. Hydroxamic acids are obtained by performing photolysis in protic solvents, whereas photolysis in aprotic solvents enables the selective release of carboxamides.

  4. Polymorphism control of p-aminobenzoic acid by isothermal anti-solvent crystallization

    Science.gov (United States)

    Garg, Rakesh Kumar; Sarkar, Debasis

    2016-11-01

    We report, for the first time, the control of polymorphism of p-aminobenzoic acid by isothermal anti-solvent crystallization using ethanol as solvent and water as anti-solvent. p-aminobenzoic (p-ABA) acid crystallizes in two distinct polymorphic forms: the α-polymorph, which is commercially available form and appears as long fibrous needles; and the β-polymorph, which appears in the form of prisms. The solubility of p-ABA was determined gravimetrically for various water/ethanol mixtures at 15 °C and isothermal anti-solvent crystallization experiments were conducted at 15 °C over a range of supersaturation ratio from 1.01 to 1.30 and at different anti-solvent addition rates of 4, 6, 8, and10 ml/h. The needle-type α-polymorph was always obtained at higher supersaturation ratio and higher flow-rates of anti-solvent addition. The prismatic β-polymorph was obtained at lower supersaturation range of 1.01-1.06 when anti-solvent was added at 4 and 6 ml/h. The obtained polymorphs were characterized using scanning electron microscopy, powder x-ray diffraction, and differential scanning calorimetry. The region of occurrence of each polymorph with respect to supersaturation ratio and anti-solvent wt% is presented for these addition rates. The careful selection of supersaturation ratio and anti-solvent addition rate can produce desired polymorph of p-ABA by anti-solvent crystallization.

  5. Separation of Acetic Acid from Aqueous Solution using Various Organic Solvents

    Directory of Open Access Journals (Sweden)

    Md. Zaved Hossain Khan

    2014-01-01

    Full Text Available 800x600 Normal 0 false false false EN-US X-NONE X-NONE MicrosoftInternetExplorer4 In the study a model has been developed to separate the acetic acid from aqueous solution by liquid-liquid extraction and find out the proper solvent for this separation. Various solvents such as n-butanol, iso butanol, amyl alcohol and ethyl acetate are used for separation of acetic acid from water. The binodal curves (mutual solubility curves for acetic acid distributed between water and an organic solvent were obtained by titrating known mixtures of two components (water and solvents with the third component acetic acid to the point of first appearance of permanent turbidity. In order to determine the tie-lines, the absorbance of the coexisting phases, obtained by the separation of ternary mixtures within the binodal curve are needed to be determined. The absorbance of each point had been determined by a UV spectrophotometer. Distribution diagrams are obtained by plotting weight percent of acetic acid in solvent phase against the weight percent of acetic acid in water phase. Selectivity diagrams are also obtained by plotting (wt. % of acetic acid / (percent of acetic acid + percent of water in solvent phase against the same quantity in the diluent phase. The separation factor is determined numerically from the tie-line data.

  6. Analysis of process configurations for CO2 capture by precipitating amino acid solvents

    NARCIS (Netherlands)

    Sanchez Fernandez, E.; Heffernan, K.; Ham, L.V. van der; Linders, M.J.G.; Brilman, D.W.F.; Goetheer, E.L.V.; Vlugt, T.J.H.

    2014-01-01

    Precipitating amino acid solvents are an alternative to conventional amine scrubbing for CO2 capture from flue gas. Process operation with these solvents leads to the formation of precipitates during absorption that need to be re-dissolved prior to desorption of CO2. The process configuration is cru

  7. Dissociation of a strong acid in neat solvents: diffusion is observed after reversible proton ejection inside the solvent shell.

    Science.gov (United States)

    Veiga-Gutiérrez, Manoel; Brenlla, Alfonso; Carreira Blanco, Carlos; Fernández, Berta; Kovalenko, Sergey A; Rodríguez-Prieto, Flor; Mosquera, Manuel; Lustres, J Luis Pérez

    2013-11-14

    Strong-acid dissociation was studied in alcohols. Optical excitation of the cationic photoacid N-methyl-6-hydroxyquinolinium triggers proton transfer to the solvent, which was probed by spectral reconstruction of picosecond fluorescence traces. The process fulfills the classical Eigen-Weller mechanism in two stages: (a) solvent-controlled reversible dissociation inside the solvent shell and (b) barrierless splitting of the encounter complex. This can be appreciated only when fluorescence band integrals are used to monitor the time evolution of the reactant and product concentrations. Band integrals are insensitive to solvent dynamics and report relative concentrations directly. This was demonstrated by first measuring the fluorescence decay of the conjugate base across the full emission band, independently of the proton-transfer reaction. Multiexponential decay curves at single wavelengths result from a dynamic red shift of fluorescence in the course of solvent relaxation, whereas clean single exponential decays are obtained if the band integral is monitored instead. The extent of the shift is consistent with previously reported femtosecond transient absorption measurements, continuum theory of solvatochromism, and molecular properties derived from quantum chemical calculations. In turn, band integrals show clean biexponential decay of the photoacid and triexponential evolution of the conjugate base in the course of the proton transfer to solvent reaction. The dissociation step follows the slowest stage of solvation, which was measured here independently by picosecond fluorescence spectroscopy in five aliphatic alcohols. Also, the rate constant of the encounter-complex splitting stage is compatible with proton diffusion. Thus, for this photoacid, both stages reach the highest possible rates: solvation and diffusion control. Under these conditions, the concentration of the encounter complex is substantial during the earliest nanosecond.

  8. Molecular microenvironments: Solvent interactions with nucleic acid bases and ions

    Science.gov (United States)

    Macelroy, R. D.; Pohorille, A.

    1986-01-01

    The possibility of reconstructing plausible sequences of events in prebiotic molecular evolution is limited by the lack of fossil remains. However, with hindsight, one goal of molecular evolution was obvious: the development of molecular systems that became constituents of living systems. By understanding the interactions among molecules that are likely to have been present in the prebiotic environment, and that could have served as components in protobiotic molecular systems, plausible evolutionary sequences can be suggested. When stable aggregations of molecules form, a net decrease in free energy is observed in the system. Such changes occur when solvent molecules interact among themselves, as well as when they interact with organic species. A significant decrease in free energy, in systems of solvent and organic molecules, is due to entropy changes in the solvent. Entropy-driven interactioins played a major role in the organization of prebiotic systems, and understanding the energetics of them is essential to understanding molecular evolution.

  9. Determination and Correlation of Solubility for D-Xylose in Volatile Fatty Acid Solvents

    Institute of Scientific and Technical Information of China (English)

    李涛; 陈飞雄; 江振西; 任保增

    2014-01-01

    The solubility of D-xylose in formic acid and binary solvents of formic acid with formic acid and acetic acid, propionic acid, n-butyric acid or isobutyric acid was measured in the temperature range from 300.35 to 325.05 K using the synthetic method by a laser monitoring technique at atmospheric pressure. The solid-liquid equilibrium data will provide essential support for industrial design and further theoretical study. The experimental data show that the solubility of D-xylose in formic acid and in the mixtures of formic acid+acetic acid (1︰1), formic acid+propionic acid (1︰1), formic acid+n-butyric acid (1︰1), and formic acid+isobutyric acid (1︰1) increases with temperature. The Apelblat equation, theλh model, and the ideal solution equation correlate the solubility data well.

  10. Electrochemical oxidation of substituted benzylamines in aquo-acetic acid medium: substituent and solvent effects

    Indian Academy of Sciences (India)

    A Thirumoorthi; K P Elango

    2007-07-01

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett’s substituent constants affording negative reaction constants. The correlation of potential values with macroscopic solvent parameters is non-linear suggesting that the operation of both specific and non-specific solvent-solvent-solute interaction mechanisms. Multiple correlation analysis of the experimental data with Kamlet-Taft solvatochromic parameters is employed.

  11. Reactive Extraction of L (+ Tartaric Acid by Amberlite LA-2 in Different Solvents

    Directory of Open Access Journals (Sweden)

    I. Inci

    2011-01-01

    Full Text Available The extraction of L(+ tartaric acid from aqueous solutions by amberlite LA-2 is a secondary amine mixture in different diluent solvents. Extraction equilibria of L(+ tartaric acid by amberlite LA-2 in 1-octanol, cyclohexane, isooctane, hexane, methyl isobutyl ketone (MIBK solvents at temperature 298.15 K have been measured. The batch extraction experiments distribution coefficients (D, loading factors ( Z and extraction efficiency (E were calculated. The maximum removal of L(+ tartaric acid is 91 % with MIBK and 0.92 mol.L-1 initial concentration of Amberlite LA-2.

  12. The effects of solvent polarity and pKa on the absorption of solvents into poly(glutaric acid-glycerol) films

    Science.gov (United States)

    In this study, solvent absorption into the matrices of poly(glutaric acid-glycerol) films has been evaluated. It was determined that the combined effects of polarity and the size and shape of the solvent molecule, rather than pKa, have the most significant influence on absorption into the films. P...

  13. No-solvent Condensation Reaction of Amino Acids and their Derivatives with Pyrandione

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Synthesis of a novel series of N-pyrandione substituted amino acids and their esters 3 via a condensation reaction between pyrandione and amino acid or their derivatives in excess ethyl orthoformate without solvent is described. The stereochemistry of 3 has been discussed.

  14. Conceptual design of a novel CO2 capture process based on precipitating amino acid solvents

    NARCIS (Netherlands)

    Sanchez Fernandez, E.; Heffernan, K.; Ham, L.V. van der; Linders, M.J.G.; Eggink, E.; Schrama, F.N.H.; Brilman, D.W.F.; Goetheer, E.L.V.; Vlugt, T.J.H.

    2013-01-01

    Amino acid salt based solvents can be used for CO2 removal from flue gas in a conventional absorption-thermal desorption process. Recently, new process concepts have been developed based on the precipitation of the amino acid zwitterion species during the absorption of CO2. In this work, a new conce

  15. Synthesis of β3-Amino Acids via Catalyst- and Solvent-Free Aza-Michael Reaction

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A safe, environmentally friendly and cost-effective method for the synthesis of β-amino acid derivatives has been developed. Treatment of α,β-unsaturated compounds with aliphatic amines furnishes β-amino acid derivatives in good to excellent yields via a catalyst- and solvent-free aza-Michael addition.

  16. Enzymatic Synthesis of Dipeptide Derivatives Containing Noncoded Amino Acids in Organic Solvents

    Institute of Scientific and Technical Information of China (English)

    YANG,Hong(杨洪); ZHOU,Chuang(周闯); TIAN,Gui-Ling(田桂玲); YE,Yun-Hua(叶蕴华)

    2002-01-01

    A series of dipeptide derivatives containing non-coded amino acis, N-Boc-4-X-Phe-Ala-NHNHNHPh (X= Cl, Br, I, NO2),were synthesized by using thermoase in organic solvents. The physical data were consistent with the same samples prepared by 3-( diethoxyphosphoryloxy)-1, 2, 3-benzotriazin-4 (3H)-one (DEPBT). Influence of different substituted groups of the non-coded amino acids and different organic solvents on the enzymatic peptide synthesis was studied.

  17. Thermal decomposition of organic solvent with nitric acid in nuclear fuel reprocessing plants

    Energy Technology Data Exchange (ETDEWEB)

    Koike, Tadao; Nishio, Gunji; Takada, Junichi; Tukamoto, Michio; Watanabe, Kouji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Miyata, Sadaichirou

    1995-02-01

    Since a thermal decomposition of organic solvent containing TBP (tributyl phosphate) with nitric acid and heavy metal nitrates is an exothermic reaction, it is possible to cause an explosive decomposition of TBP-complex materials formed by a nitration between the solvent and nitric acid, if the solvent involving TBP-complex is heated upto a thermal limit in an evaporator to concentrate a fuel liquid solution from the extraction process in the reprocessing plant. In JAERI, the demonstration test for explosive decomposition of TBP-complex by the nitration was performed to elucidate the safety margin of the evaporator in the event of hypothetical explosion under auspices of the Science and Technology Agency. The demonstration test was carried out by heating TBP/n-dodecane solvent mixed with nitric acid and uranium nitrate. In the test, the thermal decomposition behavior of the solvent was examined, and also a kinematic reaction constant and a heat formation of the TBP-complex decomposition were measured by the test. In the paper, a safety analysis of a model evaporator was conducted during accidental conditions under the explosive decomposition of the solvent. (author).

  18. Conformational analysis of glutamic acid: a density functional approach using implicit continuum solvent model.

    Science.gov (United States)

    Turan, Başak; Selçuki, Cenk

    2014-09-01

    Amino acids are constituents of proteins and enzymes which take part almost in all metabolic reactions. Glutamic acid, with an ability to form a negatively charged side chain, plays a major role in intra and intermolecular interactions of proteins, peptides, and enzymes. An exhaustive conformational analysis has been performed for all eight possible forms at B3LYP/cc-pVTZ level. All possible neutral, zwitterionic, protonated, and deprotonated forms of glutamic acid structures have been investigated in solution by using polarizable continuum model mimicking water as the solvent. Nine families based on the dihedral angles have been classified for eight glutamic acid forms. The electrostatic effects included in the solvent model usually stabilize the charged forms more. However, the stability of the zwitterionic form has been underestimated due to the lack of hydrogen bonding between the solute and solvent; therefore, it is observed that compact neutral glutamic acid structures are more stable in solution than they are in vacuum. Our calculations have shown that among all eight possible forms, some are not stable in solution and are immediately converted to other more stable forms. Comparison of isoelectronic glutamic acid forms indicated that one of the structures among possible zwitterionic and anionic forms may dominate over the other possible forms. Additional investigations using explicit solvent models are necessary to determine the stability of charged forms of glutamic acid in solution as our results clearly indicate that hydrogen bonding and its type have a major role in the structure and energy of conformers.

  19. Determination and Correlation for Solubility of Aromatic Acids in Solvents

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Solubility of benzoic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid in water, acetic acid, N,N-dimethyfformamide, N,N-dimethylacetamide, dimethyl sulphoxide and N-methyl-2-ketopyrrolidine were measured by dynamic method. The solubilities were calculated by UNIFAC group contribution method, in which new groups, BCCOOH and NCCOOH, were introduced to express the activity coefficients of aromatic acids and new interaction parameters of the new groups were expressed as the function of temperature, which were determined from the experimental data. The new interaction parameters provided good calculated result. The experimental data were also correlated with Wilson and λ-h models, and results were compared with present UNIFAC model.

  20. Spectrophotometric determination of the acidity constants of calcon in water and mixed water–organic solvents

    Directory of Open Access Journals (Sweden)

    MOHAMMAD MAZLOUM-ARDAKANI

    2009-02-01

    Full Text Available The acid–base properties of calcon (1-(2-hydroxy-1-naphthylazo-2-naphthol-4-sulfonic acid in water and mixed water–organic solvents at 25 °C at an ionic strength of 0.10 M are studied by a multiwavelength spectrophotometric method. The organic solvents used were the amphiprotic (methanol, dipolar aprotic (dimethylsulfoxide, and low basic aprotic (acetonitrile. To evaluate the pH absorbance data, a resolution method based on the combination of soft- and hard-modeling was applied. The acidity constants of all related equilibria were estimated using the whole spectral fitting of the collected data to an established factor analysis model. The data analysis program Datan was applied for determination of the acidity constants. The corresponding pKa values were determined in water and mixed water–organic solvents. Linear relationship between the acidity constants and the mole fraction of the different sol-vents in the mixtures exist. The effect of solvent properties on acid–base behavior is discussed.

  1. Preparation and evaluation of abietic acid microcapsules by a solvent evaporation technique.

    Science.gov (United States)

    Puranik, P K; Manekar, N C; Dorle, A K

    1992-01-01

    Abietic acid was isolated from rosin N Grade (ISI) by a simple process and the product was further standardized. Sulphadiazine microcapsules were prepared by the solvent evaporation technique, using abietic acid as a wall-forming material. Discrete, spherical and free-flowing microcapsules were obtained by phase separation induced by solvent evaporation using bentonite as a solid emulsifier. The prepared microcapsules were evaluated for drug content, wall thickness, flow properties, size distribution, density and in vitro dissolution studies in gastric fluid. The effect of various process variables such as agitation speed, coat-core ratio, etc., on the micromeritic and release characteristics has been described.

  2. Amino acid salt solutions as solvents in CO2 capture from flue gas

    DEFF Research Database (Denmark)

    Lerche, Benedicte Mai; Thomsen, Kaj; Stenby, Erling Halfdan

    New solvents based on the salts of amino acids have emerged as an alternative to the alkanolamine solutions, for the chemical absorption of CO2 from flue gas. But only few studies on amino acids as CO2 capturing agents have been performed so far. One of the interesting features of amino acid salt...... solutions is their ability to form solid precipitates upon the absorption of CO2. The occurrence of crystallization offers the possibility of increasing the CO2 loading capacity of the solvent. However, precipitation can also have negative effect on the CO2 capture process. The chemical nature of the solid...... of glycine, taurine, and lysine, while in the case of proline, and glutamic acid, the precipitate was found to be bicarbonate. These results give an important contribution to further understanding the potential of amino acid salt solutions in CO2 capture from flue gas....

  3. Solvent extraction of vanadium from sulfuric acid solution

    Institute of Scientific and Technical Information of China (English)

    WANG Mingyu; ZHANG Guiqing; WANG Xuewen; ZHANG Jialiang

    2009-01-01

    The behaviour of vanadium(V) extracted from sulfuric acid solution was investigated using Cyanex 923 as an cxtractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium(V) increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium(V) fi'om sulfuric acid solution at low pH conditions, and the best pH conditions for exuaction of vanadium(V) are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium(V) recovery from the sulfuric acid solution.

  4. Liquid phase ozonation of cyclohexanol using acetic acid as solvent

    Energy Technology Data Exchange (ETDEWEB)

    Encinar, J.M.; Beltran, F.J. (Departamento de Ingeneria Quimica y Energetica. Facultad de Ciencias. Badajoz (Spain)); Frades, J.M. (Departamento de Ingenieria Quimica. E.U.P. Almaden (Spain))

    1994-01-01

    The liquid phase oxidation of cyclohexanol in an acetic acid medium using a mixture of oxygen and ozone has been studied in a laboratory semi batch reactor. The influence of temperature, ozone partial pressure, initial concentration of cyclohexanol on its conversion and yield and distribution of products has been observed. Under the experimental conditions investigated formation of peroxydic compounds and mono basic acids was not relevant; the major products obtained were cyclohexanone and adipic and glutaric acids although analytical chromatograms revealed the presence of other products unidentified. Formation of these products is qualitatively explained by means of a chain-radical mechanism. Finally, it is proposed an empirical kinetic equation which relates the variables mentioned above with the reaction rates. This equation reproduces the experimental results with deviations less than 10%. (Author) 21 refs.

  5. POLY(AMINOMETHYLENEPHOSPHONIC ACID FOR SOLVENT EXTRACTION OF METAL IONS

    Directory of Open Access Journals (Sweden)

    M’hamed Kaid

    2011-09-01

    Full Text Available Diaminododecyltetramethylenetetraphosphonic acid (DADTMTPA has been investigated in liquid - liquid extraction of Zn (II and Cu (II in acetate media. The extraction of both cations was carried out in different media with the addition of CH3COONa, CH3COOH, HCl and H2SO4 at different pH values. The maximum extraction yield for copper is 70% after addition of 10 mg of sodium acetate and for zinc is 30% after addition of acetic acid at pHi = 5.5, in one step.

  6. Innovative method of direct determination of the content of paraffins, naphthenes, aromatics and sulfur compounds by capillary high-resolution gas chromatography

    Directory of Open Access Journals (Sweden)

    R. Baizhumanova

    2012-03-01

    Full Text Available Based on determination of individual Hydrocarbon (paraffins, naphthenes, aromatics and Sulphur components of fuels and their mixture on the thin bonded of absorber (the stationary phase is a 100-metre silica capillary column, containing 0.5μm film thickness of bonded dimethylpolysiloxane phase by means of the selective solvents (mobile phase combined with technique of ionization of separated compounds by Flame Ionization Detector (FID and Sulphur Chemiluminescence Detector (SCD.

  7. 环烷酸氨皂 W/O微乳液的溶水性与内聚能理论%Solubization of Microemulsion of Naphthenic Acid Saponified by NH3· H2O and Theory of Cohesive Energies

    Institute of Scientific and Technical Information of China (English)

    王桂清; 陈巧云; 李荣喜; 罗奇志

    2001-01-01

    The solubization of the W/O microemulsion of NA(naphthenic acid)/kerosene/NH3· H2O system has been investigated.The effect of salt,cosurfactant (-alcohol) on solubization of the microemulsion has been studied by the theory of cohesive energies(theory of R-ratio).The results show that theory of R-ratio may explain the effect of concentration of salt,such as LiCl,NaCl,KCl,NaNO3,Na2SO4,NH4Cl,on maximum solubization (Φ m) of the microemulsion,but can not explain the differences of the effect of these salt on Φ m(to see Fig.1).We have found that,the rateQ(Q=z/r) of salt was correlated with the effect of salt on Φ m(to see Tab.1).Theory of R-ratio can only explain the effect of fraction mass of part alconols,such as n-octyl and n-heptyl and n-hexyl alcohol on Φ m,but can not explain the effect of isobutyl alcohol,n-butyl alcohol,n-pentanol and isoamyl alconol on Φ m (to see Fig.2).So theory of R-ratio has it's limitations in explaination of the phenomenons of solubization of W/O microemulsion.

  8. SOLVENT EFFECT ON EXTRACTION OF GALLIC ACID FROM AMALAKI CHURNA (EMBLICA OFFICINALIS Gaertn. TO REDUCE MATRIX EFFECT USING HPTLC AND UV-SPECTROSCOPY WITH 12 DIFFERENT NATURE SOLVENTS

    Directory of Open Access Journals (Sweden)

    Sukla V.J.

    2012-06-01

    Full Text Available Standardization of Ayurvedic formulations is an important aspect for research in Indian medicine. In this era every Pharma company prefer to use pure extract of component for production of best product in short period of time. The literature survey reveals that no work has been reported for solvent selection of extraction of Ayurvedic drugs. Amalaki is one of the most useable ayurveda drug. So, the present study was selected with an aim to select solvent for extraction of component of interest. Standard for evaluating quality of Amalaki churna by employing various physico-chemical parameters. For solvent selection 12 different nature solvents are selected for extraction. Polar solvent selected are Water, Di methylsulfoxide (DMSO, Ethylene glycol, Acetonitrile, Di methyl formeamide (DMF and Methanol. Non polar solvents are Acetone, Acetic acid, Ethyl acetate, Chloroform, Di ethylether and Toluene. Extraction was done by maceration method. Results are taken by chromatographic and spectrophotometric methods. In observation component was easily extracted with less interfering component in non polar solvent. Gallic acid is component of interest for Amalaki and it is well extracted in Di ethyl ether as per result of chromatography and spectroscopy. Conclusion is that selection of solvent for extraction as per their component of interest from material.

  9. Oxalic acid catalyzed solvent-free one pot synthesis of coumarins

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Oxalic acid was found to be an efficient catalyst for Pechmann condensation, which includes the reaction between phenols and β-keto esters leading to formation of coumarin derivatives. The advantages of present methods are the use of cheap and easy available catalyst, solvent-free reaction conditions, better yields and shorter reaction time.

  10. Aggregation behavior of cholic acid derivatives in organic solvents and in water

    NARCIS (Netherlands)

    Willemen, H.M.

    2002-01-01

    In this thesis various cholic acid derivatives are reported that display aggregation in water or in organic solvents. Spontaneous aggregation of single molecules into larger, ordered structures occurs at the borderline of solubility. Amphiphilic compounds, or surfactants, which possess a hydrophobic

  11. The expanded Hansen approach to solubility parameters. Paracetamol and citric acid in individual solvents.

    Science.gov (United States)

    Barra, J; Lescure, F; Doelker, E; Bustamante, P

    1997-07-01

    In this study two solubility-parameter models have been compared using as dependent variables the logarithm of the mole fraction solubility, lnX2e, and ln(alpha)/U (originally used in the extended Hansen method), where alpha is the activity coefficient and U is a function of the molar volume of the solute and the volume fraction of the solvent. The results show for the first time the proton-donor and -acceptor hydrogen-bonding capacities of paracetamol, as measured by the acidic and basic partial-solubility parameters. The influence of solvents on the differential scanning calorimetry (DSC) pattern of the solid phases was also studied in relation to the solubility models tested. Citric acid was chosen as a test substance because of its high acidity and its proton donor capacity to form hydrogen bonds with basic solvents. The partial acidic and basic solubility parameters obtained from multiple regression were consistent with this property, validating the model chosen. The results show that the more direct lnX2e variable was more suitable for fitting both models, and the four-parameter model seemed better for describing the interactions between solvent and solute.

  12. Poly(L-aspartic acid) derivative soluble in a volatile organic solvent for biomedical application.

    Science.gov (United States)

    Oh, Nam Muk; Oh, Kyung Taek; Youn, Yu Seok; Lee, Eun Seong

    2012-09-01

    In order to develop a novel functional poly(L-amino acid) that can dissolve in volatile organic solvents, we prepared poly[L-aspartic acid-g-(3-diethylaminopropyl)]-b-poly(ethylene glycol) [poly(L-Asp-g-DEAP)-b-PEG] via the conjugation of 3-diethylaminopropyl (DEAP) to carboxylate groups of poly(L-Asp) (M(n) 4 K)-b-PEG (M(n) 2 K). This poly(L-aspartic acid) derivative evidenced a relatively high solubility in volatile organic solvents such as dichloromethane, chloroform, and acetone. We fabricated a model nanostructure (i.e., polymeric micelle) using poly(L-Asp-g-DEAP)-b-PEG by the film rehydration method, which involves the simple removal of the volatile organic solvent (dichloromethane) used to dissolve polymer, reducing concerns about organic solvents remaining in a nano-sized particle. Interestingly, this micelle showed the pH-stimulated release of encapsulated model drug [i.e., doxorubicin (DOX)] due to the protonation of DEAP according to the pH of the solution. We expect that this poly(L-aspartic acid) derivative promises to provide pharmaceutical potential for constituting a new stimuli-sensitive drug carrier for various drug molecules.

  13. Synthesis of new hyodeoxycholic acid thiosemicarbazone derivatives under solvent-free conditions using microwave

    Institute of Scientific and Technical Information of China (English)

    Zhi Chuan Shi; Zhi Gang Zhao; Xing Li Liu; Yu Chen

    2011-01-01

    An efficient and simple method for synthesis of new hyodeoxycholic acid thiosemicarbazone derivatives under solvent-free conditions using microwave has been developed. Its main advantages are short reaction times, good conversions and the environmentally friendly nature of the process. The preliminary results indicate that some of these compounds possess inhibitory effects against E. coli.

  14. A convenient synthesis of pyrroles catalyzed by acidic resin under solvent-free condition

    Institute of Scientific and Technical Information of China (English)

    Shi

    2010-01-01

    A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition. Macroporous strongly acidic styrol resin (D001) as a novel, efficient, cost-effective, and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions. The pyrroles were obtained in high yields in short reaction times.

  15. Environment and solute-solvent interaction effects on photo-physical behaviors of Folic acid and Folinic acid drugs

    Science.gov (United States)

    Khadem Sadigh, M.; Zakerhamidi, M. S.; Seyed Ahmadian, S. M.; Johari-Ahar, M.; Zare Haghighi, L.

    2016-12-01

    In this paper, spectral properties of Folic acid and Folinic acid as widely used drugs in the treatment of some diseases have been studied in various environments with different polarity. Our results show that the absorption, emission and stokes shifts of solute molecules depend strongly on molecular surrounding characteristics, solute-solvent interactions and, different active groups in their chemical structures. In order to investigate the contribution of specific and nonspecific interactions on various properties of drug samples, the linear solvation energy relationships concept is used. Moreover, the calculated dipole moments by means of solvatochromic method show that the high values of dipole moments in excited state are due to local intramolecular charge transfer. Furthermore, the obtained results about molecular interactions can be extended to biological systems and can indicate completely the behaviors of Folic acid and Folinic acid in polar solvents such as water in body system.

  16. A solvent extraction approach to recover acetic acid from mixed waste acids produced during semiconductor wafer process.

    Science.gov (United States)

    Shin, Chang-Hoon; Kim, Ju-Yup; Kim, Jun-Young; Kim, Hyun-Sang; Lee, Hyang-Sook; Mohapatra, Debasish; Ahn, Jae-Woo; Ahn, Jong-Gwan; Bae, Wookeun

    2009-03-15

    Recovery of acetic acid (HAc) from the waste etching solution discharged from silicon wafer manufacturing process has been attempted by using solvent extraction process. For this purpose 2-ethylhexyl alcohol (EHA) was used as organic solvent. In the pre-treatment stage >99% silicon and hydrofluoric acid was removed from the solution by precipitation. The synthesized product, Na(2)SiF(6) having 98.2% purity was considered of commercial grade having good market value. The waste solution containing 279 g/L acetic acid, 513 g/L nitric acid, 0.9 g/L hydrofluoric acid and 0.030 g/L silicon was used for solvent extraction study. From the batch test results equilibrium conditions for HAc recovery were optimized and found to be 4 stages of extraction at an organic:aqueous (O:A) ratio of 3, 4 stages of scrubbing and 4 stages of stripping at an O:A ratio of 1. Deionized water (DW) was used as stripping agent to elute HAc from organic phase. In the whole batch process 96.3% acetic acid recovery was achieved. Continuous operations were successfully conducted for 100 h using a mixer-settler to examine the feasibility of the extraction system for its possible commercial application. Finally, a complete process flowsheet with material balance for the separation and recovery of HAc has been proposed.

  17. Solid-Liquid Equilibria of Succinic Acid in Cyclohexanone, Cyclohexanol and Their Mixed Solvents

    Institute of Scientific and Technical Information of China (English)

    FAN Lihua; MA Peisheng; SONG Weiwei

    2007-01-01

    Solubilities were measured for succinic acid dissolved in cyclohexanone, cyclohexanol and 5 of their mixed solvents at the temperature range from 291.85 K to 358.37 K using a dynamic method. The solubility data were regressed by λh equation, withthe average absolute relative deviation 3.47%. The binary interaction parameter is 0.306 7 for the mixed solvent of cyclohexanone and cyclohexanol was determined by correlating the experimental solubilities with the modified λh equation. When the binary interaction parameter was determined, it can be used to extrapolate the solubilities of succinic acid in mixed solvents of cyclohexanone and cyclohexanol at any proportion. The average absolute relative deviation was 7.69% by using the modified λh equation to correlate the solubility data, however, the average absolute relative deviation was 8.89% by using NRTL equation to correlate the solubility data. The results show that the accuracy of the modified λh equation is better than that of the NRTL equation for the solubility of succinic acid in the 5 mixed solvents of cyclohexanone and cyclohexanol.

  18. Esterification of Carboxylic Acids and Diacids by Trialkyl Borate under Solvent- and Catalyst-Free Conditions

    Institute of Scientific and Technical Information of China (English)

    MANSOORI Yagoub; TATAROGLU SEYIDOV Firdovsi; BOHLOOLI Shahrbanoo; ZAMANLOO Mohammad Reza; IMANZADEH Gholam Hassan

    2007-01-01

    Esterification or transesterification reactions are usually carried out in the presence of homogeneous or heterogeneous catalysts.However,recently a new method was reported for the esterification of carboxylic acids by tributyl borate under solvent- and catalyst-free conditions.In order to show the synthetic ability of trialkyl borate esters in the esterification reactions,here,the esterification of other carboxylic acids and diacids by tributyl-,triisoamyl-,and tribenzyl borate under the same conditions were reported.Some of the prepared ester and diester products have found wide applications as plasticizers and synthetic ester base lubricants.The esterification reactions have been cleanly carried out in the absence of any solvent under catalyst-free conditions.The maximum rate belongs to isoamyl trichloroacetate (Ⅵb) which reached about 76% within about 6.5 h.On the basis of obtained findings,it seems that electron withdrawing groups on carboxylic acid facilitate the esterification reaction.

  19. Acidity constants and its dependence on solvent selection from first-principles calculations using cluster-continuum models

    Science.gov (United States)

    Pham, Hieu H.; Taylor, Christopher D.; Henson, Neil J.

    2014-08-01

    Dissociation constants of selected carboxylic acids in aqueous and organic solvents were calculated at quantum chemical level. We considered cases in which trace quantities of water may be present, as well as cases in which water was entirely absent. In the latter cases, alternative proton acceptors need to be considered. For aqueous solvent, short-range solvation effects are considered by adding explicit water molecules as the first solvent shell. In the absence of water, corresponding organic solvents are used directly as the proton acceptors and the resulted pKa are quite comparable to those obtained from previous case of aqueous solvent.

  20. The effects of solvents and structure on the electronic absorption spectra of the isomeric pyridine carboxylic acid N-oxides

    Directory of Open Access Journals (Sweden)

    Drmanić Saša Ž.

    2013-01-01

    Full Text Available The ultraviolet absorption spectra of the carboxyl group of three isomeric pyridine carboxylic acids N-oxides (picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide were determined in fourteen solvents in the wavelength range from 200 to 400 nm. The position of the absorption maxima (λmax of the examined acids showed that the ultraviolet absorption maximum wavelengths of picolinic acid N-oxide are the shortest, and those of isonicotinic acid N-oxide acid are the longest. In order to analyze the solvent effect on the obtained absorption spectra, the ultraviolet absorption frequencies of the electronic transitions in the carboxylic group of the examined acids were correlated using a total solvatochromic equation of the form max = v0 + sπ + aα+ bβ, where υmax is the absorption frequency (1/λmax, p is a measure of the solvent polarity, β represents the scale of solvent hydrogen bond acceptor basicities and α represent the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The solvent effects on the ultraviolet absorption maximums of the examined acids were discussed.

  1. Solvent extraction in the treatment of acidic high-level liquid waste : where do we stand?

    Energy Technology Data Exchange (ETDEWEB)

    Horwitz, E. P.; Schulz, W. W.

    1998-06-18

    During the last 15 years, a number of solvent extraction/recovery processes have been developed for the removal of the transuranic elements, {sup 90}Sr and {sup 137}Cs from acidic high-level liquid waste. These processes are based on the use of a variety of both acidic and neutral extractants. This chapter will present an overview and analysis of the various extractants and flowsheets developed to treat acidic high-level liquid waste streams. The advantages and disadvantages of each extractant along with comparisons of the individual systems are discussed.

  2. Local solvent acidities in β-cyclodextrin complexes with PRODAN derivatives.

    Science.gov (United States)

    Naughton, Hannah R; Abelt, Christopher J

    2013-03-28

    The local solvent acidities (SA scale) of six 6-carbonyl-2-aminonaphthalene derivatives as β-cyclodextrin complexes in water are determined through fluorescence quenching. The local polarities (E(T)(N) scale) are determined through the shift of the emission center-of-mass. The apparent SA values reflect the solvent structure surrounding the guest’s carbonyl group, whereas the apparent E(T)(N) values reveal the net polarity of the entire guest molecule. Comparison of these values affords greater insight into the structures of the host–guest complexes. Derivatives 1 and 5 show unusually large acidities, indicative of highly exposed carbonyl groups. The remaining compounds give emission intensities pointing to shielded carbonyl groups. In this study, PRODAN and its derivatives are functioning as dual channel sensors of their local environment.

  3. Choice of solvent extraction technique affects fatty acid composition of pistachio (Pistacia vera L.) oil.

    Science.gov (United States)

    Abdolshahi, Anna; Majd, Mojtaba Heydari; Rad, Javad Sharifi; Taheri, Mehrdad; Shabani, Aliakbar; Teixeira da Silva, Jaime A

    2015-04-01

    Pistachio (Pistacia vera L.) oil has important nutritional and therapeutic properties because of its high concentration of essential fatty acids. The extraction method used to obtain natural compounds from raw material is critical for product quality, in particular to protect nutritional value. This study compared the fatty acid composition of pistachio oil extracted by two conventional procedures, Soxhlet extraction and maceration, analyzed by a gas chromatography-flame ionization detector (GC-FID). Four solvents with different polarities were tested: n-hexane (Hx), dichloromethane (DCM), ethyl acetate (EtAc) and ethanol (EtOH). The highest unsaturated fatty acid content (88.493 %) was obtained by Soxhlet extraction with EtAc. The Soxhlet method extracted the most oleic and linolenic acids (51.99 % and 0.385 %, respectively) although a higher concentration (36.32 %) of linoleic acid was extracted by maceration.

  4. Amino acid salt solutions as solvents in CO2 capture from flue gas

    DEFF Research Database (Denmark)

    Lerche, Benedicte Mai; Thomsen, Kaj; Stenby, Erling Halfdan

    solutions is their ability to form solid precipitates upon the absorption of CO2. The occurrence of crystallization offers the possibility of increasing the CO2 loading capacity of the solvent. However, precipitation can also have negative effect on the CO2 capture process. The chemical nature of the solid...... loading capacity of aqueous solutions of the potassium salts of selected amino-acids (glycine, taurine, lysine proline, and glutamic acid) were examined, and the relation between the initial amino acid salt concentration and precipitation ability of each solution were determined. Experiments were...... of glycine, taurine, and lysine, while in the case of proline, and glutamic acid, the precipitate was found to be bicarbonate. These results give an important contribution to further understanding the potential of amino acid salt solutions in CO2 capture from flue gas....

  5. Thermal And Spectroscopic Analyses Of Next Generation Caustic Side Solvent Extraction Solvent Contacted With 3, 8, And 16 Molar Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Fondeur, F. F.; Fink, S. D.

    2011-12-07

    A new solvent system referred to as Next Generation Solvent or NGS, has been developed at Oak Ridge National Laboratory for the removal of cesium from alkaline solutions in the Caustic Side Solvent Extraction process. The NGS is proposed for deployment at MCU{sup a} and at the Salt Waste Processing Facility. This work investigated the chemical compatibility between NGS and 16 M, 8 M, and 3 M nitric acid from contact that may occur in handling of analytical samples from MCU or, for 3 M acid, which may occur during contactor cleaning operations at MCU. This work shows that reactions occurred between NGS components and the high molarity nitric acid. Reaction rates are much faster in 8 M and 16 M nitric acid than in 3 M nitric acid. In the case of 16 M and 8 M nitric acid, the nitric acid reacts with the extractant to produce initially organo-nitrate species. The reaction also releases soluble fluorinated alcohols such as tetrafluoropropanol. With longer contact time, the modifier reacts to produce a tarry substance with evolved gases (NO{sub x} and possibly CO). Calorimetric analysis of the reaction product mixtures revealed that the organo-nitrates reaction products are not explosive and will not deflagrate.

  6. Singlet oxygen-sensitized delayed emissions from hydrogen peroxide/gallic acid/potassium ferricyanide systems containing organic solvents

    Science.gov (United States)

    Ishii, Hiroshi; Tsukino, Kazuo; Sekine, Masahiko; Nakata, Munetaka

    2009-06-01

    Fourier-transform chemiluminescence spectra of H 2O 2/gallic acid/K 3[Fe(CN) 6] systems containing organic solvents were measured. Emission bands with peaks around 530 and 700 nm were observed in systems containing solvents with a carbonyl group such as N, N-dimethylformamide, and those with a hydroxyl group such as methanol, respectively. The relative band intensities depended strongly on the concentration of these organic solvents. The emission species are attributed to gallic acid-ferricyanide complexes excited by energy transfer from singlet oxygen dimol, ( 1O 2) 2. The effects of organic solvents are interpreted in terms of intermolecular interactions of gallic acid-ferricyanide complexes, water molecules and organic solvents.

  7. CHARACTERIZATION OF POLAR COMPONENTS IN HYTROTREATED NAPHTHENIC RUBBER PROCESS OIL

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Polar components play a very important role toward light stability of hydrotreated naphthenic rubber process oil. Polar components in hydrotreated naphthenic rubber process oil are analyzed in detail. Polar components are firstly isolated from rubber process oil by column chromatography of silica gel, and then characterized by a series of instrument technology including elemental analysis, infrared spectroscopy, APCI/MS and XPS. The results show that the polar components comprise some hetero atoms compounds of sulfur, nitrogen and oxygen. Oxygen- containing compounds such as hydroxyl, carbonyl, and carboxyl groups constitute the main body of polar components. Nitrogen - containing compounds (NH2, NH, or NO2 and - N = N - ) and sulfur - containing compounds (SO42- and PHSSPH) only account for minor percent of polar components. The molecular weight distribution of polar components mainly concentrates between 300 and 500 and a minor portion distributes from 180 to 300.

  8. Optimization of conjugated linoleic acid triglycerides via enzymatic esterification in no-solvent system

    Institute of Scientific and Technical Information of China (English)

    YI Dan; SUN Xiuqin; LI Guangyou; LIU Fayi; LIN Xuezheng; SHEN Jihong

    2009-01-01

    We compared four esterifiable enzymes. The lipase Novozym 435 possessed the highest activity for the conjugated linoleic acid esterification during the synthesis of triglycerides. The triglycerides were synthesized by esterification of glycerol and conjugated linoleic acid (CLA) in a no-solvent system using lipase catalysis. We investigated the effects of temperature, enzyme concentration, water content, and time on esterification. Enzyme and water concentrations of up to 1% of the total reaction volume and a system temperature of 60°C proved optimal for esterification. Similarly, when the esterification was carried out for 24 h, the reaction ratio improved to 94.11%. The esterification rate of the rotating screen basket remained high (87.28%) when the enzyme was re-used for the 5th time. We evaluated the substrate selectivity of lipase (NOVO 435) and determined that this lipase prefers the 10,12-octadacadienoic acid to the 9,11-octadecadienoic acid.

  9. Easy Access to Coumarin Derivatives Using Alumina Sulfuric Acid as an Efficient and Reusable Catalyst under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Ali Amoozadeh

    2013-01-01

    Full Text Available A new and efficient condition for the use of alumina sulfuric acid (ASA as a heterogeneous catalyst in the Pechmann condensation reaction in solvent-free condition for the formation of coumarins has been reported.

  10. Effect of solvent on absorption and fluorescence spectra of a typical fluorinated azo dye for its acidic and basic structures

    Science.gov (United States)

    Abdel-Halim, Shakir T.

    2011-11-01

    The effect of 15 polar solvents on absorption and fluorescence energies of a typical fluorinated azo dye, 4-(2,3,5,6-tetrafluoro-pyridin-4-yl azo)-phenol, was reported for its acidic, MH, and basic, M, structures. For MH, the absorption energy is described on the basis of multi-linear equation with Taft's π* (solvent polarity) and β (hydrogen bond acceptor) parameters while the fluorescence energy varies rectilinearly with free energy of transferring the proton to the surrounding solvent, Δ Gt°. For M, the hydrogen bonding donor ability of protic solvent, α, is a predominant factor which affects the absorption energy while in aprotic solvents, the absorption energy correlates linearly with Kirkwood function. As the ability of the solvent for hydrogen bonding increases, the absorption band width will increase in parallel with the transition energy.

  11. Application of acid-catalyzed hydrolysis of dispersed organic solvent in developing new microencapsulation process technology.

    Science.gov (United States)

    Lee, Honghwa; Lee, Sunhwa; Bhattacharjee, Himanshu; Sah, Hongkee

    2012-01-01

    The aim of this study was to evaluate a new microencapsulation technology employing an acid-catalyzed solvent extraction method in conjunction to an emulsion-based microencapsulation process. Its process consisted of emulsifying a dispersed phase of poly(D,L-lactide-co-glycolide) and isopropyl formate in an aqueous phase. This step was followed by adding hydrochloric acid to the resulting oil-in-water emulsion, in order to initiate the hydrolysis of isopropyl formate dissolved in the aqueous phase. Its hydrolysis caused the liberation of water-soluble species, that is, isopropanol and formic acid. This event triggered continual solvent leaching out of emulsion droplets, thereby initiating microsphere solidification. This new processing worked well for encapsulation of progesterone and ketoprofen that were chosen as a nonionizable model drug and a weakly acidic one, respectively. Furthermore, the structural integrity of poly(D,L-lactide-co-glycolide) was retained during microencapsulation. The new microencapsulation technology, being conceptually different from previous approaches, might be useful in preparing various polymeric particles.

  12. Electron Donor-Acceptor Interaction of 8-Hydroxyquinoline with Citric Acid in Different Solvents: Spectroscopic Studies

    Directory of Open Access Journals (Sweden)

    Demelash Jado

    2014-01-01

    Full Text Available Charge transfer complex formation between 8-hydroxyquinoline as the electron donor and citric acid as the electron acceptor has been studied spectrophotometrically in ethanol and methanol solvents at room temperature. Absorption band due to charge transfer complex formation was observed near 320 and 325 nm in ethanol and methanol, respectively. The stoichiometric ratio of the complex has been found 3 : 1 by using Job’s and conductometric titration methods. Benesi-Hildebrand equation has been applied to estimate the formation constant and molecular extinction coefficient. It was found that the value of formation constant was larger in ethanol than in methanol. The physical parameters, ionization potential, and standard free energy change of the formed complex were determined and evaluated in the ethanol and methanol solvents.

  13. Solvent extraction of organic acids from stillage for its re-use in ethanol production process.

    Science.gov (United States)

    Castro, G A; Caicedo, L A; Alméciga-Díaz, C J; Sanchez, O F

    2010-06-01

    Stillage re-use in the fermentation stage in ethanol production is a technique used for the reduction of water and fermentation nutrients consumption. However, the inhibitory effect on yeast growth of the by-products and feed components that remains in stillage increases with re-use and reduces the number of possible recycles. Several methods such as ultrafiltration, electrodialysis and advanced oxidation processes have been used in stillage treatment prior its re-use in the fermentation stage. Nevertheless, few studies evaluating the effect of solvent extraction as a stillage treatment option have been performed. In this work, the inhibitory effect of serial stillage recycling over ethanol and biomass production was determined, using acetic acid as a monitoring compound during the fermentation and solvent extraction process. Raw palm oil methyl ester showed the highest acetic acid extraction from the aqueous phase, presenting a distribution coefficient of 3.10 for a 1:1 aqueous phase mixture:solvent ratio. Re-using stillage without treatment allowed up to three recycles with an ethanol production of 53.7 +/- 2.0 g L(-1), which was reduced 25% in the fifth recycle. Alternatively, treated stillage allowed up to five recycles with an ethanol final concentration of 54.7 +/- 1.3 g L(- 1). These results show that reduction of acetic acid concentration by an extraction process with raw palm oil methyl ester before re-using stillage improves the number of recycles without a major effect on ethanol production. The proposed process generates a palm oil methyl ester that contains organic acids, among other by-products, that could be used for product recovery and as an alternative fuel.

  14. (Co-)solvent selection for single-wall carbon nanotubes: best solvents, acids, superacids and guest-host inclusion complexes.

    Science.gov (United States)

    Torrens, Francisco; Castellano, Gloria

    2011-06-01

    Analysis of 1-octanol-water, cyclohexane-water and chloroform (CHCl(3))-water partition coefficients P(o-ch-cf) allows calculation of molecular lipophilicity patterns, which show that for a given atom log P(o-ch-cf) is sensitive to the presence of functional groups. Program CDHI does not properly differentiate between non-equivalent atoms. The most abundant single-wall carbon nanotube (SWNT), (10,10), presents a relatively small aqueous solubility and large elementary polarizability, P(o-ch-cf) and kinetic stability. The SWNT solubility is studied in various solvents, finding a class of non-hydrogen-bonding Lewis bases with good solubility. Solvents group into three classes. The SWNTs in some organic solvents are cationic while in water/Triton X mixture are anionic. Categorized solubility is semiquantitatively correlated with solvent parameters. The coefficient of term β is positive while the ones of ε and V negative. The electron affinity of d-glucopyranoses (d-Glcp(n)) suggests the formation of colloids of anionic SWNTs in water. Dipole moment for d-Glcp(n)-linear increases with n until four in agreement with 18-fold helix. The I(n)(z-) and SWNT(-) are proposed to form inclusion complexes with cyclodextrin (CD) and amylose (Amy). Starch, d-Glcp, CD and Amy are proposed as SWNT co-solvents. Guests-hosts are unperturbed. A central channel expansion is suggested.

  15. (Liquid + liquid) equilibria in ternary aqueous mixtures of phosphoric acid with organic solvents at T = 298.2 K

    Energy Technology Data Exchange (ETDEWEB)

    Ghanadzadeh, H., E-mail: hggilani@guilan.ac.i [Department of Chemistry, Faculty of Science, University of Guilan, Rasht (Iran, Islamic Republic of); Department of Chemical Engineering, University of Guilan, Rasht (Iran, Islamic Republic of); Ghanadzadeh, A., E-mail: aggilani@guilan.ac.i [Department of Chemistry, Faculty of Science, University of Guilan, Rasht (Iran, Islamic Republic of); Aghajani, Z.; Abbasnejad, S.; Shekarsaraee, S. [Department of Chemistry, Faculty of Science, University of Guilan, Rasht (Iran, Islamic Republic of)

    2010-06-15

    (Liquid + liquid) equilibrium (LLE) data for the ternary mixtures of left bracewater (1) + phosphoric acid (2) + organic solvents (3)right brace were determined at T = 298.2 K and atmospheric pressure. The organic solvents were cyclohexane, 2-methyl-2-butanol (tert-amyl alcohol), and isobutyl acetate. All the investigated systems exhibit Type-1 behaviour of LLE. The immiscibility region was found to be larger for the (water + phosphoric acid + cyclohexane) ternary system. The experimental LLE results were correlated with the NRTL model, and the binary interaction parameters were obtained. The reliability of the experimental tie-line results was tested through the Othmer-Tobias and Bachman correlation equations. Distribution coefficients and separation factors were evaluated over the immiscibility regions and a comparison of the extracting capabilities of the solvents was made with respect to these factors. The experimental results indicate the superiority of cyclohexane as the preferred solvent for the extraction of phosphoric acid from its aqueous solutions.

  16. Diffusion Coefficient of Tin(II) Methanesulfonate in Ionic Liquid and Methane Sulfonic Acid (MSA) Solvent

    Science.gov (United States)

    Yang, Kok Kee; Mahmoudian, M. R.; Ebadi, Mehdi; Koay, Hun Lee; Basirun, Wan Jeffrey

    2011-12-01

    Voltammetry and chronoamperometry for the electrodeposition of tin from Tin(II) methane sulfonate mixed with ionic liquid and methane sulfonate acid at room temperature was studied. Cyclic voltammetry shows redox waves of Tin(II), which proves that the electrodeposition of tin from Tin(II) methane sulfonate is a diffusion-controlled process. The diffusion coefficient of Tin(II) ions in the solvent mixture showed good agreement from both voltammetry and chronoamperometry results. The diffusion coefficient of Tin(II) in the mixture was much smaller than in aqueous solution, and it depends on the anion of the ionic liquid.

  17. Solvent free one pot synthesis of amidoalkyl naphthols over phosphotungstic acid

    Directory of Open Access Journals (Sweden)

    Divya P. Narayanan

    2017-07-01

    Full Text Available Montmorillonite KSF clay was effectively modified by the encapsulation of phosphotungstic acid into the clay layers via sonication followed by incipient wet impregnation method. The prepared catalysts were characterized by X-ray diffraction (XRD, Fourier-transform infrared spectroscopy (FTIR and scanning electron microscopy (SEM techniques. The catalytic activities of the prepared systems were investigated in the solvent free synthesis of amidoalkyl naphthols by the multicomponent one-pot condensation of an aldehyde, β-naphthol and an amide or urea. Excellent yield, shorter reaction time, easy work-up, and reusability of the catalyst are the main attractions of this green procedure.

  18. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Directory of Open Access Journals (Sweden)

    Marcia E. Richard

    2013-10-01

    Full Text Available A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

  19. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Science.gov (United States)

    Richard, Marcia E; Fraccica, Daniel V; Garcia, Kevin J; Miller, Erica J; Ciccarelli, Rosa M; Holahan, Erin C; Resh, Victoria L; Shah, Aakash; Findeis, Peter M

    2013-01-01

    Summary A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers. PMID:24204410

  20. Enzymatic hybridization of α-lipoic acid with bioactive compounds in ionic solvents.

    Science.gov (United States)

    Papadopoulou, Athena A; Katsoura, Maria H; Chatzikonstantinou, Alexandra; Kyriakou, Eleni; Polydera, Angeliki C; Tzakos, Andreas G; Stamatis, Haralambos

    2013-05-01

    The lipase-catalyzed molecular hybridization of α-lipoic acid (LA) with bioactive compounds pyridoxine, tyrosol and tyramine was performed in ionic solvents and deep eutectic solvents. The biocatalytic reactions were catalyzed by Candida antarctica lipase B immobilized onto various functionalized multi-walled carbon nanotubes (f-CNTs-CaLB), as well as by commercial Novozym 435. The use of f-CNTs-CaLB leads, in most cases, to higher conversion yields as compared to Novozym 435. The nature and ion composition of ionic solvents affect the performance of the biocatalytic process. The highest conversion yield was observed in (mtoa)NTf2. The high enzyme stability and the relatively low solubility of substrates in specific media account for the improved biocatalytic synthesis of molecular hybrids of LA. Principal component analysis was used to screen for potential lipoxygenase inhibitors. In vitro studies showed that the synthesized compounds exhibit up to 10-fold increased inhibitory activity on lipoxygenase mediated lipid peroxidation as compared to parent molecules.

  1. Preparation and Characterization of High Purity Enriched10B Boric Acid via Anti-Solvent Recrystallization

    Institute of Scientific and Technical Information of China (English)

    张卫江; 刘天雨; 徐姣

    2016-01-01

    Self-made enriched10B boric acid as raw material was purified by recrystallization. The effects of final crystallization temperature, crystallization time, stirring speed, crystallization frequency and other factors on the purity were investigated. The appropriate operating condition was that the final crystallization temperature and time were 5,℃and 10 h respectively under a low-speed stirring for crystallizing twice, which would make the purity and yield of boric acid reach 99.94% and 95.36%, respectively. Taking this as foundation, recrystallization process was optimized with acetone as anti-solvent, whose amount was the most important index. The boric acid solution was added into acetone and recrystallized under the same condition, and the purity and yield of boric acid would reach 99.98% and 99.61%, respectively. The product detected by XRD was confirmed as boric acid crystal. Main ion concentration in the product was detected by ICP, which basically met the national standard of high purity. Crystal morphology of boric acid was observed by SEM.

  2. Aqueous or solvent based surface modification: The influence of the combination solvent - organic functional group on the surface characteristics of titanium dioxide grafted with organophosphonic acids

    Science.gov (United States)

    Roevens, Annelore; Van Dijck, Jeroen G.; Geldof, Davy; Blockhuys, Frank; Prelot, Benedicte; Zajac, Jerzy; Meynen, Vera

    2017-09-01

    To alter the versatility of interactions at its surface, TiO2 is modified with organophosphonic acids (PA). A thorough understanding of the role of all synthesis conditions is necessary to achieve controlled functionalization. This study reports on the effect of using water, toluene and their mixtures when performing the modification of TiO2 with PA. Sorption and calorimetry measurements of surface interactions with various probing species clearly indicate that, by grafting PA in water, clear differences appear in the distribution of organic groups on the surface. Also the functional group of the PA determines the impact of using water as solvent. Modification in toluene results in a higher modification degree for propylphosphonic acid (3PA), as the solvent-solute interaction may hinder the grafting with phenylphosphonic acid (PhPA) in toluene. Water is preferred as solvent for PhPA modification as stabilizing π-OH interactions enhance surface grafting overcoming the competitive interaction of water at the surface as observed with 3PA. By using water in toluene mixtures for the functionalization of TiO2 with 3PA, the degree of functionalization is higher than when only water or toluene is used. Furthermore, adding small amounts of water leads to the formation of titanium propylphosphonates, next to surface grafting.

  3. Enzymatic Lipophilization of Phenolic Acids through Esterification with Fatty Alcohols in Organic Solvents

    DEFF Research Database (Denmark)

    Yang, Zhiyong; Guo, Zheng; Xu, Xuebing

    2012-01-01

    In this study, we investigated and optimized the synthesis of lipophilized esters between selected phenolic acids and fatty alcohols in a binary solvent system, which is composed of hexane and butanone. The effect of different proportion of hexane and butanone was firstly studied by changing...... the volume ratio from 85:15 to 45:55. It was found that the conversion strongly depended on the proportion of hexane and butanone in the reaction system. Following the effect of carbons of fatty alcohol chains on estererification performance with dihydrocaffeic acid (DHCA) was evaluated by choosing different...... fatty alcohols from C4 to C18. The conversion of DHCA was significantly affected by the carbons of fatty alcohol chains. Roughly 95% conversion was achieved within 3 days when DHCA was esterified with hexanol (C6), while only 56% and 44% conversion were achieved when esterified with 1-butanol...

  4. Solubility and solution thermodynamics of 2,5-thiophenedicarboxylic acid in (water + ethanol) binary solvent mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yang; Zhang, Qi; Cao, Cuicui; Cheng, Limin [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China); Shi, Ying [Taiyuan Qiaoyou Chemical Industrial Co. Ltd., Taiyuan 030025 (China); Yang, Wenge [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China); Hu, Yonghong, E-mail: yonghonghu11@126.com [State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009 (China)

    2014-09-20

    Highlights: • The solubility increased with increasing temperature. • The solubility decreased with the rise of the ratio of the water. • The solubility data were fitted using Apelblat equation, CNIBS/R–K and JA model. • The Gibbs energy, enthalpy and entropy were calculated by the van’t Hoff analysis. - Abstract: In this paper, we focused on solubility and solution thermodynamics of 2,5-thiophenedicarboxylic acid. By gravimetric method, the solubility of 2,5-thiophenedicarboxylic acid was measured in (water + ethanol) binary solvent mixtures from 278.15 K to 333.15 K under atmosphere pressure. The solubility data were fitted using modified Apelblat equation, a variant of the combined nearly ideal binary solvent/Redlich–Kister (CNIBS/R–K) model and Jouyban–Acree model. Computational results showed that the modified Apelblat equation has the lowest MD (mean deviation). In addition, the thermodynamic properties of the solution process, including the Gibbs energy, enthalpy, and entropy were calculated by the van’t Hoff analysis.

  5. System Development from Organic Solvents to Ionic Liquids for Synthesiz-ing Ascorbyl Esters with Conjugated Linoleic Acids

    DEFF Research Database (Denmark)

    Yang, Zhiyong; Schultz, Lise; Guo, Zheng;

    2012-01-01

    The aim of this paper is to screen suitable reaction systems for the modification of antioxidants through enzy-matic synthesis. Enzymatic esterification of ascorbic acid with conjugated linoleic acid (CLA) was investigated as a mod-el. Four organic solvents and five different enzymes were evaluated....... Results show that only Novozym® 435 turned out to be a useful enzymatic preparation for the production of ascorbyl-CLA ester. The optimum reaction conditions in the or-ganic solvent system were 4 h at 55°C and at a molar ratio of 5 (CLA/ascorbic acid). The esterification reaction was trans...

  6. Ionic liquids as novel solvents for the synthesis of sugar fatty acid ester.

    Science.gov (United States)

    Mai, Ngoc Lan; Ahn, Kihun; Bae, Sang Woo; Shin, Dong Woo; Morya, Vivek Kumar; Koo, Yoon-Mo

    2014-12-01

    Sugar fatty acid esters are bio-surfactants known for their non-toxic, non-ionic, and high biodegradability . With great emulsifying and conditioning effects, sugar fatty acids are widely used in the food, pharmaceutical, and cosmetic industries. Biosynthesis of sugar fatty acid esters has attracted growing attention in recent decades. In this study, the enzymatic synthesis of sugar fatty acid esters in ionic liquids was developed, optimized, and scaled up. Reaction parameters affecting the conversion yield of lipase-catalyzed synthesis of glucose laurate from glucose and vinyl laurate (i.e. temperature, vinyl laurate/glucose molar ratio, and enzyme loads) were optimized by response surface methodology (RSM). In addition, production was scaled up to 2.5 L, and recycling of enzyme and ionic liquids was investigated. The results showed that under optimal reaction conditions (66.86 °C, vinyl laurate/glucose molar ratio of 7.63, enzyme load of 73.33 g/L), an experimental conversion yield of 96.4% was obtained which is close to the optimal value predicted by RSM (97.16%). A similar conversion yield was maintained when the reaction was carried out at 2.5 L. Moreover, the enzymes and ionic liquids could be recycled and reused effectively for up to 10 cycles. The results indicate the feasibility of ionic liquids as novel solvents for the biosynthesis of sugar fatty acid esters.

  7. Alkenyl Carboxylic Acid: Engineering the Nanomorphology in Polymer-Polymer Solar Cells as Solvent Additive.

    Science.gov (United States)

    Zhang, Yannan; Yuan, Jianyu; Sun, Jianxia; Ding, Guanqun; Han, Lu; Ling, Xufeng; Ma, Wanli

    2017-04-19

    We have investigated a series of commercially available alkenyl carboxylic acids with different alkenyl chain lengths (trans-2-hexenoic acid (CA-6), trans-2-decenoic acid (CA-10), 9-tetradecenoic acid (CA-14)) for use as solvent additives in polymer-polymer non-fullerene solar cells. We systematically investigated their effect on the film absorption, morphology, carrier generation, transport, and recombination in all-polymer solar cells. We revealed that these additives have a significant impact on the aggregation of polymer acceptor, leading to improved phase segregation in the blend film. This in-depth understanding of the additives effect on the nanomorphology in all-polymer solar cell can help further boost the device performance. By using CA-10 with the optimal alkenyl chain length, we achieved fine phase separation, balanced charge transport, and suppressed recombination in all-polymer solar cells. As a result, an optimal power conversion efficiency (PCE) of 5.71% was demonstrated which is over 50% higher than that of the as-cast device (PCE = 3.71%) and slightly higher than that of devices with DIO treatment (PCE = 5.68%). Compared with widely used DIO, these halogen-free alkenyl carboxylic acids have a more sustainable processing as well as better performance, which may make them more promising candidates for use as processing additives in organic non-fullerene solar cells.

  8. Efficient Extraction of Astaxanthin from Phaffia rhodozyma with Polar and Non-polar Solvents after Acid Washing

    Institute of Scientific and Technical Information of China (English)

    YIN Chunhua; YANG Shuzhen; LIU Xiaolu; YAN Hai

    2013-01-01

    method of extracting astaxanthin from Phaffia rhodozyma with various solvents after acid washing was investigated.The extraction efficiency was distinctly increased after acid washing of P.rhodozyma cells.When the concentration of HCl was 0.4 mol·L-,the highest extraction efficiency of astaxanthin was achieved which was about three times higher than the control.Acetone or benzene as single polar or non-polar solvent was the most effective solvent in our research.With a combination of isopropanol and n-hexane (volume ratio of 2 ∶ 1),the maximal extraction efficiency was achieved,approximately 60% higher than that obtained with a single solvent.The liquid-solid ratio and the extracting time were also optimized.Under the optimum extraction conditions,the extraction yield of astaxanthin exceeded 98%.

  9. Biogeochemical anomaly above oil-containing structures in an arid zone. [Growth stimulation of plants by sodium naphthenate used for prospecting

    Energy Technology Data Exchange (ETDEWEB)

    Grishchenko, O.M.

    1983-01-01

    Visual biological anomalies above the oil-containing structures are characterized by bright green coloring of the vegetation cover, gigantism of the plants, extended vegetation period of the plants, deformity of the plants, etc. Biological anomalies are associated with geological features and are observed only above the zone of fault disorders of the earth's crust, above deep faults. A conclusion is drawn about the presence above the oil-bearing structures in the arid zone of a biogeochemical anomaly whose origin is explained by the biological activity of oil and its derivatives. The petroleum growth matter is the sodium salt of naphthene acid, a growth stimulator of plants and animals. The oils of the USSR contain 0.8-4.8% naphthene acids, which effuse through the faults into the root area levels of the soil. As a result of stimulation of growth and development by the petroleum growth matter, the vegetation period of the plants is prolonged. Under the influence of natural petroleum growth substances, the height and productivity of the anomalous plants increases 2-3-fold. Formation and manifestation of signs of biogeochemical anomalies above the oil-bearing structures in the arid zone predetermine the following conditions: presence of fault disorders of the earth's crust; salinity of the root area of the soil layer necessary for neutralization of the naphthene acids with subsequent formation of the biologically active naphthenates; aridity of the desert landscape; plain relief excluding color diversity in vegetation cover because of nonuniform wetting, etc. The established biogeochemical anomaly can be used in prospecting and exploration of oil, gas and bitumen, and also in determining the fault disorders of the earth's crust.

  10. Efficient production of fatty acid methyl ester from waste activated bleaching earth using diesel oil as organic solvent.

    Science.gov (United States)

    Kojima, Seiji; Du, Dongning; Sato, Masayasu; Park, Enoch Y

    2004-01-01

    Fatty acid methyl ester (FAME) production from waste activated bleaching earth (ABE) discarded by the crude oil refining industry was investigated using fossil fuel as a solvent in the esterification of triglycerides. Lipase from Candida cylindracea showed the highest stability in diesel oil. Using diesel oil as a solvent, 3 h was sufficient to obtain a yield of approximately 100% of FAME in the presence of 10% lipase from waste ABE. Kerosene was also a good solvent in the esterification of triglycerides embedded in the waste ABE. Fuel analysis showed that the FAME produced using diesel oil as a solvent complied with the Japanese diesel standard and the 10% residual carbon amount was lower than that of FAME produced using other solvents. Use of diesel oil as solvent in the FAME production from the waste ABE simplified the process, because there was no need to separate the organic solvent from the FAME-solvent mixture. These results demonstrate a promising reutilization method for the production of FAME, for use as a biodiesel, from industrial waste resources containing waste vegetable oils.

  11. Fabrication of Janus particles composed of poly (lactic-co-glycolic) acid and hard fat using a solvent evaporation method.

    Science.gov (United States)

    Matsumoto, Akihiro; Murao, Satoshi; Matsumoto, Michiko; Watanabe, Chie; Murakami, Masahiro

    2016-01-01

    The feasibility of fabricating Janus particles based on phase separation between a hard fat and a biocompatible polymer was investigated. The solvent evaporation method used involved preparing an oil-in-water (o/w) emulsion with a mixture of poly (lactic-co-glycolic) acid (PLGA), hard fat, and an organic solvent as the oil phase and a polyvinyl alcohol aqueous solution as the water phase. The Janus particles were formed when the solvent was evaporated to obtain certain concentrations of PLGA and hard fat in the oil phase, at which phase separation was estimated to occur based on the phase diagram analysis. The hard fat hemisphere was proven to be the oil phase using a lipophilic dye Oil Red O. When the solvent evaporation process was performed maintaining a specific volume during the emulsification process; Janus particles were formed within 1.5 h. However, the formed Janus particles were destroyed by stirring for over 6 h. In contrast, a few Janus particles were formed when enough water to dissolve the oil phase solvent was added to the emulsion immediately after the emulsification process. The optimized volume of the solvent evaporation medium dominantly formed Janus particles and maintained the conformation for over 6 h with stirring. These results indicate that the formation and stability of Janus particles depend on the rate of solvent evaporation. Therefore, optimization of the solvent evaporation rate is critical to obtaining stable PLGA and hard fat Janus particles.

  12. Online analytical investigations on solvent-, temperature- and water vapour-induced phase transformations of citric acid

    Energy Technology Data Exchange (ETDEWEB)

    Helmdach, L.; Ulrich, J. [Martin-Luther-Universitaet Halle-Wittenberg, Zentrum fuer Ingenieurwissenschaft, Verfahrenstechnik/TVT, Halle (Saale) (Germany); Feth, M.P. [Sanofi-Aventis Deutschland GmbH, Chemical and Process Development Frankfurt Chemistry, Frankfurt (Germany)

    2012-09-15

    It was demonstrated exemplarily for the crystallization of citric acid that the usage of an ultrasound device as well as Raman spectroscopy enables the inline measurement and the control of phase transitions. The influence of different solvent compositions (water and ethanol-water) on the crystallization of citric acid was investigated. By increasing the ethanol content the transformation point was shifted towards higher temperatures. In addition, a strong impact on the nucleation point as well as on the crystal habit was detected in ethanol-water mixtures. The results lead to the assumption that a citric acid solvate exists, which is, however, highly unstable upon isolation from mother liquor and converts fast into the known anhydrate or monohydrate forms of citric acid. The presence of such a solvate, however, could not be proven during this study. Furthermore, factors such as temperature and humidity which might influence the phase transition of the solid product were analyzed by Hotstage-Raman Spectroscopy and Water Vapor Sorption Gravimetry-Dispersive Raman Spectroscopy. Both, temperature as well as humidity show a strong influence on the behaviour of CAM. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Solvent Composition is Critical for Carbodiimide Cross-Linking of Hyaluronic Acid as an Ophthalmic Biomaterial

    Directory of Open Access Journals (Sweden)

    Jui-Yang Lai

    2012-10-01

    Full Text Available Hyaluronic acid (HA is one of the most important ophthalmic biomaterials, while also being used for tissue engineering and drug delivery. Although chemical cross-linking is an effective way to improve the material performance, it may as a consequence be detrimental to the living cells/tissues. Given that the cross-linking efficiency is mediated by the solvent composition during the chemical modification, this study aims to explore the stability and biocompatibility of carbodiimide cross-linked HA in relation to material processing conditions by varying the acetone/water volume ratio (from 70:30 to 95:5 at a constant 1-ethyl-3-(3-dimethyl aminopropyl carbodiimide (EDC concentration of 100 mM. Our results indicated that after the EDC treatment in the presence of an acetone/water mixture (85:15, v/v, the HA hydrogel membranes have the lowest equilibrium water content, the highest stress at break and the greatest resistance to hyaluronidase digestion. Live/Dead assays and pro-inflammatory cytokine expression analyses showed that the cross-linked HA hydrogel membranes, irrespective of the solvent composition, are compatible with human RPE cell lines without causing toxicity and inflammation. However, it should be noted that the test samples prepared by the cross-linking in the presence of acetone/water mixtures containing 70, 75, and 95 vol % of acetone slightly inhibit the metabolic activity of viable ARPE-19 cultures, probably due to the alteration in the ionic interaction between the medium nutrients and polysaccharide biomaterials. In summary, the water content, mechanical strength and RPE cell proliferative capacity strongly depends on the solvent composition for carbodiimide cross-linking of HA materials.

  14. Identification of Flavonoids (Quercetin, Gallic acid and Rutin from Catharanthus roseus Plant Parts using Deep Eutectic Solvent

    Directory of Open Access Journals (Sweden)

    Asma Nisar

    2017-02-01

    Full Text Available Green technology is the most important topic in the pharmaceutical field because it reduces the cost of medicines and minimizes the environmental impact of the field and is better for human health and safety. Green chemistry emphasizes that the solvent should be nontoxic, safe, cheap, green, readily available, recyclable, and biodegradable. Deep eutectic solvents, a new type of green solvent, have some renowned properties—for instance, high thermal stability, low vapor pressure, low cost, biodegradability, and high viscosity. In this study, deep eutectic solvents made up of choline chloride-glycerol (1:2 were used for the extraction and isolation of flavonoid (rutin, gallic acid, and quercetin from Catharanthus roseus plant parts, flower petal, leaves, stem, and root. The amounts of rutin and quercetin in flower petal are 29.46 and 6.51%, respectively, whereas, rutin, gallic acid, and quercetin amounts in leaves are 25.16, 8.57, and 10.47%, respectively. In stem the amounts of rutin, gallic acid, and quercetin are 13.02, 5.89, and 7.47%, respectively. In root, only quercetin has been obtained that is 13.49%. The HPLC is an analytical method, which was found to be an excellent technique for determination of rutin, gallic acid, and quercetin using deep eutectic solvent extraction from plant parts of Catharanthus roseus.

  15. [Determination of residual solvents in 7-amino-3-chloro cephalosporanic acid by gas chromatography].

    Science.gov (United States)

    Ma, Li; Yao, Tong-wei

    2011-01-01

    To develop a gas chromatography method for determination of residual solvents in 7-amino-3-chloro cephalosporanic acid (7-ACCA). The residual levels of acetone, methanol, dichloromethane, ethyl acetate, isobutanol, pyridine and toluene in 7-ACCA were measured by gas chromatography using Agilent INNOWAX capillary column (30 m × 0.32 mm,0.5 μm). The initial column temperature was 70° maintained for 6 min and then raised (10°C/min) to 160°C for 1 min. Nitrogen gas was used as carrier and FID as detector. The flow of carrier was 1.0 ml/min, the temperature of injection port and detector was 200°C and 250°C, respectively. The limits of detection for acetone, methanol, dichloromethane, ethyl acetate, isobutanol, pyridine, toluene in 7-ACCA were 2.5 μg/ml, 1.5 μg/ml, 15 μg/ml, 2.5 μg/ml, 2.5 μg/ml, 2.5 μg/ml and 11 μg/ml, respectively. Only acetone was detected in the sample, and was less than the limits of Ch.P. The method can effectively detect the residual solvents in 7-ACCA.

  16. Effect of solvent on the extraction of lanthanides with picrolonic acid

    Energy Technology Data Exchange (ETDEWEB)

    Ali, A.; Saeed, M.M. [Pakistan Institute of Nuclear Science and Technology (PINSTECH), Islamabad (Pakistan). Chemistry Div.; Rehman, H. [Pakistan Institute of Nuclear Science and Technology (PINSTECH), Islamabad (Pakistan). Central Analytical Facility Div.; Anwar, J. [Punjab Univ., Lahore (Pakistan). Inst. of Chemistry

    2010-07-01

    Extraction of Eu(III), Tb(III) and Lu(III), as representatives of lanthanides, has been studied with picrolonic acid [1-p-nitrophenyl-3-methyl-4-nitro-5-pyrazolone (HPA)] as extractant in various solvents such as acetylacetone (ACAC), 1-octanol (ONL), n-hexanol (HNL), 1-butanol (nBNL), 2-butanol (iBNL), cyclohexanone (CHN), n-butyl ether (BE), di(1,2-dichloroethyl)ether (DCEE), diisobutylketone (DIBK), benzene and toluene from aqueous solution of pH 1-2, having ionic strength of 0.01 mol dm{sup -3} (K{sup +}/H{sup +}, Cl{sup -}). The composition of the extracted adduct has been determined as M(PA){sub 3} except in DCEE where it is M(PA){sub 3}.(HPA). Extraction constants (log K{sub ex}) were calculated and on the basis of log K{sub ex}, the role of diluents in the extraction process has been discussed. The solvents with respect to their extractability of the rare earth metal ions can be arranged in the order ACAC > DIBK > BE> DCEE > ONL > HNL > CHN. (orig.)

  17. Two-stage dilute-acid and organic-solvent lignocellulosic pretreatment for enhanced bioprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Brodeur, G.; Telotte, J.; Stickel, J. J.; Ramakrishnan, S.

    2016-11-01

    A two stage pretreatment approach for biomass is developed in the current work in which dilute acid (DA) pretreatment is followed by a solvent based pretreatment (N-methyl morpholine N oxide -- NMMO). When the combined pretreatment (DAWNT) is applied to sugarcane bagasse and corn stover, the rates of hydrolysis and overall yields (>90%) are seen to dramatically improve and under certain conditions 48 h can be taken off the time of hydrolysis with the additional NMMO step to reach similar conversions. DAWNT shows a 2-fold increase in characteristic rates and also fractionates different components of biomass -- DA treatment removes the hemicellulose while the remaining cellulose is broken down by enzymatic hydrolysis after NMMO treatment to simple sugars. The remaining residual solid is high purity lignin. Future work will focus on developing a full scale economic analysis of DAWNT for use in biomass fractionation.

  18. EXTRACTION OF MALIC ACID WITH ALIQUAT-336 IN EXISTENCE OF DILUENT SOLVENTS

    Directory of Open Access Journals (Sweden)

    Mehmet BİLGİN

    2001-03-01

    Full Text Available In this study, the effect of diluents in different structures on the extraction of malic acid from aqueous solutions with Aliquat-336, named chemically as tricapril metyl ammonium chloride, was investigated. Diluting solvents used in experiments are heptane, toluene, kerosene, cyclohexane and methyl isobuthyl ketone (MIBK. Furthermore, the effect of MIBK+Heptan mixture in 1:1 volume ratio on the extraction was investigated also. The extraction was performed at room temperature by means of a shaker. The distribution coefficients and loading factors were calculated from the experimentally determined results, presented as tables and graphics, and compared with each other. Among the diluents used in this study, the best results were obtained with MIBK.

  19. Physicochemical properties and oral bioavailability of ursolic acid nanoparticles using supercritical anti-solvent (SAS) process.

    Science.gov (United States)

    Yang, Lei; Sun, Zhen; Zu, Yuangang; Zhao, Chunjian; Sun, Xiaowei; Zhang, Zhonghua; Zhang, Lin

    2012-05-01

    The objective of the study was to prepare ursolic acid (UA) nanoparticles using the supercritical anti-solvent (SAS) process and evaluate its physicochemical properties and oral bioavailability. The effects of four process variables, pressure, temperature, drug concentration and drug solution flow rate, on drug particle formation during SAS process, were investigated. Particles with mean particle size ranging from 139.2±19.7 to 1039.8±65.2nm were obtained by varying the process parameters. The UA was characterised by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, thermal gravimetric analysis, specific surface area, dissolution test and bioavailability test. It was concluded that physicochemical properties and bioavailability of crystalline UA could be improved by physical modification, such as particle size reduction and generation of amorphous state using SAS process. Further, SAS process was a powerful methodology for improving the physicochemical properties and bioavailability of UA.

  20. Recovery of Acetic Acid from An Ethanol Fermentation Broth by Liquid-Liquid Extraction (LLE) Using Various Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Thi Thu Huong; Kim, Tae Hyun [Kongju National University, Cheonan (Korea, Republic of); Um, Byung Hwan [Hankyong National University, Anseong (Korea, Republic of)

    2015-12-15

    Liquid-liquid extraction (LLE) using various solvents was studied for recovery of acetic acid from a synthetic ethanol fermentation broth. The microbial fermentation of sugars presented in hydrolyzate gives rise to acetic acid as a byproduct. In order to obtain pure ethanol for use as a biofuel, fermentation broth should be subjected to acetic acid removal step and the recovered acetic acid can be put to industrial use. Herein, batch LLE experiments were carried out at 25°C using a synthetic fermentation broth comprising 20.0 g l{sup -1} acetic acid and 5.0 g l{sup -1} ethanol. Ethyl acetate (EtOAc), tri-n-octylphosphine oxide (TOPO), tri-n-octylamine (TOA), and tri-n-alkylphosphine oxide (TAPO) were utilized as solvents, and the extraction potential of each solvent was evaluated by varying the organic phase-to-aqueous phase ratios as 0.2, 0.5, 1.0, 2.0, and 4.0. The highest acetic acid extraction yield was achieved with TAPO; however, the lowest ethanol-to-acetic acid extraction ratio was obtained using TOPO. In a single-stage batch extraction, 97.0 % and 92.4 % of acetic acid could be extracted using TAPO and TOPO when the ratio of organic-to-aqueous phases is 4:1 respectively. A higher solvent-to-feed ratio resulted in an increase in the ethanol-to-acetic acid ratio, which decreased both acetic acid purity and acetic acid extraction yield.

  1. Effect of Solvent Additives on the Solution Aggregation of Phenyl-C61-Butyl Acid Methyl Ester (PCBM)

    KAUST Repository

    Tummala, Naga Rajesh

    2015-11-24

    High-boiling-point solvent additives, employed during the solution processing of active-layer formulations, impact the efficiency of bulk hetero-junction (BHJ) organic solar cells by influencing the morphological / topological features of the multicomponent thin film. Here, we aim at a better understanding of how these additives change the aggregation landscape in the casting solution prior to film deposition via a multi-scale computational study of the aggregation phenomena of phenyl-C61-butyric-acid methyl ester (PCBM) in various solutions. The energetic landscape of PCBM-solvent / solvent-additive intermolecular interactions is evaluated at the electronic-structure level through symmetry-adapted perturbation theory to determine the nature and strength of non-covalent forces important to aggregation. Molecular dynamics simulations highlight how the choice of solvent and solvent additives control the formation of molecular aggregates. Our results indicate that high-boiling-point solvent additives change the effective interactions among the PCBM and casting-solvent molecules and alter the equilibrium PCBM aggregate sizes in solution.

  2. Recrystallization and shape control of crystals of the organic dye acid green 27 in a mixed solvent.

    Science.gov (United States)

    Cong, Huai-Ping; Yu, Shu-Hong

    2007-01-01

    Recrystallization of the unstructured dye acid green 27 (AG27) in a mixed solvent of alcohol (ethanol or methanol) and water was systematically studied. The results demonstrated that AG27 crystals with uniform sizes and controllable shapes can be produced by simply changing the volume ratio of ethanol (or methanol) and deionized water (DIW). Rodlike and shuttlelike AG27 crystals can be selectively synthesized. The XRD analyses revealed the periodic structures of the organic crystals. Furthermore, crystallization in another mixed solvent of N,N-dimethylformamide (DMF) and DIW results in the formation of longer fibers with high aspect ratio, which further validates the remarkable effects of mixed solvent on the shape of the AG27 crystals. This method of recrystallization in a mixed solvent is expected to facilitate the synthesis of other functional organic crystals with unusual shapes.

  3. Peroxidase activity of bacterial cytochrome P450 enzymes: modulation by fatty acids and organic solvents.

    Science.gov (United States)

    Rabe, Kersten S; Erkelenz, Michael; Kiko, Kathrin; Niemeyer, Christof M

    2010-08-01

    The modulation of peroxidase activity by fatty acid additives and organic cosolvents was determined and compared for four bacterial cytochrome P450 enzymes, thermostable P450 CYP119A1, the P450 domain of CYP102A1 (BMP), CYP152A1 (P450(bsbeta)), and CYP101A1 (P450(cam)). Utilizing a high-throughput microplate assay, we were able to readily screen more than 100 combinations of enzymes, additives and cosolvents in a convenient and highly reproducible assay format. We found that, in general, CYP119A1 and BMP showed an increase in peroxidative activity in the presence of fatty acids, whereas CYP152A1 revealed a decrease in activity and CYP101A1 was only slightly affected. In particular, we observed that the conversion of the fluorogenic peroxidase substrate Amplex Red by CYP119A1 and BMP was increased by a factor of 38 or 11, respectively, when isopropanol and lauric acid were present in the reaction mixture. The activity of CYP119A1 could thus be modulated to reach more than 90% of the activity of CYP152A1 without effectors, which is the system with the highest peroxidative activity. For all P450s investigated we found distinctive reactivity patterns, which suggest similarities in the binding site of CYP119A1 and BMP in contrast with the other two proteins studied. Therefore, this study points towards a role of fatty acids as activators for CYP enzymes in addition to being mere substrates. In general, our detailed description of fatty acid- and organic solvent-effects is of practical interest because it illustrates that optimization of modulators and cosolvents can lead to significantly increased yields in biocatalysis.

  4. The influence of the solvent on organic reactivity. Part II. Hydroxylic solvent effects on the reaction rates of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enylacetic and 2-(2-substituted phenylacetic acids

    Directory of Open Access Journals (Sweden)

    VERA V. KRSTIC

    2004-09-01

    Full Text Available The rate constants for the reaction of diazodiphenylmethane with 2-(2-substituted cyclohex-1-enylacetic acids and 2-(2-substituted phenylacetic acids, previously determined in seven hydroxylic solvents, were correlated using the total solvatochromic equation, of the form: log k = log k0 + sp* + aa + bb, the two-parameter model, log log k = log k0 + sp* + aa, and a single parameter model k = log k0 + sp* + bb, where p* is a measure of the solvent polarity, b represents the scale of solvent hydrogen bond acceptor basicities and a represents the scale of solvent hydrogen bond donor acidities. The correlations of the kinetic data were carried out by means of multiple linear regression analysis and the solvent effects on the reaction rates were analysed in terms of initial state and transition state contributions.

  5. Enhanced esterification of oleic acid and methanol by deep eutectic solvent assisted Amberlyst heterogeneous catalyst.

    Science.gov (United States)

    Pan, Ying; Alam, Md Asraful; Wang, Zhongming; Wu, Jingcheng; Zhang, Yi; Yuan, Zhenhong

    2016-11-01

    In present study, esterification of oleic acid with methanol using deep eutectic solvent (DES) assisted Amberlyst heterogeneous catalyst was investigated to produce biodiesel. Results showed that esterification efficiency was enhanced by the DES. The combined effect of DES on Amberlyst BD20 (BD20) is better than Amberlyst 15 (A-15) due to different structure. The optimal reaction conditions were 12:1M ratio of methanol to oleic acid, 20%(wt/wt) catalyst (BD20-DES (2:8) and A-15-DES (8:2)) at 85°C for 100min with agitating at 200rpm. The mechanism involved in catalysis and their capacity to reuse were studied. We proposed, Choline chloride-glycerol (Chcl-gly) DES could enhance the Amberlyst function due to the hydrogen bond effect on both DES and water. BD20 has fewer pores than A-15, have desirable performance in decreasing the inhibition the water during esterification of high FFA content and provide better performance in reuse.

  6. Choline chloride-based deep eutectic solvents as additives for optimizing chromatographic behavior of caffeic acid

    Energy Technology Data Exchange (ETDEWEB)

    Li, Guizhen; Zhu, Tao; Lei, Yingjie [Tianjin University of Technology, Tianjin (China)

    2015-10-15

    A series of deep eutectic solvents (DESs) were prepared using glycerol and choline chloride (ChCl), and Fourier transform infrared spectrometer (FT-IR) was used to analyze the spectra of glycerol, choline chloride and DESs based on glycerol and choline chloride. Then DESs were used as the additives of mobile phase to optimize chromatographic behavior of caffeic acid in high performance liquid chromatography (HPLC). A 17-run Box-Behnken design (BBD) was employed to evaluate effect of DESs as additives by analyzing the maximum theoretical plate number. Three factors, reaction temperature (60 .deg. C, 80 .deg. C, 100 .deg. C), molar ratio of glycerol and choline chloride (2 : 1, 3 : 1, 4 : 1, n/n), and volume percent of additives (0.05%, 0.10%, 0.15%, v/v), were investigated in BBD. The optimum experiment condition was that of reaction temperature (80 .deg. C), molar ratio of glycerol and ChCl (3 : 1, n/n), and volume percent of additive (0.10%, v/v). The mean chromatographic theoretical plate number of the caffeic acid this condition was 1567.5, and DESs as additives shorten the retention time and modify the chromatogram shape, proving DESs as additives for effective theoretical plate number and column efficiency in HPLC.

  7. Dispersion-free solvent extraction of Cr(VI) from acidic solutions using hollow fiber contactor.

    Science.gov (United States)

    Alguacil, Francisco J; Alonso, Manuel; Lopez, Félix A; Lopez-Delgado, Aurora; Padilla, Isabel

    2009-10-15

    The use of dispersión-free solvent extraction, through microporous hydrophobic membrane has been investigated. The hollow fiber contactor, with surface area of 1.4 m2 was used to extract Cr(VI) (0.005-0.12 g/L from aqueous sulphuric acidic media (pH 2.5-4.2 +/- 0.05). Several parameters such as extractant concentration, feed acidity and metal concentration in the initial aqueous solution were investigated. Results revealed that 15% v/v Cyanex 923 in Exxsol D-100 as organic phase and feed in the 2.5 pH range, gave optimum extraction (exceeding 95%) of Cr(VI) and it was possible to strip using 10 g/L hydrazine sulfate (also with recoveries exceeding 95%). In this step, Cr(VI) is immediately reduced to the less hazardous Cr(III) state. Results also showed that under the various experimental conditions, chromium(VI) extraction was rate-controlled by the interfacial reaction on the membrane surface. Typical overall mass transfer coefficients values are 4.2 x 10(-5) and 3.6 x 10(-6) cm/s for extraction and stripping operations, respectively.

  8. Synthesis of naphthoxazinone derivatives using silica-bonded -sulfonic acid as catalyst under solvent-free conditions

    Indian Academy of Sciences (India)

    Khodabakhsh Niknam; Parisa Abolpour

    2015-07-01

    Silica-bonded -sulfonic acid is employed as a recyclable catalyst for the synthesis of naphthoxazinone derivatives from the reaction of -naphthol, aromatic aldehydes and urea at 150°C under solvent-free conditions. The heterogeneous catalyst was recycled for five runs after the reaction of -naphthol, benzaldehyde and urea without losing its catalytic activity.

  9. Dimethylurea/citric acid as a highly efficient deep eutectic solvent for the multi-component reactions

    Indian Academy of Sciences (India)

    Behnaz Bafti; Hojatollah Khabazzadeh

    2014-05-01

    Dimethylurea/citric acid deep eutectic solvent was used as a dual catalyst and a green reaction medium for the efficient synthesis of bis(indolyl)methanes, quinolines and aryl-4, 5-diphenyl-1H-imidazoles. Ease of recovery and reusability of DES with high activity makes this method efficient and eco-friendly.

  10. An Efficient Method for Synthesis of N-tert-Butyl Amides Using Oxalic Acid Dihydrate in Solvent-Free Condition

    Directory of Open Access Journals (Sweden)

    Masoud Mokhtary

    2014-01-01

    Full Text Available An efficient method for the synthesis of N-tert-butyl amides by reaction of nitriles with tert-butyl acetate or tert-butanol is described using oxalic acid dihydrate in solvent-free condition. The result showed that tert-butyl acetate served as a relatively better source of tert-butyl carbocation than tert-butanol.

  11. Characterization of Polyamide 66 membranes prepared by phase inversion using formic acid and hydrochloric acid such as solvents

    Directory of Open Access Journals (Sweden)

    Patrícia Poletto

    2011-12-01

    Full Text Available The membranes properties prepared from water/formic acid (FA/ polyamide 66 (PA66 and water/hydrochloric acid (HCl/polyamide 66 (PA 66 systems has been studied. The different solvents interact distinctly with the polymer, affecting the membrane morphology. The asymmetric structure of the membranes showed a dense top layer and a porous sublayer. The membranes M-HCl prepared from HCl/PA 66 system showed a larger dense layer (around 23 μm in compared to those prepared from FA/PA 66 system (M-FA (around 10 μm. The membrane morphology was a determinant factor in results of water absorption, porosity and pure water flux. The lower thickness of dense layer in M-FA membranes resulted in a higher water absorption and, consequently, porosity, approximately 50%, compared with M-HCl membranes, approximately 15%. The same trend was observed to permeate flux, the lower thickness of dense layer higher pure water flux.

  12. Kinetic investigation of a solvent-free, chemoenzymatic reaction sequence towards enantioselective synthesis of a β-amino acid ester.

    Science.gov (United States)

    Strompen, Simon; Weiss, Markus; Ingram, Thomas; Smirnova, Irina; Gröger, Harald; Hilterhaus, Lutz; Liese, Andreas

    2012-06-01

    A solvent-free, chemoenzymatic reaction sequence for the enantioselective synthesis of β-amino acid esters has been kinetically and thermodynamically characterized. The coupled sequence comprises a thermal aza-Michael addition of cheap starting materials and a lipase catalyzed aminolysis for the kinetic resolution of the racemic ester. Excellent ee values of >99% were obtained for the β-amino acid ester at 60% conversion. Kinetic constants for the aza-Michael addition were obtained by straightforward numerical integration of second-order rate equations and nonlinear fitting of the progress curves. A different strategy had to be devised for the biocatalytic reaction. Initially, a simplified Michaelis-Menten model including product inhibition was developed for the reaction running in THF as an organic solvent. Activity based parameters were used instead of concentrations in order to facilitate the transfer of the kinetic model to the solvent-free system. Observed solvent effects not accounted for by the use of thermodynamic activities were incorporated into the kinetic model. Enzyme deactivation was observed to depend on the ratio of the applied substrates and also included in the kinetic model. The developed simple model is in very good agreement with the experimental data and allows the simulation and optimization of the solvent-free process.

  13. Effect of Solvent Dielectric Constant and Acidity on the OH Vibration Frequency in Hydrogen-Bonded Complexes of Fluorinated Ethanols.

    Science.gov (United States)

    Pines, Dina; Keinan, Sharon; Kiefer, Philip M; Hynes, James T; Pines, Ehud

    2015-07-23

    Infrared spectroscopy measurements were used to characterize the OH stretching vibrations in a series of similarly structured fluoroethanols, RCH2OH (R = CH3, CH2F, CHF2, CF3), a series which exhibits a systematic increase in the molecule acidity with increasing number of F atoms. This study, which expands our earlier efforts, was carried out in non-hydrogen-bonding solvents comprising molecules with and without a permanent dipole moment, with the former solvents being classified as polar solvents and the latter designated as nonpolar. The hydrogen bond interaction in donor-acceptor complexes formed in solution between the fluorinated ethanol H-donors and the H-acceptor base DMSO was investigated in relation to the solvent dielectric and to the differences ΔPA of the gas phase proton affinities (PAs) of the conjugate base of the fluorinated alcohols and DMSO. We have observed that νOH decreases as the acidity of the alcohol increases (ΔPA decreases) and that νOH varies inversely with ε, exhibiting different slopes for nonpolar and polar solvents. These 1/ε slopes tend to vary linearly with ΔPA, increasing with increasing acidity. These experimental findings, including the ΔPA trends, are described with our recently published two-state Valence Bond-based theory for acid-base H-bonded complexes. Lastly, the correlation of the alcohol's conjugate base PAs with Taft σ* values of the fluorinated ethyl groups CH(n)F(3-n)CH2- provides a connection of the inductive effects for these groups with the acidity parameter ΔPA associated with the H-bonded complexes.

  14. An Efficient Solvent Free Synthesis of 1,8-Dioxo-octahydroxanthene Using p-Toluene Sulfonic Acid

    Institute of Scientific and Technical Information of China (English)

    BAYAT, Mohammad; IMANIEH, Hossien; HOSSIENI, Seyydeh Hajar

    2009-01-01

    A simple and efficient method for the synthesis of 1,8-dioxo-octahydroxanthene by using p-toluenesulfonic acid as a catalyst under solvent free conditions is described, which involves cyclizafion of 2,2-arylmethylenebis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) that was obtained firstly by the reaction of dimedone with aromatic aldehydes in water as solvent and catalyst at room temperature. The experimental procedures in the two steps are very simple and the products are formed in excellent yields.

  15. Sample Preparation for Headspace GC Analysis of Residual Solvents in Hyaluronic Acid Derivative Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hoon Joo; Kim, Dong Min; Yang, Jeong Soo [LG life Sciences, Ltd./R and D Park, Daejeon (Korea, Republic of); Kim, Chan Wha [Korea University, Seoul (Korea, Republic of)

    2006-02-15

    The aim of this study is to develop efficient sample preparation method for HS-GC analysis of residual solvents in HA derivative fiber. Compared to direct extraction of residual solvents from HA derivative fiber, the extraction through the hydrolysis of HA derivative fiber by HAse gave more complete and higher reproducible quantification of residual solvent. To validate HS-GC analysis method of residual solvents, specificity, limits of detection and quantification, linearity, accuracy and precision are investigated in the study. HA derivative fiber was hydrolyzed using HAse for headspace gas chromatographic analysis of residual solvents of ethanol, acetone and isopropanol in HA derivative fiber. This study showed that the developed method had specificity, linearity, accuracy and precision. In addition, it demonstrated that HS-GC coupled with matrix-breaking method such as hydrolysis was available for the determination of residual solvents in a matrix like HA derivative fiber.

  16. Stability of coordination compounds of Ni2+ and Co2+ ions with succinic acid anion in water-ethanol solvents

    Science.gov (United States)

    Tukumova, N. V.; Dieu Thuan, Tran Thi; Usacheva, T. R.; Koryshev, N. E.; Sharnin, V. A.

    2017-04-01

    Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water-ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution ( X EtOH = 0-0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water-ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y2-).

  17. Thallium extraction from hydrochloric acid media into a deep eutectic solvent using bis(2-ethylhexyl) phosphate

    Science.gov (United States)

    Tran, Kate; Volia, Merinda; Tereshatov, Evgeny; Folden, Charles, III

    2016-09-01

    The chemical properties of superheavy elements are relatively unknown due to their short half-lives and difficulty of production. In preparation for a future experiment to study the chemical properties of element 113, separation techniques have been used to study the behavior of its homologs, In and Tl. Previous work studied the liquid-liquid extraction of radioactive 201Tl (t1 / 2 = 3 . 04 d) from various concentrations of HCl into a mixture of menthol and lauric acid that formed a so-called deep eutectic solvent (DES). This work focuses on the effects of adding an extraction agent, bis(2-ethylhexyl) phosphate (HDEHP), to the DES on the efficiency of thallium extraction. The extraction of Tl(I) was generally poor, both with and without HDEHP added. In contrast, 111In (t1 / 2 = 2 . 80 d) showed significant extraction using HDEHP added to the same DES. This difference in behavior could potentially be exploited in a future experiment on the chemistry of element 113. National Science Foundation.

  18. Deep Eutectic Solvents Modified Molecular Imprinted Polymers for Optimized Purification of Chlorogenic Acid from Honeysuckle.

    Science.gov (United States)

    Li, Guizhen; Wang, Wei; Wang, Qian; Zhu, Tao

    2016-02-01

    Deep eutectic solvents (DES) were synthesized with choline chloride (ChCl), and DES modified molecular imprinted polymers (DES-MIPs), DES modified non-imprinted polymers (DES-NIPs, without template), MIPs and NIPs were prepared in an identical procedure. Fourier transform infrared spectrometer (FT-IR) and field emission scanning electron microscopy (FE-SEM) were used to characterize the obtained polymers. Rebinding experiment and solid-phase extraction (SPE) were used to prove the high selectivity adsorption properties of the polymers. Box-Behnken design (BBD) with three factors was used to optimize the extraction condition of chlorogenic acid (CA) from honeysuckles. The optimum extraction conditions were found to be ultrasonic time optimized (20 min), the volume fraction of ethanol (60%) and ratio of liquid to material (15 mL g(-1)). Under these conditions, the mean extraction yield of CA was 12.57 mg g(-1), which was in good agreement with the predicted BBD model value. Purification of hawthorn extract was achieved by SPE process, and SPE recoveries of CA were 72.56, 64.79, 69.34 and 60.08% by DES-MIPs, DES-NIPs, MIPs and NIPs, respectively. The results showed DES-MIPs had potential for promising functional adsorption material for the purification of bioactive compounds.

  19. Solvent-mediated pseudo-quadruple hydrogen-bond motifs in three lamotrigine-carboxylic acid complexes.

    Science.gov (United States)

    Sridhar, Balasubramanian; Nanubolu, Jagadeesh Babu; Ravikumar, Krishnan

    2013-10-01

    Lamotrigine, an antiepileptic drug, has been complexed with three aromatic carboxylic acids. All three compounds crystallize with the inclusion of N,N-dimethylformamide (DMF) solvent, viz. lamotriginium [3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazin-2-ium] 4-iodobenzoate N,N-dimethylformamide monosolvate, C9H8Cl2N5(+)·C7H4IO2(-)·C3H7NO, (I), lamotriginium 4-methylbenzoate N,N-dimethylformamide monosolvate, C9H7Cl2N5(+)·C8H8O2(-)·C3H7NO, (II), and lamotriginium 3,5-dinitro-2-hydroxybenzoate N,N-dimethylformamide monosolvate, C9H8Cl2N5(+)·C7H3N2O7(-)·C3H7NO, (III). In all three structures, proton transfer takes place from the acid to the lamotrigine molecule. However, in (I) and (II), the acidic H atom is disordered over two sites and there is only partial transfer of the H atom from O to N. In (III), the corresponding H atom is ordered and complete proton transfer has occurred. Lamotrigine-lamotrigine, lamotrigine-acid and lamotrigine-solvent interactions are observed in all three structures and they thereby exhibit isostructurality. The DMF solvent extends the lamotrigine-lamotrigine dimers into a pseudo-quadruple hydrogen-bonding motif.

  20. Enzymatic Synthesis of Glucose-Based Fatty Acid Esters in Bisolvent Systems Containing Ionic Liquids or Deep Eutectic Solvents

    Directory of Open Access Journals (Sweden)

    Kai-Hua Zhao

    2016-09-01

    Full Text Available Sugar fatty acid esters (SFAEs are biocompatible nonionic surfactants with broad applications in food, cosmetic, and pharmaceutical industries. They can be synthesized enzymatically with many advantages over their chemical synthesis. In this study, SFAE synthesis was investigated by using two reactions: (1 transesterification of glucose with fatty acid vinyl esters and (2 esterification of methyl glucoside with fatty acids, catalyzed by Lipozyme TLIM and Novozym 435 respectively. Fourteen ionic liquids (ILs and 14 deep eutectic solvents (DESs were screened as solvents, and the bisolvent system composed of 1-hexyl-3-methylimidazolium trifluoromethylsulfonate ([HMIm][TfO] and 2-methyl-2-butanol (2M2B was the best for both reactions, yielding optimal productivities (769.6 and 397.5 µmol/h/g, respectively which are superior to those reported in the literature. Impacts of different reaction conditions were studied for both reactions. Response surface methodology (RSM was employed to optimize the transesterification reaction. Results also demonstrated that as co-substrate, methyl glucoside yielded higher conversions than glucose, and that conversions increased with an increase in the chain length of the fatty acid moieties. DESs were poor solvents for the above reactions presumably due to their high viscosity and high polarity.

  1. Effects of Different Solvents on the Surface Acidic Oxygen-containing Functional Groups on Xanthoceras sorbifolia Shell

    Directory of Open Access Journals (Sweden)

    Linan Liu

    2014-03-01

    Full Text Available This study reports the preparation of a novel biomaterial from a forestry residue - Xanthoceras sorbifolia shell (XSS - by solvent modification. The effects of acid and base (hydrochloric acerbic, acetic acid, sodium hydroxide, ammonia water and some organic solvents (ethanol, acetone, ethyl acetate, chloroform, petroleum ether, and n-hexane on the surface acidic functional groups (SAFGs on XSS were investigated. The amount of SAFGs was quantified using acid and alkali chemical titration methods, and the characteristics of virgin XSS were compared with treated ones by FT-IR spectroscopy. It was found that acid solutions can increase the concentration of SAFGs, while alkaline solutions reduce it. The XSS treated in 0.5 M HCl has the largest number of total acidic functional groups and phenolic hydroxyl groups. The shell extracted with 2 M acetic acid has the highest concentration of carboxyl. The SAFG contents were remarkably increased by treatments with ethanol and acetone, due to the outstanding enhancement of phenolic hydroxyl. These changes in the SAFGs of XSS brought about by treatments with various solutions could be a theoretical foundation for modifying this residue to create a new type of highly efficient absorbent material.

  2. Structural evidence for solvent-stabilisation by aspartic acid as a mechanism for halophilic protein stability in high salt concentrations.

    Science.gov (United States)

    Lenton, Samuel; Walsh, Danielle L; Rhys, Natasha H; Soper, Alan K; Dougan, Lorna

    2016-07-21

    Halophilic organisms have adapted to survive in high salt environments, where mesophilic organisms would perish. One of the biggest challenges faced by halophilic proteins is the ability to maintain both the structure and function at molar concentrations of salt. A distinct adaptation of halophilic proteins, compared to mesophilic homologues, is the abundance of aspartic acid on the protein surface. Mutagenesis and crystallographic studies of halophilic proteins suggest an important role for solvent interactions with the surface aspartic acid residues. This interaction, between the regions of the acidic protein surface and the solvent, is thought to maintain a hydration layer around the protein at molar salt concentrations thereby allowing halophilic proteins to retain their functional state. Here we present neutron diffraction data of the monomeric zwitterionic form of aspartic acid solutions at physiological pH in 0.25 M and 2.5 M concentration of potassium chloride, to mimic mesophilic and halophilic-like environmental conditions. We have used isotopic substitution in combination with empirical potential structure refinement to extract atomic-scale information from the data. Our study provides structural insights that support the hypothesis that carboxyl groups on acidic residues bind water more tightly under high salt conditions, in support of the residue-ion interaction model of halophilic protein stabilisation. Furthermore our data show that in the presence of high salt the self-association between the zwitterionic form of aspartic acid molecules is reduced, suggesting a possible mechanism through which protein aggregation is prevented.

  3. Conformation of a coarse-grained protein chain (an aspartic acid protease) model in effective solvent by a bond-fluctuating Monte Carlo simulation

    Science.gov (United States)

    Pandey, R. B.; Farmer, B. L.

    2008-03-01

    In a coarse-grained description of a protein chain, all of the 20 amino acid residues can be broadly divided into three groups: Hydrophobic (H) , polar (P) , and electrostatic (E) . A protein can be described by nodes tethered in a chain with a node representing an amino acid group. Aspartic acid protease consists of 99 residues in a well-defined sequence of H , P , and E nodes tethered together by fluctuating bonds. The protein chain is placed on a cubic lattice where empty lattice sites constitute an effective solvent medium. The amino groups (nodes) interact with the solvent (S) sites with appropriate attractive (PS) and repulsive (HS) interactions with the solvent and execute their stochastic movement with the Metropolis algorithm. Variations of the root mean square displacements of the center of mass and that of its center node of the protease chain and its gyration radius with the time steps are examined for different solvent strength. The structure of the protease swells on increasing the solvent interaction strength which tends to enhance the relaxation time to reach the diffusive behavior of the chain. Equilibrium radius of gyration increases linearly on increasing the solvent strength: A slow rate of increase in weak solvent regime is followed by a faster swelling in stronger solvent. Variation of the gyration radius with the time steps suggests that the protein chain moves via contraction and expansion in a somewhat quasiperiodic pattern particularly in strong solvent.

  4. The extraction of aromatic amino acids with binary and ternary mixtures of hydrophilic solvents

    Science.gov (United States)

    Mokshina, N. Ya.; Pakhomova, O. A.; Niftaliev, S. I.

    2007-11-01

    The extraction of tyrosine and phenylalanine with binary and ternary mixtures of hydrophilic solvents from aqueous salt solutions was studied, and several tendencies were observed. Simplex-lattice planning of experiment was used for the optimization of the composition of solvent mixtures. It was shown that the extraction systems developed could be employed for the almost complete extraction of tyrosine and phenylalanine from aqueous solutions.

  5. Spectrophotometric determination of acidity constants of 2-(2-Thiazolylazo)-Cresol in various water-organic solvent media mixtures using chemometrics methods.

    Science.gov (United States)

    Momeni-Isfahani, Tahereh; Niazi, Ali

    2014-01-01

    The combination of soft- and hard-modeling was used to the spectrophotometric studies of the acidity constants of 2-(2-Thiazolylazo)-Cresol (TAC) at 25°C and at ionic strength 0.1 mol L(-1) in pure water as well as in aqueous media containing variable percentages (10-50%) of organic solvents. The organic solvents used were methanol, ethanol, dimethyl formamide (DMF) and 1,4-dioxane. The acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data to an established factor analysis model. DATAN program was applied for determining acidity constants and pure spectra of different form of TAC. Results show that the acidity constants of TAC are influenced as the percentages of solvents added to the solution. The corresponding pKa values in solvent-water mixtures were determined. There are linear relationships between acidity constants and the mole fraction of organic solvents in the solvent mixtures. The effects of various solvents on absorption properties and acidity constants of each component are also discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Influence of Extractive Solvents on Lipid and Fatty Acids Content of Edible Freshwater Algal and Seaweed Products, the Green Microalga Chlorella kessleri and the Cyanobacterium Spirulina platensis

    Directory of Open Access Journals (Sweden)

    Jarmila Vavra Ambrozova

    2014-02-01

    Full Text Available Total lipid contents of green (Chlorella pyrenoidosa, C, red (Porphyra tenera, N; Palmaria palmata, D, and brown (Laminaria japonica, K; Eisenia bicyclis, A; Undaria pinnatifida, W, WI; Hizikia fusiformis, H commercial edible algal and cyanobacterial (Spirulina platensis, S products, and autotrophically cultivated samples of the green microalga Chlorella kessleri (CK and the cyanobacterium Spirulina platensis (SP were determined using a solvent mixture of methanol/chloroform/water (1:2:1, v/v/v, solvent I and n-hexane (solvent II. Total lipid contents ranged from 0.64% (II to 18.02% (I by dry weight and the highest total lipid content was observed in the autotrophically cultivated cyanobacterium Spirulina platensis. Solvent mixture I was found to be more effective than solvent II. Fatty acids were determined by gas chromatography of their methyl esters (% of total FAMEs. Generally, the predominant fatty acids (all results for extractions with solvent mixture I were saturated palmitic acid (C16:0; 24.64%–65.49%, monounsaturated oleic acid (C18:1(n-9; 2.79%–26.45%, polyunsaturated linoleic acid (C18:2(n-6; 0.71%–36.38%, α-linolenic acid (C18:3(n-3; 0.00%–21.29%, γ-linolenic acid (C18:3(n-6; 1.94%–17.36%, and arachidonic acid (C20:4(n-6; 0.00%–15.37%. The highest content of ω-3 fatty acids (21.29% was determined in Chlorella pyrenoidosa using solvent I, while conversely, the highest content of ω-6 fatty acids (41.42% was observed in Chlorella kessleri using the same solvent.

  7. Ultrasound-assisted extraction (UAE) and solvent extraction of papaya seed oil: yield, fatty acid composition and triacylglycerol profile.

    Science.gov (United States)

    Samaram, Shadi; Mirhosseini, Hamed; Tan, Chin Ping; Ghazali, Hasanah Mohd

    2013-10-10

    The main objective of the current work was to evaluate the suitability of ultrasound-assisted extraction (UAE) for the recovery of oil from papaya seed as compared to conventional extraction techniques (i.e., Soxhlet extraction (SXE) and solvent extraction (SE)). In the present study, the recovery yield, fatty acid composition and triacylglycerol profile of papaya seed oil obtained from different extraction methods and conditions were compared. Results indicated that both solvent extraction (SE, 12 h/25 °C) and ultrasound-assisted extraction (UAE) methods recovered relatively high yields (79.1% and 76.1% of total oil content, respectively). Analysis of fatty acid composition revealed that the predominant fatty acids in papaya seed oil were oleic (18:1, 70.5%-74.7%), palmitic (16:0, 14.9%-17.9%), stearic (18:0, 4.50%-5.25%), and linoleic acid (18:2, 3.63%-4.6%). Moreover, the most abundant triacylglycerols of papaya seed oil were triolein (OOO), palmitoyl diolein (POO) and stearoyl oleoyl linolein (SOL). In this study, ultrasound-assisted extraction (UAE) significantly (p < 0.05) influenced the triacylglycerol profile of papaya seed oil, but no significant differences were observed in the fatty acid composition of papaya seed oil extracted by different extraction methods (SXE, SE and UAE) and conditions.

  8. Ultrasound-Assisted Extraction (UAE and Solvent Extraction of Papaya Seed Oil: Yield, Fatty Acid Composition and Triacylglycerol Profile

    Directory of Open Access Journals (Sweden)

    Hasanah Mohd Ghazali

    2013-10-01

    Full Text Available The main objective of the current work was to evaluate the suitability of ultrasound-assisted extraction (UAE for the recovery of oil from papaya seed as compared to conventional extraction techniques (i.e., Soxhlet extraction (SXE and solvent extraction (SE. In the present study, the recovery yield, fatty acid composition and triacylglycerol profile of papaya seed oil obtained from different extraction methods and conditions were compared. Results indicated that both solvent extraction (SE, 12 h/25 °C and ultrasound-assisted extraction (UAE methods recovered relatively high yields (79.1% and 76.1% of total oil content, respectively. Analysis of fatty acid composition revealed that the predominant fatty acids in papaya seed oil were oleic (18:1, 70.5%–74.7%, palmitic (16:0, 14.9%–17.9%, stearic (18:0, 4.50%–5.25%, and linoleic acid (18:2, 3.63%–4.6%. Moreover, the most abundant triacylglycerols of papaya seed oil were triolein (OOO, palmitoyl diolein (POO and stearoyl oleoyl linolein (SOL. In this study, ultrasound-assisted extraction (UAE significantly (p < 0.05 influenced the triacylglycerol profile of papaya seed oil, but no significant differences were observed in the fatty acid composition of papaya seed oil extracted by different extraction methods (SXE, SE and UAE and conditions.

  9. Screening and characterization of cocrystal formation of metaxalone with short-chain dicarboxylic acids induced by solvent-assisted grinding approach

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hong-Liang; Wu, Tieh-Kang; Lin, Shan-Yang, E-mail: sylin@mail.ypu.edu.tw

    2014-01-10

    Graphical abstract: Solvent-assisted grinding approach can create a cocrystal between metaxalone and succinic acid, fumaric acid or maleic acid. The cocrystal formation was easily screened and identified using a unique DSC-FTIR microspectroscopy. - Highlights: • Solvent-assisted grinding can easily create a cocrystal formation. • Metaxalone and n = 2 of short-chain dicarboxylic acids can form cocrystal. • The cocrystal formation is also easily induced by a unique DSC-FTIR microspectroscopy. - Abstract: A solvent-assisted grinding approach was used to investigate the possible cocrystal formation between metaxalone and short-chain dicarboxylic acids (HOOC-(CH{sub 2}){sub n}-COOH, n = 0–3). Differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) microspectroscopy, and powder X-ray diffraction (PXRD) were used to verify the cocrystal formation between metaxalone and each dicarboxylic acid. As a standard reference, a cocrystal was prepared by solvent evaporation method. The cocrystal formation was also quickly estimated by using a one-step simultaneous DSC-FTIR microspectroscopy. The present study indicates that only n = 2 of short-chain dicarboxylic acids such as succinic acid, fumaric acid and maleic acid can form a cocrystal with metaxalone through solvent-assisted grinding in a short time. Moreover, this cocrystal formation was easily screened and estimated using a unique DSC-FTIR microspectroscopy.

  10. Penelitian pengaruh naphthenic oil dan carbon black terhadap sifat kekerasan lis kaca mobil

    Directory of Open Access Journals (Sweden)

    Any Setyaningsih

    1999-07-01

    Full Text Available This research have a purpose to know influence naphthenic oil and car bon black about properties hardness weather strip for auto mobile. Compound wea ther strip for auto mobile make for Natural Rubber (RSS and sintetic rubber (SBR 1502 with in creasing ingrediens such plasticizer, activator, filler, anti oxidant, accelerator and vulkanizing agent. Compount formula making variation naphthenic oil 3,5 and 7 part along with carbon black 45,50 and 55 part result hardness test with value 67 shore A for compount with naphthenic oil 7 part and carbon black 50 part and after perform make in to fill requrements SNI 1490 – 89 A weather strip auto mobile.

  11. Recovery of Vanadium from H2SO4-HF Acidic Leaching Solution of Black Shale by Solvent Extraction and Precipitation

    Directory of Open Access Journals (Sweden)

    Xingbin Li

    2016-03-01

    Full Text Available The recovery of vanadium from sulfuric and hydrofluoric mixed acid solutions generated by the direct leaching of black shale was investigated using solvent extraction and precipitation methods. The process consisted of reduction, solvent extraction, and stripping, followed by precipitation and calcination to yield vanadium pentoxide. The influence of various operating parameters on the extraction and recovery of vanadium was studied. Vanadium (IV was selectively extracted using a mixture of 10% (v/v di(2-ethylhexylphosphoric acid and 5% (v/v tri-n-butylphosphate in sulfonated kerosene. Using six extraction and five stripping stages, the extraction efficiency for vanadium was 96.7% and the stripping efficiency was 99.7%. V2O5 with a purity of 99.52% was obtained by oxidation of the loaded strip solution and precipitation of ammonium polyvanadate at pH 1.8 to 2.2, followed by calcination of the dried precipitate at 550 °C for 2 h. It was concluded that the combination of solvent extraction and precipitation is an efficient method for the recovery of vanadium from a multi-element leach solution generated from black shale.

  12. Effect of organic co-solvents on the solvation enthalpies of amino acids and dipeptides in mixed aqueous solutions

    Science.gov (United States)

    Badelin, V. G.; Tyunina, E. Yu.

    2011-09-01

    Transition enthalpies (Δtr H o) of substances from water to binary solutions were calculated at 298.15 K on the basis of standard dissolution enthalpies (Δsol H o) for six amino acids and five dipeptides in the mixtures of water with organic solvents of various chemical natures. The enthalpy pair coefficients of interaction h xy for biomolecules with organic component of mixture were estimated within the formalism of the McMillan-Mayer theory. The change in the character of the interaction of the components of solution was demonstrated in dependence on the physicochemical properties of the solvent and nature of the side radical of the dissolved bioorganic substance. Quantitative estimation of the type of interaction of the substance with the solvent was performed on the basis of correlation ratios relating the enthalpy characteristics of bioorganic substances to properties of organic cosolvents. It was shown that in the solutions under study, the effects of both the specific (mainly electron donor) and non-specific solvation of amino acids and peptides are observed.

  13. Availability and cost estimate of a high naphthene, modified aviation turbine fuel

    Science.gov (United States)

    Prok, George M.

    1988-01-01

    Information from an Air Force study was used to determine the potential availability and cost of a modified conventional fuel with a naphthene content which could have a thermal stability near that of JP-7 for high-speed civil transports. Results showed sufficient capacity for a fuel made of a blend of 50 percent naphthenic straight run kerosene and 50 percent hydrocracked product, assuming a near-term requirement of 210,000 BBL per day. Fuel cost would be as low as 62.5 to 64.5 cents per gallon, assuming 20 dollars per barrel for crude.

  14. Extraction of Betulin, Trimyristin, Eugenol and Carnosic Acid Using Water-Organic Solvent Mixtures

    Directory of Open Access Journals (Sweden)

    Fulgentius N. Lugemwa

    2012-08-01

    Full Text Available A solvent system consisting of ethyl acetate, ethyl alcohol and water, in the volume ratio of 4.5:4.5:1, was developed and used to extract, at room temperature, betulin from white birch bark and antioxidants from spices (rosemary, thyme, sage, and oregano and white oak chips. In addition, under reflux conditions, trimyristin was extracted from nutmeg using the same solvent system, and eugenol from olives was extracted using a mixture of salt water and ethyl acetate. The protocol demonstrates the use of water in organic solvents to extract natural products from plants. Measurement of the free-radical scavenging activity using by 2,2-diphenyl-1-picrylhydrazyl (DPPH indicated that the extraction of plant material using ethyl acetate, ethyl alcohol and water (4.5:4.5:1, v/v/v was exhaustive when carried out at room temperature for 96 h.

  15. Thermodynamically based solvent design for enzymatic saccharide acylation with hydroxycinnamic acids in non-conventional media

    DEFF Research Database (Denmark)

    Zeuner, Birgitte; Kontogeorgis, Georgios; Riisager, Anders

    2012-01-01

    Enzyme-catalyzed synthesis has been widely studied with lipases (EC 3.1.1.3), but feruloyl esterases (FAEs; EC 3.1.1.73) may provide advantages such as higher substrate affinity and regioselectivity in the synthesis of hydroxycinnamate saccharide esters. These compounds are interesting because...... of their amphiphilicity and antioxidative potential. Synthetic reactions using mono- or disaccharides as one of the substrates may moreover direct new routes for biomass upgrading in the biorefinery. The paper reviews the available data for enzymatic hydroxycinnamate saccharide ester synthesis in organic solvent systems...... as well as other enzymatic hydroxycinnamate acylations in ionic liquid systems. The choice of solvent system is highly decisive for enzyme stability, selectivity, and reaction yields in these synthesis reactions. To increase the understanding of the reaction environment and to facilitate solvent screening...

  16. Numerical simulation of the solvate structures of acetylsalicylic acid in supercritical carbon dioxide containing polar co-solvents

    Science.gov (United States)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Kumeev, R. S.; Golubev, V. A.

    2016-07-01

    Hydrogen-bonded complexes of acetylsalicylic acid with polar co-solvents in supercritical carbon dioxide, modified by methanol, ethanol, and acetone of 0.03 mole fraction concentration, are studied by numerical methods of classical molecular dynamics simulation and quantum chemical calculations. The structure, energy of formation, and lifetime of hydrogen-bonded complexes are determined, along with their temperature dependences (from 318 to 388 K at constant density of 0.7 g cm-3). It is shown that the hydrogen bonds between acetylsalicylic acid and methanol are most stable at 318 K and are characterized by the highest value of absolute energy. At higher supercritical temperatures, however, the longest lifetime is observed for acetylsalicylic acid-ethanol complexes. These results correlate with the known literature experimental data showing that the maximum solubility of acetylsalicylic acid at density values close to those considered in this work and at temperatures of 318 and 328 K is achieved when using methanol and ethanol as co-solvents, respectively.

  17. Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

    Science.gov (United States)

    del Valle, J C; García Blanco, F; Catalán, J

    2015-04-02

    The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).

  18. N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate as a novel, efficient, and reusable solid acid catalyst for acylation under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Nader Ghaffari Khaligh; Parisa Ghods Ghasem-Abadi

    2014-01-01

    N-Sulfonic acid poly(4-vinylpyridinum) hydrogen sulfate has been developed as a recyclable solid acid catalyst for the acetylation of alcohols, phenols, thiols, and amines, as well as the 1,1- diacetyla-tion of aldehydes under solvent-free conditions at room temperature. The acetylated products were formed in good to excellent yields over short reaction times, and the catalyst could be readily re-covered by filtration and used several times without any discernible loss in activity. The hydrogen sulfate anion of the catalytic system was found to play a critical role in enhancing the reaction time and yield of the acetylation reaction.

  19. Solvent Effects on Complexation of Molybdenum(VI) with Nitrilotriacetic Acid in Different Aqueous Solutions of Propanol

    Institute of Scientific and Technical Information of China (English)

    MOHAMMADI Behrouz; MOHAMMADI Jalal

    2007-01-01

    By using spectrophotometric and potentiometric techniques the formation constants of the species formed in the systems H++Mo(VI)+nitrilotriacetic acid and H++nitrilotriacetic acid have been determined in aqueous solutions plex was determined by the continuous variation method. It was shown that molybdenum(VI) forms a mononuclear 1 : 1 complex with nitrilotriacetic acid of the type MoO3L-3 at -1g[H+]=5.8. The formation constants in various media were analyzed in terms of Kamlet and Taft's parameters. Linear relationships were observed when 1g Ks was plotted versus p*. Finally, the results were discussed in terms of the effect of solvent on complexation.

  20. Enrichment of omega-3 fatty acids in cod liver oil via alternate solvent winterization and enzymatic interesterification.

    Science.gov (United States)

    Lei, Qiong; Ba, Sai; Zhang, Hao; Wei, Yanyan; Lee, Jasmine Yiqin; Li, Tianhu

    2016-05-15

    Enrichment of omega-3 fatty acids in cod liver oil via alternate operation of solvent winterization and enzymatic interesterification was attempted. Variables including separation method, solvent, oil concentration, time and temperature were optimized for the winterization. Meanwhile, Novozyme 435, Lipozyme RM IM and Lipozyme TL IM were screened for interesterification efficiency under different system air condition, time and temperature. In optimized method, alternate winterization (0.1g/mL oil/acetone, 24h, -80°C, precooled Büchner filtration) and interesterification (Lipozyme TL IM, N2 flow, 2.5h, 40°C) successfully doubled the omega-3 fatty acid content to 43.20 mol%. (1)H NMR was used to determine omega-3 fatty acid content, and GC-MS to characterize oil product, which mainly contained DHA (15.81 mol%) and EPA (20.23 mol%). The proposed method offers considerable efficiency and reduce production cost drastically. Oil produced thereof is with high quality and of particular importance for the development of omega-3 based active pharmaceutical ingredients.

  1. {beta}-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    Energy Technology Data Exchange (ETDEWEB)

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F. [Wesleyan Univ., Middletown, CT (United States)

    1995-03-24

    {beta}-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 {degrees}C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6-{sup 2}H{sub 2}]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 {plus_minus} 0.01. These values support the B{sub AC}2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other {beta}-lactams. The measured {beta}-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 {plus_minus} 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A{sub AC}1 mechanism with an intermediate acylium ion. If this were so, the calculated {beta}-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 {plus_minus} 0.01. This suggests an early A{sub AC}1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A{sub AC}1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 {plus_minus} 0.00 in 1 M HCl and 0.22 {plus_minus} 0.01 in 33.3 wt % H{sub 2}SO{sub 4}. 1 fig., 3 tabs.

  2. Site-specific solvent exposure analysis of a membrane protein using unnatural amino acids and {sup 19}F nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Pan; Li, Dong [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230026 (China); Chen, Hongwei [High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui 230031 (China); Xiong, Ying [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230026 (China); Tian, Changlin, E-mail: cltian@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui 230031 (China)

    2011-10-22

    Highlights: {yields} Solvent isotope shift analysis of {sup 19}F-tfmF in different H{sub 2}O/D{sub 2}O molar ratio. {yields} Correlation between solvent isotope shift of {sup 19}F-spins and solvent exposure analysis. {yields} Solvent exposure analysis of membrane proteins. -- Abstract: Membrane proteins play an essential role in cellular metabolism, transportation and signal transduction across cell membranes. The scarcity of membrane protein structures has thus far prevented a full understanding of their molecular mechanisms. Preliminary topology studies and residue solvent exposure analysis have the potential to provide valuable information on membrane proteins of unknown structure. Here, a {sup 19}F-containing unnatural amino acid (trimethylfluoro-phenylalanine, tfmF) was applied to accomplish site-specific {sup 19}F spin incorporation at different sites in diacylglycerol kinase (DAGK, an Escherichia coli membrane protein) for site-specific solvent exposure analysis. Due to isotope effect on {sup 19}F spins, a standard curve for {sup 19}F-tfmF chemical shifts was drawn for varying solvent H{sub 2}O/D{sub 2}O ratios. Further site-specific {sup 19}F solvent isotope shift analysis was conducted for DAGK to distinguish residues in water-soluble loops, interfacial areas or hydrophobic membrane regions. This site-specific solvent exposure analysis method could be applied for further topological analysis of other membrane proteins.

  3. Exploration of a ternary deep eutectic solvent of methyltriphenylphosphonium bromide/chalcone/formic acid for the selective recognition of rutin and quercetin in Herba Artemisiae Scopariae.

    Science.gov (United States)

    Ma, Wanwan; Tang, Baokun; Row, Kyung Ho

    2017-08-01

    Methyltriphenylphosphonium bromide/chalcone/formic acid, a green ternary deep eutectic solvent, was applied as a functional monomer and dummy template simultaneously in the synthesis of a new molecularly imprinted polymer. Ternary deep eutectic solvent based molecularly imprinted polymers are used as a solid-phase extraction sorbent in the separation and purification of rutin and quercetin from Herba Artemisiae Scopariae combined with high-performance liquid chromatography. Fourier transform infrared spectroscopy and field-emission scanning electron microscopy were applied to characterize the deep eutectic solvent based molecularly imprinted polymers synthesized using different molar ratios of chalcone. The static and competitive adsorption tests were performed to examine the recognition ability of the molecularly imprinted polymers to rutin and quercetin. The ternary deep eutectic solvent consisting of formic acid/chalcone/methyltriphenylphosphonium bromide (1:0.05:0.5) had the best molecular recognition effect. After optimization of the washing solvents (methanol/water, 1:9) and eluting solvents (acetonitrile/acetic acid, 9:1), a reliable analytical method was developed for strong recognition towards rutin and quercetin in Herba Artemisiae Scopariae with satisfactory extraction recoveries (rutin: 92.48%, quercetin: 94.23%). Overall, the chalcone ternary deep eutectic solvent-based molecularly imprinted polymer coupled with solid-phase extraction is an effective method for the selective purification of multiple bioactive compounds in complex samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. RAPID SOLVENT-FREE MICROWAVE ASSISTED SYNTHESIS OF SOME N’-BENZYLIDENE SALICYLIC ACID HYDRAZIDES

    Directory of Open Access Journals (Sweden)

    Tutuk Budiati

    2012-06-01

    Full Text Available Condensation reaction has been carried out for the synthesis of some N'-benzylidene-2-hydroxybenzohydrazides using microwave assisted solvent-free method. The structures of all the products obtained in the present work are supported by spectral and analytical data (UV, IR, and 1H-NMR spectroscopy. The desired hydrazides are in 62-80% yields under microwave irradiation. The reaction was completed in 8-10 min.

  5. Study of the resolution of amino acids and aminoalcohols in organic solvents.

    Science.gov (United States)

    Orsini, F; Pelizzoni, F; Ghioni, C

    1995-06-01

    The enzymatic resolution of racemic phenylglycine, phenylglycinol and phenylalaninol has been studied in organic solvents under a variety of experimental conditions. Subtilisin in 3-methyl-3-pentanol was effective for the resolution of phenylglycine esters, via N-acylation with trifluoroethyl butyrate. Porcine pancreatic lipase in ethyl acetate gave satisfactory results in the resolution of phenylglycinol and phenylalaninol; theα orβ position of the phenyl group was found to influence both the rate and the chemioselectivity of the reaction.

  6. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

    Institute of Scientific and Technical Information of China (English)

    Ben Li; Cuiping Wang; Guang Chen; Zhiqiang Zhang

    2013-01-01

    Highly active,air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents.Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture,water/propanol mixture and neat water respectively,the corresponding yields of cross-coupling heteroaryl-aryls were satisfied.The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPdl and POPd2,and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step.Compared with other solid phase transfer catalysts,TBAB was tested as the ideal one.The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents.Notably,in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products.However in terms of the liquid phase transfer catalyst of PEGs,mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase,which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  7. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents.

    Science.gov (United States)

    Li, Ben; Wang, Cuiping; Chen, Guang; Zhang, Zhiqiang

    2013-06-01

    Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  8. Lanthanide Coordination Polymers with 4,4'-Azobenzoic Acid: Enhanced Stability and Magnetocaloric Effect by Removing Guest Solvents.

    Science.gov (United States)

    Zhang, Shaowei; Duan, Eryue; Han, Zongsu; Li, Leilei; Cheng, Peng

    2015-07-06

    Three lanthanide coordination polymers (Ln-CPs) formulated as [Ln(azdc)(HCOO)]n [Ln = Gd(III) (1), Tb(III) (2), Dy(III) (3); H2azdc = 4,4'-azobenzoic acid] have been successfully obtained by the solvothermal reaction of Ln(III) ions with H2azdc ligands in the mixed solvent N,N-dimethylformamide (DMF)/H2O. Compared with our previous work on Ln-CPs with H2azdc ligands, [Gd2(azdc)3(DMA)2]n·2nDMA (1'; DMA = dimethylacetamide), in which the DMA molecules coordinate to Gd(III) ions that are replaced by HCOO(-) groups in 1, resulting in the distinct structures and properties of the final products. Adjacent Ln(III) ions in 1-3 are connected by HCOO(-) groups through bridging and chelating modes to give 2D layers, which are further linked by azdc(2-) ligands to produce 3D frameworks. Magnetic results declare that antiferromagnetic couplings exist in 1, although two different magnetic interactions among adjacent Gd(III) ions derived from antiferromagnetic interactions of the smaller Gd-O-Gd angles (Gd···Gd distances) and weak ferromagnetic interactions of the larger Gd-O-Gd angles (Gd···Gd distances) coexist in 1. Furthermore, the magnetocaloric effect (MCE) value of 1 is 1.5 times as large as that of 1'. More importantly, 1 exhibits excellent stabilities toward air, thermal, solvent, and acid/alkaline conditions. The results manifest that the crystalline structure of 1 can be stable at at least 425 °C supported by the in situ variable-temperature powder X-ray diffraction patterns and thermogravimetric analyses, in air for at least 3 months, and in common solvents for more than 1 week, as well as in aqueous solutions ranging from pH = 2 to 12 for more than 1 week.

  9. Indium recovery from acidic aqueous solutions by solvent extraction with D2EHPA: a statistical approach to the experimental design

    Directory of Open Access Journals (Sweden)

    Fortes M.C.B.

    2003-01-01

    Full Text Available This experimental work presents the optimization results of obtaining a high indium concentration solution and minimum iron poisoning by solvent extraction with D2EHPA solubilized in isoparaffin and exxsol. The variables studied in the extraction step were D2EHPA concentration, acidity of the aqueous phase and time of contact between phases. Different hydrochloric and sulfuric acid concentrations were studied for the stripping step. The optimum experimental conditions resulted in a solution with 99% indium extraction and less than 4% iron. The construction of a McCabe-Thiele diagram indicated two theoretical countercurrent stages for indium extraction and at least six stages for indium stripping. Finally, the influence of associated metals found in typical sulfate leach liquors from zinc plants was studied. Under the experimental conditions for maximum indium extraction, 96% indium extraction was obtained, iron extraction was about 4% and no Ga, Cu and Zn were co-extracted.

  10. THE EFFECT OF SULPHURIC ACID CONCENTRATION ON SOLVENT EXTRACTION OF ReO4 - BY THE LONG-CHAIN ALIPHATIC TERTIARY AMINES AND ALCOHOLS

    Directory of Open Access Journals (Sweden)

    Aleksander G. Kasikov

    2010-06-01

    Full Text Available The effect of sulphuric acid concentration on solvent extraction of ReO4- by the long-chain aliphatic tertiary amines and alcohols in a wide range of H2SO4 concentrations in initial solutions is discussed. It has been established that the influence of the sulphuric acid concentration on rhenium solvent extraction is largely due to the extraction process mechanism. In the case of the anion-exchange mechanism, ReO4- is best extracted from weakly acidic solutions, whereas when the hydrate-solvate mechanism takes place – from solutions containing 4-7 mole/l H2SO4.

  11. Multicarboxylic acids as environment-friendly solvents and in situ crosslinkers for chitosan/PVA nanofibers with tunable physicochemical properties and biocompatibility.

    Science.gov (United States)

    Pangon, Autchara; Saesoo, Somsak; Saengkrit, Nattika; Ruktanonchai, Uracha; Intasanta, Varol

    2016-03-15

    Monocarboxylic acids are common solvents for chitosan to fabricate nanofibers however the unpleasant odor and the additional step of fiber stabilization using crosslinkers, which might cause toxicity, are always the points to be aware of. The present work demonstrates the potential use of multicarboxylic acids as environment-friendly solvents and in situ crosslinking agents for chitosan electrospinning. The use of these solvents leads to the tunable physicochemical properties, cellular compatibility, and cost effective production. By changing di-, to tri-, and tetracarboxylic acids combining with the simple thermal treatment, the stability and mechanical properties of the nanofibrous mats, especially the elastic modulus and elongation at break, can be altered. The resulting nanofibers exhibit biocompatibility favorable for proliferation and adhesion of the osteoblast cells. The multicarboxylic acids allow us lab-scale reproducibility and possibility to semi-production of nanofibrous chitosan using Nanospider™.

  12. Using a Simulated Industrial Setting for the Development of an Improved Solvent System for the Recrystallization of Benzoic Acid: A Student-Centered Project

    Science.gov (United States)

    Hightower, Timothy R.; Heeren, Jay D.

    2006-01-01

    Recrystallization of benzoic acid is an excellent way to remove insoluble impurities. In a traditional organic laboratory experiment, insoluble impurities are removed through the recrystallization of benzoic acid utilizing water as the recrystallization solvent. It was our goal to develop a peer-led, problem-solving organic laboratory exercise…

  13. A green method for the synthesis of bis-indolylmethanes and 3,3 -indolyloxindole derivatives using cellulose sulfuric acid under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Heshmatollah; Alinezhad; Asefeh; Hagh; Haghighi; Fatemeh; Salehian

    2010-01-01

    A highly efficient green protocol for the preparation of bis-indolylmethanes,bis-2-methylindolylmethanes,bis-1-methylindolylmethanes and 3,3'-diindolyloxindole derivatives from the reaction of indoles with various aldehydes and ketones in the presence of cellulose sulfuric acid under solvent-free conditions is reported.The significant features of this procedure are high yields of the products,mild reaction,solvent-free condition and non-toxicity of the catalyst.

  14. Iodine Catalyzed One-pot Synthesis of 3,4-Dihydroquinazolin-4-ones from Anthranilic Acids, Ortho Esters and Amines under Solvent-free Conditions

    Institute of Scientific and Technical Information of China (English)

    WANG,Hong-She; ZENG,Jun-E

    2008-01-01

    A simple and efficient procedure has been developed for the one-pot synthesis of 3,4-dihydroquinazolin-4-ones from anthranilic acids, ortho esters and amines using a catalytic amount of iodine under solvent-free conditions to afford the corresponding products in excellent yields. The direct use of commercially available catalyst, mild and solvent-free reaction conditions, short reaction time, easy workup and excellent yields are the advantages of the present protocol.

  15. A study of parameters affecting the solvent extraction of lactic acid from fermentation broth

    OpenAIRE

    Udachan,I. S.; Sahoo, A.K.

    2014-01-01

    Lactic acid has recently been drawing much interest as a raw material for biodegradable polymer. One of the promising technologies for recovery of lactic acid from fermentation broth is reactive liquid - liquid extraction. Equilibrium studies on the reactive extraction of lactic acid with trioctylamine (TOA) in various organic phases and its re-extraction into aqueous solutions were carried out. In this study distribution coefficient, extractability, stripping efficiency of various active and...

  16. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    Energy Technology Data Exchange (ETDEWEB)

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  17. Enthalpy of mixing of methacrylic acid with organic solvents at 293 K

    Science.gov (United States)

    Sergeev, V. V.

    2016-03-01

    The enthalpies of mixing of binary systems of methacrylic acid with acetonitrile, benzene, hexane, 1,2-dichloroethane, and acetic acid are measured calorimetrically at 293 K and atmospheric pressure. The enthalpy of mixing of all the studied binary systems is positive over the range of concentrations.

  18. Enantioselective esterification of (R,S)-2-methylalkanoic acid with Carica papaya lipase in organic solvents.

    Science.gov (United States)

    Chang, Chun-Sheng; Ho, Ssu-Ching

    2011-11-01

    Isooctane was the best reaction medium for the enantioselective esterification of (R,S)-2-methylalkanoic acid with n-butanol using Carica papaya lipase as catalyst. Increasing linear alkyl-chain length of racemic 2-methylalkanoic acids from ethyl to hexyl increased the enantioselectivity (E) from 2.1 to 98.2 for the esterification of racemic 2-methylalkanoic acids with n-butanol at 35°C. Decreasing reaction temperature from 40 to 20°C increased the enantioselectivity (E) from 14 to 33 for the esterification of racemic 2-methylhexanoic acids with n-butanol. We obtained a maximum enantioselectivity, of E = 24.3, for the enantioselective esterification of racemic 2-methylhexanoic acids with n-butanol in isooctane at water activity 0.33, and at 35°C.

  19. Liquid phase esterification of acetic acid over WO3 promoted β-SiC in a solvent free system.

    Science.gov (United States)

    Mishra, Gopa; Behera, Gobinda C; Singh, S K; Parida, K M

    2012-12-21

    A series of tungstate promoted β-SiC catalysts was synthesized by a wetness impregnation method. The as synthesized catalysts were unambiguously characterized by XRD, Raman, FTIR, XPS, UV-Vis DRS, TEM, BET surface areas and FE-SEM, and simultaneously the total amount of the acidity of the catalysts was estimated by NH(3)-TPD. The catalytic activities of the synthesized materials were tested in the liquid phase esterification of acetic acid with n-butanol in a solvent free medium. The reaction parameters were optimized to a temperature of 120 °C, molar ratio of butanol and acetic acid of 1:2 and a reaction time of 6 h after performing a number of experiments. Under the optimum conditions, the catalytic esterification revealed a significant effect of 88% conversion with 100% selectivity to butyl acetate in 20 wt% WO(3)/β-SiC. This is the first report on the effective utilization of β-SiC as a catalyst support for liquid phase esterification of acetic acid.

  20. Effect of solvents and methods of stirring in extraction of lycopene, oleoresin and fatty acids from over-ripe tomato.

    Science.gov (United States)

    López-Cervantes, Jaime; Sánchez-Machado, Dalia I; Valenzuela-Sánchez, Karla P; Núñez-Gastélum, José A; Escárcega-Galaz, Ana A; Rodríguez-Ramírez, Roberto

    2014-03-01

    Lycopene and oleoresin extraction from powder of tomato over-ripe by three agitation methods and four solvents have been evaluated. Also, tomato powder and the oleoresins were characterized biochemically. On average, the moisture content of powder was found to be 4.30, ash 8.90, proteins 11.23 and lipids 4.35 g 100 g(-1). The best oleoresin extraction yield was achieved by combining sonication and acetone at 1.43 g 100 g(-1). The greatest amount of lycopene (65.57 ± 0.33 mg 100 g(-1)) was also obtained using the same treatment. The presence of trans-lycopene was positively confirmed by HPLC and FTIR. In oleoresins, linoleic acid (C18:2n6) was the predominant with 50% of total fatty acids, whereas stearic acid (C18:0) is presented in a smaller proportion (5%). A simple and suitable method for extraction of lycopene from over-ripe tomato was optimized. In industrial applications, tomato by-products are a viable source of analytes, such as lycopene and unsaturated fatty acids.

  1. Relationship between physicochemical parameters of alpha-amino acids and those of the chlorinated solvents in the case of the L/L partition as supra molecular complexes

    Energy Technology Data Exchange (ETDEWEB)

    Oana popescu, D.; Constantinescu, T.; Mutihac, L.

    1997-09-01

    In order to explain the dependence of the distribution coefficient (D) between water and three different chlorinated solvents (methylene chloride, chloroform and 1,2-dichloroethane) of some alpha-amino acids (leucine, tryptophane, phenylalanine, methionine, valine and isoleucine), as supramolecular complexes of [EC...R-CH-(NH{sub 3})-COOH]``+A``- type, (EC=18-C-6; A``-=the anion originated in tropaeoline 00), a correlation was established by means of a multilinear regression analysis performed between different characteristics of the alpha-amino acids and those of the solvents involved. This study evidence a good correlation (r>0.81) between some of the characteristics of alpha-amino acids (pi, pH, pKa{sub 2}), and of the solvent Sigma Beta``H{sub 2}, pi``H{sub 2} R``H{sub 2} or sigma alpha``H{sub 2}, just mentioned. (Author) 21 refs.

  2. An Efficient and Simple Reaction: Solvent-Free Preparation of Rosolic Acid Under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    LI Min; ZHANG Qi-jun; YANG Jun-wei; TONG Shan-ling; YANG Ke-er; XIAO Feng-shou; K. P. Ng. Dennisx; YAN Yan

    2008-01-01

    @@ 1 Introduction Rosolic acid, also called as resinous acid, is a trihydroxyphenyl methane dye mainly used as an oxidation resistant indicator in acid-base titration with sharp color change depending on the pH, from 5.0(yellow) to 6.8(pink)[1,2]. It is also used as an initial reactant in the syntheses of 4,4',4"-tris(acyloxy)trityl chloride and its bromide for protection of primary hydroxyl groups[3], and a monomer in polyreaction to prepare color polymer fiber as pH probe[4].

  3. Synthesis of glycerides containing n-3 fatty acids and conjugated linoleic acid by solvent-free acidolysis of fish oil.

    Science.gov (United States)

    Garcia, H S; Arcos, J A; Ward, D J; Hill, C G

    2000-12-05

    Menhaden oil, a rich source of n-3 fatty acids, was interesterified with conjugated linoleic acid (CLA) in a reaction medium composed solely of substrates and either free or immobilized commercial lipase preparations. Of five lipases tested, an immobilized preparation from Mucor miehei provided the fastest rate of incorporation of CLA into fish oil acylglycerols; however, and as observed with most of the lipases utilized, a significant proportion of the n-3 fatty acid residues were liberated in the process. A soluble lipase from Candida rugosa converted free CLA to acylglycerol residues while leaving the n-3 fatty acid residues virtually untouched. Even though the reaction rate was slower for this enzyme than for the other four lipase preparations, the specificity of the free C. rugosa lipase gives it the greatest potential for commercial use in preparing fish oils enriched in CLA residues but still retaining their original n-3 fatty acid residues.

  4. Sulfanilic acid catalyzed solvent-free synthesis of 1,5-benzodiazepine derivatives

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Sulfanilic acid has been found to be an efficient catalyst for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones. This method is simple, effective and environmentally friendly and gives better yields.

  5. Ternary choline chloride/caffeic acid/ethylene glycol deep eutectic solvent as both a monomer and template in a molecularly imprinted polymer.

    Science.gov (United States)

    Fu, Najing; Liu, Xiao; Li, Liteng; Tang, Baokun; Row, Kyung Ho

    2017-05-01

    A molecularly imprinted polymer based on a ternary deep eutectic solvent comprised of choline chloride/caffeic acid/ethylene glycol was prepared. The caffeic acid in the ternary deep eutectic solvent was used as both a monomer and template. The molecularly imprinted polymer based on the ternary deep eutectic solvent was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, field-emission scanning electron microscopy, Brunauer-Emmett-Teller surface area analysis, atomic force microscopy, and elemental analysis. A series of molecularly imprinted polymers based on choline chloride/caffeic acid/ethylene glycol with different molar ratios was prepared and applied to the molecular recognition of polyphenols. A comparison of the recognition ability of molecularly imprinted polymers to polyphenols revealed that the choline chloride/caffeic acid/ethylene glycol (1:0.4:1, molar ratio) molecularly imprinted polymer had the best molecular recognition effect with 132 μg/g of protocatechuic acid, 104 μg/g of catechins, 80 μg/g of epicatechin, and 123 μg/g of caffeic acid in 6 h, as well as good molecular recognition ability for polyphenols from a Radix Asteris sample. These results show that the ternary deep eutectic solvent based molecularly imprinted polymer is a potential medium that can be applied to drug purification, drug delivery, and drug analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Solvent Effects on the Monomer/Hydrogen-Bonded Dimer Equilibrium in Carboxylic Acids: (+)-(S)-Ketopinic Acid as a Case Study.

    Science.gov (United States)

    Rodríguez Ortega, Pilar Gema; Montejo Gámez, Manuel; Márquez López, Fernando; López González, Juan Jesús

    2016-06-21

    The hydrogen-bond-assisted self-association process of a chiral semirigid carboxylic acid, namely, (+)-(S)-ketopinic acid, has been studied. The multiconformational monomer/dimer equilibrium has been evaluated by means of a concentration-dependent FTIR study that enabled the experimental equilibrium constants of the dimer formation reaction (Kdim ) to be determined in two solvents of different polarity. In CDCl3 , dimeric forms predominate, even in diluted solutions (KdimCF =5.074), whereas in CD3 CN the self-association process is hindered and monomers are always the main species, irrespective of solute concentration (KdimAN =0.194). The reliability of the dimerization constants and the derived mono- and dimeric experimental fractions have been proven by means of accurate matching between the experimental vibrational circular dichroism spectra of the species and the theoretical spectra generated by considering the simultaneous weighted contributions of the concomitant monomers and dimers.

  7. Effects of solvent polarity on the absorption and fluorescence spectra of chlorogenic acid and caffeic acid compounds: determination of the dipole moments.

    Science.gov (United States)

    Belay, Abebe; Libnedengel, Ermias; Kim, Hyung Kook; Hwang, Yoon-Hwae

    2016-02-01

    The effects of solvent polarity on absorption and fluorescence spectra of biologically active compounds (chlorogenic acid (CGA) and caffeic acids (CA)) have been investigated. In both spectra pronounced solvatochromic effects were observed with shift of emission peaks larger than the corresponding UV-vis electronic absorption spectra. From solvatochromic theory the ground and excited-state dipole moments were determined experimentally and theoretically. The differences between the excited and ground state dipole moment determined by Bakhshiev, Kawski-Chamma-Viallet and Reichardt equations are quite similar. The ground and excited-state dipole moments were determined by theoretical quantum chemical calculation using density function theory (DFT) method (Gaussian 09) and were also similar to the experimental results. The HOMO-LUMO energy band gaps for CGA and CFA were calculated and found to be 4.1119 and 1.8732 eV respectively. The results also indicated the CGA molecule is more stable than that of CFA. It was also observed that in both compounds the excited state possesses a higher dipole moment than that of the ground state. This confirms that the excited state of the hydroxycinnamic compounds is more polarized than that of the ground state and therefore is more sensitive to the solvent.

  8. Preparation of γ-aminopropyltriethoxysilane cross-linked poly(aspartic acid) superabsorbent hydrogels without organic solvent.

    Science.gov (United States)

    Meng, Hongyu; Zhang, Xin; Sun, Shenyu; Tan, Tianwei; Cao, Hui

    2016-01-01

    Poly(aspartic acid) (PASP) hydrogel is a type of biodegradable and biocompatible polymer with high water absorbing ability. Traditionally, the production of PASP hydrogel is expensive, complex, environmentally unfriendly, and consumes a large amount of organic solvents, e.g. dimethylformamide or dimethylsulfoxide. This study introduces a one-step synthesis of PASP resin, in which the organic phase was replaced by distilled water and γ-aminopropyltriethoxysilane was used as the cross-linker. Absorbent ability and characteristics were determined by swelling ratio, FTIR, (13)C SSNMR, and SEM. In vitro cytotoxicity evaluation and animal skin irritation tests showed the hydrogel has body-friendly properties. Preparing PASP hydrogel in aqueous solution is promising and finds its use in many applications.

  9. Determination of Activity Coefficients of di-(2-ethylhexyl) Phosphoric Acid Dimer in Select Organic Solvents Using Vapor Phase Osmometry

    Energy Technology Data Exchange (ETDEWEB)

    Michael F. Gray; Peter Zalupski; Mikael Nilsson

    2013-08-01

    Effective models for solvent extraction require accurate characterization of the nonideality effects for each component, including the extractants. In this study, the nonideal behavior of the industrial extractant di(2-ethylhexyl) phosphoric acid has been investigated using vapor pressure osmometry (VPO). From the osmometry data, activity coefficients for the HDEHP dimer were obtained based on a formulation of the regular solution theory of Scatchard and Hildebrand, and the Margules two- and three-suffix equations. The results show similarity with a slope-analysis based relation from previous literature, although important differences are highlighted. The work points towards VPO as a useful technique for this type of study, but care must be taken with the choice of standard and method of analysis.

  10. A study of parameters affecting the solvent extraction of lactic acid from fermentation broth

    Directory of Open Access Journals (Sweden)

    I. S. Udachan

    2014-09-01

    Full Text Available Lactic acid has recently been drawing much interest as a raw material for biodegradable polymer. One of the promising technologies for recovery of lactic acid from fermentation broth is reactive liquid - liquid extraction. Equilibrium studies on the reactive extraction of lactic acid with trioctylamine (TOA in various organic phases and its re-extraction into aqueous solutions were carried out. In this study distribution coefficient, extractability, stripping efficiency of various active and inert diluents with TOA as extractant were investigated, which were higher for active diluents. The effects of operating temperature, speed of agitation, agitation time and diluent composition on extraction efficiency were also studied. Temperature and extraction efficiency were inversely proportional to each other, whereas extraction efficiency was little affected by speed of agitation and agitation time.

  11. Application of microemulsions in determination of chromium naphthenate in gasoline by flame atomic absorption spectroscopy.

    Science.gov (United States)

    Du, B; Wei, Q; Wang, S; Yu, W

    1997-10-01

    A new method using microemulsified samples is presented. It is for the determination of chromium naphthenate in gasoline by flame absorption spectroscopy. The method has the advantage of simplicity, speed and the use of aqueous standards for calibration instead of organic standards. Coexistent elements do not disturb the determination. Results obtained by this method were better than those obtained by other methods for the same samples.

  12. Air formaldehyde and solvent concentrations during surface coating with acid-curing lacquers and paints in the woodworking and furniture industry.

    Science.gov (United States)

    Thorud, Syvert; Gjolstad, Merete; Ellingsen, Dag G; Molander, Paal

    2005-06-01

    An investigation of contemporary exposure to formaldehyde and organic solvents has been carried out during surface coating with acid-curing lacquers and paints in the Norwegian woodworking and furniture industry over a period of 3 years. The investigation covered 27 factories of different sizes and with different types of production, and totally 557 parallel formaldehyde and solvent samples were collected. The formaldehyde concentration (geometric mean) was 0.15 ppm (range 0.01-1.48 ppm) with about 10% of the samples exceeding the Norwegian occupational exposure limit of 0.5 ppm. The solvent concentration as additive effect (geometric mean) was 0.13 (range 0.0004-5.08) and about 5% of the samples exceeded the Norwegian occupational exposure limit. The most frequently occurring solvents from acid-curing lacquers were n-butyl acetate, ethanol, ethyl acetate and 1-butanol, which were found in 88-98% of the samples. Toluene, n-butyl acetate and 1-butanol were the only solvents with maximum concentrations exceeding their respective occupational exposure limits. Curtain painting machine operators were exposed to the highest concentrations of both formaldehyde (geometric mean 0.51 ppm, range 0.08-1.48 ppm) and organic solvents (additive effect, geometric mean 1.18, range 0.02-5.08). Other painting application work tasks such as automatic and manual spray-painting, manual painting and dip painting, showed on average considerably lower concentrations of both formaldehyde (geometric means 0.07-0.16 ppm) and organic solvents (additive effect, geometric mean 0.02-0.18). Non-painting work tasks also displayed moderate concentrations of formaldehyde (geometric means 0.11-0.17 ppm) and organic solvents (additive effect, geometric mean 0.04-0.07).

  13. Solvent Acidity and Basicity in Polar Media and their Role in Solvation

    Science.gov (United States)

    1994-04-20

    statistically less useful in LSERs (see Table 1). A related acidity scale is the Kosower Z which is based on the absorption bond associated with an...Koninklinge Dana. Vidensk. Selsk., 7 (1926). 12. U. Mayer, V. Gutmann, and W. Gerger, Monatsh. Chem., 106 (1975) 1235. 13. E.M. Kosower , J. Am. Chem. Soc

  14. Solvent-extractable lipids in an acid andic forest soil; variations with dept and season

    NARCIS (Netherlands)

    Naafs, Derck Ferdinand Werner; Bergen, P.F. van; Boogert, S.J.; Leeuw, J.W. de

    2004-01-01

    Total lipid extracts from an acid andic soil profile located on Madeira Island (Portugal) were analysed using gas chromatography (GC) and GC–mass spectrometry (GC/MS). The profile was covered mainly by grass. Bulk soil characteristics determined included soil pH (H2O) ranging from 4.5 to 4.0 and TOC

  15. The Salts of Fatty Acids as Precursors for Preparation of Silver Nanoparticles in Organic Solvents

    Directory of Open Access Journals (Sweden)

    V. N. Glushko

    2016-08-01

    Full Text Available The silver salts of fatty acids were studied as precursors for the preparation of colloidal dispersions of silver nanoparticles and UHMWPE (ultra-high-molecular-weight polyethylene composite with silver nanoparticles, as well as the composition, the spectra and SEM (scanning electron microscopy results.

  16. Solubility of R12 in Naphthenic Refrigeration Oil and in Squalane

    Science.gov (United States)

    Tanaka, Yoshiyuki; Nakata, Masami; Kubota, Hironobu; Makita, Tadashi

    A new apparatus has been designed and constructed in order to obtain reliable solubility data of refrigerants in refrigeration oils and was used to measure the solubilities of dichlorodifluoromethane (R12) into a naphthenic refrigeration oil and squalane C30H62, a model substance of lubricating oil with definite chemical structure and molecular weight, in the temperaturer range from 293 to 323 K under pressure up to 1.2 MPa. The uncertainty of the solubility data obtained is less than 1 %. The equilibrium pressure increases smoothly with increasing R12 composition up to saturated vapor pressure of R12 in both (R12 + naphthenic refrigeration oil) and (R12 + squalane) systems. The experimental data for (R 12 + naphthenic refrigeration oil) system were compared with literature vaJues. It was found the present results agreed quite well with literature values. For (R12 + squalane) system the activity coefficients of R 12 in liquid phase were calculated from the solubility data and the equation of state of R 12. The activity coefficients were correlated with the composition of liquid phase based on the Margules equation. The correlating equation obtained can reproduce the experimental data with a mean deviation of 2.3 %.

  17. The Role of Concentration and Solvent Character in the Molecular Organization of Humic Acids

    Directory of Open Access Journals (Sweden)

    Martina Klučáková

    2016-10-01

    Full Text Available The molecular organization of humic acids in different aqueous solutions was studied over a wide concentration range (0.01–10 g·dm−3. Solutions of humic acids were prepared in three different media: NaOH, NaCl, and NaOH neutralized by HCl after dissolution of the humic sample. Potentiometry, conductometry, densitometry, and high resolution ultrasound spectrometry were used in order to investigate conformational changes in the humic systems. The molecular organization of humic acids in the studied systems could be divided into three concentration ranges. The rearrangements were observed at concentrations of ~0.02 g·dm−3 and ~1 g·dm−3. The first “switch-over point” was connected with changes in the hydration shells of humic particles resulting in changes in their elasticity. The compressibility of water in the hydration shells is less than the compressibility of bulk water. The transfer of hydration water into bulk water increased the total compressibility of the solution, reducing the ultrasonic velocity. The aggregation of humic particles and the formation of rigid structures in systems with concentrations higher than 1 g·dm−3 was detected.

  18. The Solvent Extraction of Cadmium From Phosphoric Acid Solution By3-Methyl-Quinoxaline-2-Thione in Toluene Diluent

    Directory of Open Access Journals (Sweden)

    anae Baki Senhaji

    2016-12-01

    Full Text Available The solvent extraction of cadmium (II from phosphoric acid 2.5M by 3-methyl-2 (1H-quinoxaline-thione Vol32No6_SOLV_SANA_for1 is investigated in various experimental conditions. Obtained results show a variation of extraction of Cd with pH, and Vol32No6_SOLV_SANA_for2 concentration. The conventional methods of slope analysis can’t be performed successfully for understanding interaction mechanisms. A technique combining slope analysis with the variation of overall extraction constant with pH is performed in this case. There is no predominant removal mechanism, cadmium is extracted as complexes in Vol32No6_SOLV_SANA_for3 stoichiometry varying between 1:1:0 and 1:3:3. The extraction reaction is a complex process including ion exchange-ion pair formation,organic and inorganic complexation, H3PO4deprotonation and solvatation phenomena. A best recovery of 43 to 60% is achieved in acidic conditions with CLH = 0.26M

  19. A viscous solvent enables information transfer from gene-length nucleic acids in a model prebiotic replication cycle

    Science.gov (United States)

    He, Christine; Gállego, Isaac; Laughlin, Brandon; Grover, Martha A.; Hud, Nicholas V.

    2017-04-01

    Many hypotheses concerning the nature of early life assume that genetic information was once transferred through the template-directed synthesis of RNA, before the emergence of coded enzymes. However, attempts to demonstrate enzyme-free, template-directed synthesis of nucleic acids have been limited by 'strand inhibition', whereby transferring information from a template strand in the presence of its complementary strand is inhibited by the stability of the template duplex. Here, we use solvent viscosity to circumvent strand inhibition, demonstrating information transfer from a gene-length template (>300 nt) within a longer (545 bp or 3 kb) duplex. These results suggest that viscous environments on the prebiotic Earth, generated periodically by water evaporation, could have facilitated nucleic acid replication—particularly of long, structured sequences such as ribozymes. Our approach works with DNA and RNA, suggesting that viscosity-mediated replication is possible for a range of genetic polymers, perhaps even for informational polymers that may have preceded RNA.

  20. Sulfamic acid: An efficient, cost-effective and green catalyst for crossed-aldol condensation of ketones with aromatic aldehydes under solvent-free

    Institute of Scientific and Technical Information of China (English)

    Amin Rostami; Firoz Ahmad-Jangi

    2011-01-01

    Aromatic aldehydes undergo crossed-aldol condensation with ketones in the presence of catalytic amount of sulfamic acid (SA) to afford the corresponding α,β-unsaturated aldol products under solvent-free conditions in good to high yields at 45-80 ℃.

  1. Trichloroisocyanuric acid as an efficient homogeneous catalyst for the chemoselective synthesis of 2-substituted oxazolines, imidazolines and thiazolines under solvent-free condition

    Directory of Open Access Journals (Sweden)

    Hojati Fatemeh Seyedeh

    2012-01-01

    Full Text Available Trichloroisocyanuric acid as a commercially available and inexpensive catalyst has been used in a new, facile and efficient procedure for the synthesis of 2-oxazolines, 2-imidazolines and 2-thiazolines through the reaction of nitriles with 2-aminoethanol, ethylenediamine or 2-aminoethanthiol under solvent -free conditions.

  2. Synthesis of 1-amidoalkyl-2-naphthols based on a three-component reaction catalyzed by boric acid as a solid heterogeneous catalyst under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Zahed Karimi-Jaberi

    2012-12-01

    Full Text Available An efficient method for the preparation of 1-amidoalkyl-2-naphthols has been described using a multi-component, one-pot condensation reaction of 2-naphthol, aldehydes and amides in the presence of boric acid under solvent-free conditions.DOI: http://dx.doi.org/10.4314/bcse.v26i3.18

  3. Melamine trisulfonic acid as a highly efficient catalyst for the synthe-sis of 14-aryl-14H-dibenzo[a,j]xanthenes under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Abdolkarim Zare

    2014-02-01

    Full Text Available Melamine trisulfonic acid (MTSA is utilized as a highly efficient catalyst for the solvent-free condensation of 2-naphthol with arylaldehydes under conventional thermal or microwave irradiation to give 14-aryl-14H-dibenzo[a,j]xanthenes in high to excellent yields and in short reaction times.

  4. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .3. EFFECT OF SULFOLANE ON THE EQUILIBRIUM CONVERSION

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1992-01-01

    The liquid-phase hydration of cyclohexene, a pseudo-first-order reversible reaction catalyzed by a strong acid ion-exchange resin, was investigated in solvent mixtures of water and sulfolane. Macroporous Amberlite XE 307 was used because of its superior catalytic activity. Chemical equilibrium conve

  5. Solvent effect on molecular structure, IR spectra, thermodynamic properties and chemical stability of zoledronic acid: DFT study.

    Science.gov (United States)

    Liu, Qingzhu; Qiu, Ling; Wang, Yang; Lv, Gaochao; Liu, Guiqing; Wang, Shanshan; Lin, Jianguo

    2016-04-01

    Zoledronic acid (ZL) has been used widely for treating skeletal diseases because of its high potency in inhibiting bone resorption. A detailed understanding of its physicochemical characteristics may be of great significance in both medicinal chemistry and structural biology for the design of novel bisphosphonates with higher activity. In the present work, the monoclinic (IM) and triclinic (IT) polymorphs of ZL in the gas phase and the aqueous phase were studied by density functional theory (DFT) method at the B3LYP/6-311++G** level. The polarizable continuum model (PCM) was employed to study the solvent effect on structures and properties. The optimized IM and IT conformations in both phases are in reasonable agreement with the experimental structures with the overall mean absolute percent deviation (MAPD%) less than 3.1 %. The presence of intramolecular hydrogen bond within both conformations was identified in the solvent. The IR spectra were simulated and assigned in detail, which agreed well with the experimental data. The intramolecular hydrogen bonding interactions resulted in the shift of vibrational frequencies of hydroxyl to the low band by 12-22 cm(-1) and 24-26 cm(-1) for IM and IT conformations, respectively. Their thermodynamic properties were also calculated based on the harmonic vibrational analysis, including standard heat capacity (C(°)p,m), entropy (S(°)m), and enthalpy (H(°)m). The molecular stability, hydrogen bonding interaction and other electronic properties have been further analyzed by the natural bond orbital (NBO), atoms in molecules (AIM), molecular electrostatic potential (MEP) and frontier molecular orbital (FMO) analysis.

  6. Obtention of Free Fatty Acids of Macauba Oil (Acrocomia Aculeata in Organic Solvent Free System

    Directory of Open Access Journals (Sweden)

    Caroline Portilho Trentini

    2014-05-01

    Full Text Available The present study aimed to investigate the enzymatic hydrolysis of oil Macaúba, to obtain a hydrolyzate rich in free fatty acids (FFA for later use in step esterification. The effect of process variables (percentage of catalyst, temperature and water content was evaluated in the FFA yield, using a factorial experimental design 23, where the positive and significant effect of the variables was observed. The results reported yields of 50.5% in FFA in 6 hours of reaction at 60ºC, water percentage of 15 wt% and catalyst percentage of 5 wt%.

  7. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions.

    Science.gov (United States)

    Brun, Elodie; Safer, Abdelmounaim; Carreaux, François; Bourahla, Khadidja; L'helgoua'ch, Jean-Martial; Bazureau, Jean-Pierre; Villalgordo, Jose Manuel

    2015-06-23

    We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  8. Microwave-Assisted Condensation Reactions of Acetophenone Derivatives and Activated Methylene Compounds with Aldehydes Catalyzed by Boric Acid under Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Elodie Brun

    2015-06-01

    Full Text Available We here disclosed a new protocol for the condensation of acetophenone derivatives and active methylene compounds with aldehydes in the presence of boric acid under microwave conditions. Implementation of the reaction is simple, healthy and environmentally friendly owing to the use of a non-toxic catalyst coupled to a solvent-free procedure. A large variety of known or novel compounds have thus been prepared, including with substrates bearing acid or base-sensitive functional groups.

  9. The solution properties of mefenamic acid and a closely related analogue are indistinguishable in polar solvents but significantly different in nonpolar environments.

    Science.gov (United States)

    Lee, Eun Hee; Byrn, Stephen R; Pinal, Rodolfo

    2012-12-01

    This study investigates the cosolute effects of mefenamic acid (XA) and flufenamic acid (FA). These compounds serve as model of a drug discovery lead compound and a structural analogue. The activity coefficients of XA and FA in different solvents were obtained from solubility measurements at 25°C. The effect of varying concentrations of FA on the solubility of XA in four different solvents, including toluene, cyclohexane, ethanol, and an ethanol-water mixture (80:20, v/v), was investigated. The magnitude of change in the activity coefficient of XA in the presence of FA in different solvents was used to elucidate the thermodynamic effect of FA on the solubility of XA. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy were used to obtain molecular level information about the interactions of the compounds in solution. The presence of FA increases XA solubility in toluene and in cyclohexane as much as seven-fold. Conversely, in ethanol and the ethanol-water mixture, similar levels of FA have essentially no effect on the solubility of XA. The solution properties investigated show that despite the close structural similarity between XA and FA, the two compounds are strongly distinguishable in nonpolar solvents. Conversely, the solution properties of the same two solutes are indistinguishable in polar solvents. A solubilization model based on solute-cosolute interactions is presented.

  10. SEPARATION OF SATURED AND UNSATURATED FATTY ACIDS FROM PALM FATTY ACIDS DISTILLATES IN CONTINUOUS MULTISTAGE COUNTERCURRENT COLUMNS WITH SUPERCRITICAL CARBON DIOXIDE AS SOLVENT: A PROCESS DESIGN METHODOLOGY

    Directory of Open Access Journals (Sweden)

    Nélio Teixeira MACHADO

    1997-12-01

    Full Text Available In this work the separation of multicomponent mixtures in counter-current columns with supercritical carbon dioxide has been investigated using a process design methodology. First the separation task must be defined, then phase equilibria experiments are carried out, and the data obtained are correlated with thermodynamic models or empirical functions. Mutual solubilities, Ki-values, and separation factors aij are determined. Based on this data possible operating conditions for further extraction experiments can be determined. Separation analysis using graphical methods are performed to optimize the process parameters. Hydrodynamic experiments are carried out to determine the flow capacity diagram. Extraction experiments in laboratory scale are planned and carried out in order to determine HETP values, to validate the simulation results, and to provide new materials for additional phase equilibria experiments, needed to determine the dependence of separation factors on concetration. Numerical simulation of the separation process and auxiliary systems is carried out to optimize the number of stages, solvent-to-feed ratio, product purity, yield, and energy consumption. Scale-up and cost analysis close the process design. The separation of palmitic acid and (oleic+linoleic acids from PFAD-Palm Fatty Acids Distillates was used as a case study.

  11. Solvent-selective membranes for automating sequential liquid release and routing of nucleic acid purification protocols on a simple spindle motor

    OpenAIRE

    Gaughran, Jennifer; Kinahan, David J.; Mishra, Rohit; Ducrée, Jens

    2016-01-01

    By incorporating a set of membranes which selectively dissolve upon contact with aqueous or or-ganic solvents at strategic locations on a disc cartridge, we succeeded to fully automate the solid-phase extraction of nucleic acids by varying the spin rate of a low-cost spindle motor. A solvent- and phase-selective graphene oxide (GO) membrane governs the routing of flows to designated elution and waste chambers. The serial release of on-board sample and reagents is centrifugo-pneumatically con...

  12. Solvent extraction of neodymium(Ⅲ ) from acidic nitrate medium using Cyanex 921 in kerosene

    Institute of Scientific and Technical Information of China (English)

    Nandita Panda; Niharbala Devi; Sujata Mishra

    2012-01-01

    The extraction of neodymium(Ⅲ ) from acidic nitrate medium was investigated using Cyanex 921 as extractant in kerosene.The metal concentration in the aqueous phase before and after extraction was determined spectrophotometrically by Arsenazo Ⅲ method.The complete equilibration was achieved in 15 min.The effects of shaking time,nitric acid concentration,nitrate concentration,extractant concentration,and temperature on the extraction were studied.The extraction of Nd(Ⅲ) was found to increase very slowly with increase in concentration of HNO3 in the range of 0.001-0.008 mol/L and then decreased when 0.01 mol/L HNO3 was used.The percentage of extraction was increased with increase in nitrate concentration from 0.01-0.45 mol/L and then decreased when nitrate concentration increased to 0.5 mol/L.Quantitative extraction of Nd(Ⅲ) (98%) was obtained from the aqueous phase containing 0.001 mol/L HNO3 and 0.1 mol/L KNO3 using 0.5mol/L Cyanex 921.On the basis of slope analysis,the extracted complex in the organic phase was proposed to be Nd(NO3)3.2Cyanex 921.The extraction of Nd(Ⅲ) was found to increase with increase in concentration of metal ion in the range of 0.001-0.05 mol/L from 0.001mol/L HNO3 and 0.1 mol/L KNO3 with 0.1 mol/L Cyanex 921.The percentage of extraction of neodymium was found to decrease with increase in temperature.From temperature variation studies,the negative value of △H indicated the extraction reaction to be exothermic and the negative value of △S indicated the formation of a stable complex.Almost 100% Nd(Ⅲ) was recovered from the fully loaded organic phase using 0.002 mol/L H2SO4 and 0.01 mol/L HC1.

  13. Countercurrent Chromatographic Separation of Lipophilic Ascorbic Acid Derivatives and Extract from Kadsura Coccinea Using Hydrophobic Organic-Aqueous Two-Phase Solvent Systems.

    Science.gov (United States)

    Shinomiya, Kazufusa; Li, Heran; Kitanaka, Susumu; Ito, Yoichiro

    2009-01-01

    Countercurrent chromatographic (CCC) separation of lipophilic ascorbic acid derivatives and the crude extract from Kadsura Coccinea was performed using the type-J multilayer coil planet centrifuge with a hydrophobic organic-aqueous two-phase solvent system composed of n-hexane/ethyl acetate/ethanol/aqueous 0.1% trifluoroacetic acid at the volume ratio of (5 : 5 : 6 : 2). The lipophilic ascorbic acid derivatives were separated in the order of L-ascrobyl 2,6-dibutyrate, L-ascorbyl 6-palmitate and L-ascorbyl 6-stearate by eluting the lower phase as the mobile phase, and L-ascorbyl 2,6-dipalmitate was separated by eluting the upper phase at the opposite direction. The above solvent system was then applied to the CCC separation of the extract prepared from K. coccinea. With lower phase mobile, the extract was mainly separated into two peaks corresponding to lignans and triterpenoids accordingly. The HPLC analysis of the fractions showed that the former peak contained Kadsulignan N, Schizandrin H and Neokadsuranin as lignans, and the latter peak, Micranoic acid A, Neokadsuranic acid B and beta-Sitosterol as triterpenoids. The overall results indicate that the hydrophobic organic-aqueous two-phase solvent system used in the present studies was useful for the CCC separation of lignans and triterpenoids present in the natural products.

  14. Halogenated solvent remediation

    Science.gov (United States)

    Sorenson, Kent S.

    2004-08-31

    Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

  15. A time-resolved spectroscopy and density functional theory study of the solvent dependent photochemistry of fenofibric acid.

    Science.gov (United States)

    Li, Ming-De; Ma, Jiani; Su, Tao; Liu, Mingyue; Phillips, David Lee

    2013-02-07

    The solvent dependent photochemistry of fenofibric acid (FA) was studied by femtosecond transient absorption and nanosecond time-resolved resonance Raman experiments and density functional theory calculations. In acetonitrile-rich solution, a typical nπ* triplet state FA ((3)FA) is formed through a highly efficient intersystem crossing and then the (3)FA species undergoes some reaction with water to generate a ketyl radical intermediate at low water concentrations. In contrast, nπ* (3)FA changes from a reaction with water to generate a ketyl radical intermediate at lower water concentrations to a decarboxylation reaction with the assistance of water molecules to produce a biradical intermediate at higher water concentrations in water-rich solutions. The decarboxylation reaction leads to the formation of the FA carbanion in 50% phosphate buffer solution and the FA carbanion is observed on the picosecond to nanosecond time scale and the cleavage of the FA carbanion gives rise to the enolate 3(-) anion at later nanosecond delay times. As regards fenofibrate (FB), it only exhibits a benzophenone-like photochemistry, which consists of some reaction with water to generate a ketyl radical intermediate, being observed in the different aqueous solutions.

  16. Spectrophotometric and spectroscopic studies of charge transfer complexes of p-toluidine as an electron donor with picric acid as an electron acceptor in different solvents.

    Science.gov (United States)

    Singh, Neeti; Khan, Ishaat M; Ahmad, Afaq

    2010-04-01

    The charge transfer complexes of the donor p-toluidine with pi-acceptor picric acid have been studied spectrophotometrically in various solvents such as carbon tetrachloride, chloroform, dichloromethane acetone, ethanol, and methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (K(CT)), molar extinction coefficient (epsilon(CT)), standard free energy (DeltaG(o)), oscillator strength (f), transition dipole moment (mu(EN)), resonance energy (R(N)) and ionization potential (I(D)). The results indicate that the formation constant (K(CT)) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used.

  17. Spectrophotometric studies on the charge-transfer interaction between p-nitroaniline with chloranilic acid as π-acceptor in different polar solvents

    Science.gov (United States)

    Singh, Neeti; Ahmad, Afaq

    2017-01-01

    The charge transfer interaction between the donor p-nitroaniline with the acceptor chloranilic acid has been studied spectrophotometrically in various solvents such as chloroform, ethanol, and methanol at room temperature. The results indicate that formation of CTC in non-polar solvent is high. The stoichiometry of the complex was found to be 1:1 ratio by straight-line method between donor and acceptor with maximum absorption bands. The data are discussed in terms of formation constant (KCT), molar extinction coefficient (εCT), standard free energy (ΔG), oscillator strength (f), transition dipole moment (μN), resonance energy (RN) and ionization potential (ID). The results indicate that the formation constant (KCT) for the complex was shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents that were used. The formation of the complex has been confirmed by UV-visible, FT-IR, and 1H NMR techniques.

  18. Modelling copper solvent extraction from acidic sulphate solutions using MOC 45

    Directory of Open Access Journals (Sweden)

    Alguacil, F. J.

    1998-05-01

    Full Text Available A mathematical model to predict the extraction has been developed for the Cu-MOC 45 system. The model consists of sets of nonlinear mass action and mass balance equations where the dimerization of the oxime was also considered. The predictive model calculated the equilibrium concentrations from the total oxime concentration, total copper concentration, initial pH value and the O/A volume phase ratio. The model suggests that the extraction of copper can be defined by the existence of two species into the organic solution: CuR2 (kext = 4.2 and Cu(HR22 (kext = 10.000- The initial oxime concentration defines the predominancy in the organic solution of both species. The model can be used to predict copper extraction isotherm as well as copper stripping with sulphuric acid.

    Se desarrolla un modelo matemático para predecir el proceso de extracción en el sistema Cu-MOC 45. El modelo consiste en un conjunto de ecuaciones en el que se considera la dimerización de la oxima. El modelo permite predecir la extracción a partir de las concentraciones totales de la oxima y del cobre, del pH inicial y de la relación de fases O/A. La extracción de cobre responde a la existencia de dos especies en la fase orgánica: CuR2 (kext = 4,2 y Cu(HR22 (kext = 10.000. La predominancia de una u otra especie en esta fase depende de la concentración inicial de la oxima. El modelo también puede predecir las isotermas de extracción y la reextracción de cobre mediante ácido sulfúrico.

  19. Nanostructured alkyl carboxylic acid-based restricted access solvents: Application to the combined microextraction and cleanup of polycyclic aromatic hydrocarbons in mosses.

    Science.gov (United States)

    Caballero-Casero, N; Çabuk, H; Martínez-Sagarra, G; Devesa, J A; Rubio, S

    2015-08-26

    Alkyl carboxylic acid-based nanostructured solvents, synthesized in mixtures of tetrahydrofuran (THF) and water through self-assembly and coacervation, were proved to behave as restricted access liquids. Both physical and chemical mechanisms were found responsible for exclusion of macromolecules such as proteins and polysaccharides. The potential of these solvents for extracting small molecules from complex solid samples, without interference from large biomolecules, was here evaluated. For this purpose, they were applied to the extraction of 14 priority polycyclic aromatic hydrocarbons (PAHs) from mosses prior to their separation by liquid chromatography and fluorescence detection (LC-FLD). Sample treatment involved the vortex shaking of 200 mg of moss with 200 μL of decanoic acid-based solvent for 5 min, subsequent centrifugation for 8 min and analysis of the extract by LC-FLD using external calibration. Proteins precipitated during extraction because of both the decrease of the dielectric constant of the solution caused by THF and the formation of macromolecular complexes with decanoic acid. Polysaccharides were not solubilized in the aqueous cavities of the solvent because of their size exclusion. In-house method validation was performed according to the recommendations of the European Commission Decision 202/657/EC. Method detection and quantification limits for the different PAHs were in the ranges 0.04-0.24 and 0.14-0.80 μg kg(-1), respectively. The method was applied to the determination of different moss species collected in both polluted and unpolluted sites in the South of Spain. Recoveries were within the range 71-110%. The results obtained show that solvents with restricted access properties have the potential to expand the scope of application of restricted access materials to areas other than biological fluids because of their suitability to combine analyte isolation and sample cleanup of solid samples in a single step.

  20. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path.

    Science.gov (United States)

    Daschakraborty, Snehasis; Kiefer, Philip M; Miller, Yifat; Motro, Yair; Pines, Dina; Pines, Ehud; Hynes, James T

    2016-03-10

    The protonation of methylamine base CH3NH2 by carbonic acid H2CO3 within a hydrogen (H)-bonded complex in aqueous solution was studied via Car-Parrinello dynamics in the preceding paper (Daschakraborty, S.; Kiefer, P. M.; Miller, Y.; Motro, Y.; Pines, D.; Pines, E.; Hynes, J. T. J. Phys. Chem. B 2016, DOI: 10.1021/acs.jpcb.5b12742). Here some important further details of the reaction path are presented, with specific emphasis on the water solvent's role. The overall reaction is barrierless and very rapid, on an ∼100 fs time scale, with the proton transfer (PT) event itself being very sudden (water solvent changes little until the actual PT occurrence; this results from the very strong driving force for the reaction, as indicated by the very favorable acid-protonated base ΔpKa difference. Further solvent rearrangement follows immediately the sudden PT's production of an incipient contact ion pair, stabilizing it by establishment of equilibrium solvation. The solvent water's short time scale ∼120 fs response to the incipient ion pair formation is primarily associated with librational modes and H-bond compression of water molecules around the carboxylate anion and the protonated base. This is consistent with this stabilization involving significant increase in H-bonding of hydration shell waters to the negatively charged carboxylate group oxygens' (especially the former H2CO3 donor oxygen) and the nitrogen of the positively charged protonated base's NH3(+).

  1. Improved biocompatibility of novel poly(L-lactic acid/ß-tricalcium phosphate scaffolds prepared by an organic solvent-free method

    Directory of Open Access Journals (Sweden)

    Zhao XF

    2011-07-01

    Full Text Available Xue-Feng Zhao1,2, Xiao-Dong Li3, Yun-Qing Kang4, Quan Yuan1,21State Key Laboratory of Oral Diseases, Sichuan University, Chengdu, People's Republic of China; 2West China School of Stomatology, Sichuan University, Chengdu, People's Republic of China; 3Affiliated Hospital of Stomatology and College of Stomatology, Chongqing Medical University, Chongqing, People's Republic of China; 4College of Materials Science and Engineering, Sichuan University, Chengdu, People's Republic of ChinaAbstract: A porous poly(L-lactic acid/ß-tricalcium phosphate (PLLA/ß-TCP composite scaffold was fabricated using a novel technique comprising powder mixing, compression molding, low-temperature treatment, and particulate leaching without any organic solvent. The effect of this scaffold on osteoblast proliferation and differentiation was evaluated in vitro. The fabricated scaffold had a homogeneously interconnected porous structure with a porosity of 70% and compressive strength of 1.35 MPa. The methylthiazol tetrazolium values and alkaline phosphatase (ALP activity of osteoblasts seeded on the solvent-free scaffold were significant higher than those of the control. Using real-time PCR, gene expressions of ALP, osteocalcin, and type 1 collagen were shown to be upregulated. As the method does not use any organic solvent, it eliminates problems associated with organic solvent residue and therefore improves the cell compatibility. It has a promising potential for the preparation of porous scaffold for bone tissue engineering.Keywords: biocompatibility, biomaterials, composites, poly(L-lactic acid, ß-tricalcium phosphate

  2. Solvent degradation products in nuclear fuel processing solvents

    Energy Technology Data Exchange (ETDEWEB)

    Shook, H.E. Jr.

    1988-06-01

    The Savannah River Plant uses a modified Purex process to recover enriched uranium and separate fission products. This process uses 7.5% tri-n-butyl phosphate (TBP) dissolved in normal paraffin hydrocarbons for the solvent extraction of a nitric acid solution containing the materials to be separated. Periodic problems in product decontamination result from solvent degradation. A study to improve process efficiency has identified certain solvent degradation products and suggested mitigation measures. Undecanoic acid, lauric acid, and tridecanoic acid were tentatively identified as diluent degradation products in recycle solvent. These long-chain organic acids affect phase separation and lead to low decontamination factors. Solid phase extraction (SPE) was used to concentrate the organic acids in solvent prior to analysis by high performance liquid chromatography (HPLC). SPE and HPLC methods were optimized in this work for analysis of decanoic acid, undecanoic acid, and lauric acid in solvent. Accelerated solvent degradation studies with 7.5% TBP in normal paraffin hydrocarbons showed that long-chain organic acids and long-chain alkyl butyl phosphoric acids are formed by reactions with nitric acid. Degradation of both tributyl phosphate and hydrocarbon can be minimized with purified normal paraffin replacing the standard grade presently used. 12 refs., 1 fig., 3 tabs.

  3. Synthesis and Evaluation of Naphthenic Sulphonate Used for Enhancing Oil Recovery%新型三次采油用环烷基磺酸盐的制备与评价

    Institute of Scientific and Technical Information of China (English)

    郑学芳; 廉琪; 朱红; 王芳辉; 贾丹丹; 王东军

    2013-01-01

    在实验室用发烟硫酸对环烷基润滑油进行磺化反应,然后经过氨水中和,制备新型环烷基磺酸盐驱油剂。最佳反应条件为:反应温度为70℃,发烟硫酸与环烷基润滑油体积比为1:4,反应时间为10 h。对产物用红外光谱、核磁共振1H、元素分析进行结构分析后显示,产物为饱和的环烷基磺酸盐。对产物进行界面活性性能测试,结果表明该驱油剂在不加碱及其他助剂的情况下,能使胜利油田孤东三区、四区、六区、七区的油水界面张力降低到超低值10-3 mN×m-1及以下,最低值达到6×10-4 mN×m-1。该驱油剂抗盐能力优异,在NaCl浓度为(2.5~17)×103 mg×L-1以及Ca2+、Mg2+离子浓度低于500 mg×L-1时都有较好的驱油能力。%A novel naphthenic sulphonate was prepared in laboratory by sulphonation of the naphthenic lubricating oil with fuming sulfuric acid. The optimum preparation reaction temperature found is 70℃, the optimum volume ratio of fuming sulfuric acid to naphthenic lubricating oil is 1:4, the optimum reaction time is 10 h. The structure of the product was characterized by infrared spectra, 1H-NMR and elemental analysis. The results indicate that the product is saturated naphthenic sulphonate. The evaluation of the interfacial activity properties of the product shows that, when the naphthenic sulphonate was used in several blocks in Shengli oilfield without alkali and other additives, the interfacial tension between crude oil and water could be reduce to a ultra-low value, such as low as 10-3 mN×m-1, and the lowest value of the interfacial tension can be reduced to 6×10-4 mN×m-1. The naphthenic sulphonate possesses good salt-resisting capacity, even when the concentration of NaCl is in the range of 2.5×103 mg×L-1 to 17×103 mg×L-1, or the concentration of Ca2+and Mg2+is below 500 mg×L-1, it still can reduce the oil-water interfacial tension to 10-3 mN×m-1.

  4. Solvent-free oxidation of aldehydes to acids by TBHP using environmental-friendly MnO$^{−1}_{4}$-exchanged Mg-Al hydrotalcite catalyst

    Indian Academy of Sciences (India)

    Vasant R Choudhary; Deepa K Dumbre; Vijay S Narkhede

    2012-07-01

    A number of hydrotalcite (Mg-Al, Mn-Al, Co-Al, Ni-Al, Mg-Fe, Mg-Cr and Cu-Al) catalysts, with or without MnO$^{−1}_{4}$-exchange, were evaluated for their performance in the solvent-free oxidation of benzaldehyde to benzoic acid by tert-butyl hydroperoxide under reflux in the absence of any solvent. The MnO$^{−1}_{4}$-exchanged Mg-Al-hydrotalcite (Mg/Al = 10) showed high activity in the oxidation of different aromatic and aliphatic aldehydes to their corresponding acids and also showed excellent reusability in the oxidation process which is environmental-friendly.

  5. Choline chloride (ChCl) and monosodium glutamate (MSG)-based green solvents from optimized cactus malic acid for biomass delignification.

    Science.gov (United States)

    Yiin, Chung Loong; Quitain, Armando T; Yusup, Suzana; Uemura, Yoshimitsu; Sasaki, Mitsuru; Kida, Tetsuya

    2017-08-10

    This work aimed to develop an efficient microwave-hydrothermal (MH) extraction of malic acid from abundant natural cactus as hydrogen bond donor (HBD) whereby the concentration was optimized using response surface methodology. The ideal process conditions were found to be at a solvent-to-feed ratio of 0.008, 120°C and 20min with 1.0g of oxidant, H2O2. Next generation environment-friendly solvents, low transition temperature mixtures (LTTMs) were synthesized from cactus malic acid with choline chloride (ChCl) and monosodium glutamate (MSG) as hydrogen bond acceptors (HBAs). The hydrogen-bonding interactions between the starting materials were determined. The efficiency of the LTTMs in removing lignin from oil palm biomass residues, empty fruit bunch (EFB) was also evaluated. The removal of amorphous hemicellulose and lignin after the pretreatment process resulted in an enhanced digestibility and thermal degradability of biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Conformational preferences of 3-(dimethylazinoyl)propanoic acid as a function of pH and solvent; intermolecular versus intramolecular hydrogen bonding.

    Science.gov (United States)

    Nkansah, Richard A; Liu, Yang; Alley, Olivia J; Gerken, James B; Drake, Michael D; Roberts, John D

    2009-03-20

    The conformational equilibrium of 3-(dimethylazinoyl)propanoic acid (DMAPA, azinoyl = N(+)(O(-)) has a weak pH-dependence in D(2)O, with a slight preference for trans in alkaline solutions. The acid ionization constants of the protonated amine oxide and carboxylic functional groups as determined by NMR spectroscopy were 7.9 x 10(-4) and 6.3 x 10(-6), respectively. The corresponding value of K(1)/K(2) of 1.3 x 10(2) is not deemed large enough to provide experimental NMR evidence for a significant degree of intramolecular hydrogen bonding in D(2)O. Conformational preferences of DMAPA are mostly close to statistical (gauche/trans = 2/1) in other protic solvents, e.g., alcohols. However, the un-ionized form of DMAPA appears to be strongly intramolecularly hydrogen-bonded and gauche in aprotic solvents.

  7. An efficient Biginelli one-pot synthesis of new benzoxazole-substituted dihydropyrimidinones and thiones catalysed by trifluoro acetic acid under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    D.Shobha; M.Adharvana Chari; K.H.Ahn

    2009-01-01

    An efficient synthesis of benzoxazole-substituted 3,4-dihydropyrimidinones(DHPMs)using trifluoro acetic acid as the catalyst for the first time from an aldehyde,β-keto ester and benzoxazole-substituted urea/thiourea under solvent-free conditions is described.Compared to the classical Biginelli reaction conditions,this new method consistently has the advantage of excellent yields(80-91%)and short reaction time(40-130 min)at reflux temperature.

  8. Knoevenagel condensation of α,β-unsaturated aromatic aldehydes with barbituric acid under non-catalytic and solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    An efficient route for the synthesis of 5-(arylpropenylidine)-2,4,6-pyrimidinetrione 3 from an appropriate α,β-unsaturated aromatic aldehydes 1 and barbituric acid 2 under both non-catalytic and solvent-free microwave irradiation conditions was described. In this way, a range of biologically important compounds 3 was obtained in good to excellent yields (86-98 %) in a very short reaction time (30-80 s).

  9. Co-precipitation of asiatic acid and poly( l-lactide) using rapid expansion of subcritical solutions into liquid solvents

    Science.gov (United States)

    Sane, Amporn; Limtrakul, Jumras

    2011-09-01

    Poly( l-lactide) (PLLA) nanoparticles loaded with asiatic acid (AA) were successfully produced by rapid expansion of a subcritical solution into an aqueous receiving solution containing a dispersing agent. A mixture of carbon dioxide (CO2) and ethanol (EtOH) with a weight ratio of 1:1 was used as the solvent for AA and PLLA. Two surfactants, Pluronic F127 and sodium dodecyl sulfate were employed. The former was found to be more effective for stabilizing AA-loaded PLLA nanoparticles, as a rapid expansion into a 0.1 wt% Pluronic F127 solution produced a stable nanosuspension consisting mainly of well-dispersed, individual nanoparticles. The effects of rapid expansion-processing conditions—AA to PLLA weight ratio and pre-expansion temperature (Tpre)—on the size and morphology of composite nanoparticles, and the loading capacity and entrapment efficiency of AA in PLLA nanoparticles, were systematically investigated. It was found that AA-loaded PLLA nanoparticles with a size range of 30-100 nm were consistently fabricated by rapid expansion at Tpre of 70-100 °C and AA to PLLA weight ratios of 1:2 and 1:4, and with a constant pre-expansion pressure of 330 bar. The Tpre and AA to PLLA weight ratio had no significant effects on the size of the nanoparticles. The AA to PLLA weight ratio is a controlling parameter for both the loading capacity and the entrapment efficiency of AA in PLLA nanoparticles. The loading capacity and entrapment efficiency increased from 8-11 to 16-21 wt%, and 38-57 to 50-62 wt%, respectively, when the AA to PLLA weight ratio changed from 1:4 to 1:2. However, increasing the Tpre from 70 to 100 °C decreased both the loading capacity and entrapment efficiency of AA in PLLA nanoparticles by 20-30%.

  10. 5-Hydroxymethylfurfural (5-HMF Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal Conditions and Potential of Concentrated Aqueous Organic Acids as Reactive Solvent System

    Directory of Open Access Journals (Sweden)

    Nadine Essayem

    2012-09-01

    Full Text Available 5-Hydroxymethylfurfural (5-HMF is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Brønsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/glucose ratio is used. By contrast, we disclose in this work that the reaction of fructose in concentrated aqueous solutions of carboxylic acids, formic, acetic or lactic acids, used as reactive solvent media, leads to the selective dehydration of fructose in 5-HMF with yields up to 64% after 2 hours at 150 °C. This shows the potential of such solvent systems for the clean and easy production of 5-HMF from carbohydrates. The influence of adding solid catalysts to the carboxylic acid media was also reported, starting from glucose.

  11. Effect of solvent on drug release and a spray-coated matrix of a sirolimus-eluting stent coated with poly(lactic-co-glycolic acid).

    Science.gov (United States)

    Choi, Jiyeon; Jang, Bu Nam; Park, Bang Ju; Joung, Yoon Ki; Han, Dong Keun

    2014-08-26

    Sirolimus (SRL) release from the biodegradable poly(l-lactic-co-glycolic acid) (PLGA) matrix was investigated for the application of drug-eluting stents (DES). In particular, this study focused on whether various organic solvents affect the interaction between SRL and PLGA and the formation of microstructures during ultrasonic coating. The SRL-loaded PLGA coated by tetrahydrofuran or acetone showed a significant initial burst, whereas that from acetonitrile was constantly released during a period of 21 days. On the basis of these results, the interactions at the molecular level of SRL with the polymer matrix were estimated according to various organic solvents. Although the topographies of the coated surface were obviously different, the correlation between surface roughness and SRL release was very poor. Irrespective of organic solvents, FT-IR data showed significantly weak SRL-PLGA interactions. From the result of wide-angle X-ray diffraction, it was confirmed that SRL was dispersed in an amorphous state in the polymer matrix after ultrasonic coating. The glass-transition temperature was also influenced by organic solvents, resulting in a plasticizing effect. The particle size of SRL appeared to determine the release profile from the PLGA matrix, which was the combination of diffusion and polymer degradation at an SRL size of more than 800 nm and the Fickian release at that of less than 300 nm. Therefore, organic solvents can lead to a heterogeneous microstructure in the SRL-loaded PLGA matrix, which is at or near the surface, consisting of aggregated drug- and polymer-rich regions. It is expected that the drug release can be controlled by physicochemical properties of organic solvents, and this study can be used effectively for localized drug release in biomedical devices such as drug-eluting stents.

  12. 降低精对苯二甲酸溶剂系统醋酸消耗的研究%Research and Implementation of Decreasing the Acetic Acid Consumption in Purified Terephthalic Acid Solvent System

    Institute of Scientific and Technical Information of China (English)

    徐圆; 朱群雄

    2008-01-01

    Decreasing the acetic acid consumption in purified terephthalic acid(PTA) solvent system has become a hot issue with common concern.In accordance with the technical features.the electrical conductivity is in direct proportion to the acetic acid content.General regression neural network(GRNN)is used to establish the model of electrical conductivity on the basis of mechanism analysis,and then particle swarm optimization (PSO)algorithm with the improvement of mertia weight and population diversity is proposed to regulate the operatmg conditions.Thus.the method of decreasing the acid lossS is derived and applied to PTA solvent system in a chemical plant.Cases studies show that the precision of modeling and optimization are higher.The results also provide the optimal operating conditions,which decrease the cost and improve the profit.

  13. Highly efficient solvent-free synthesis of pyranopyrazoles by a Brønsted-acidic ionic liquid as a green and reusable catalyst

    Indian Academy of Sciences (India)

    Javad Ebrahimi; Ali Mohammadi; Vahid Pakjoo; Esan Bahramzade; Amir Habibi

    2012-09-01

    A simple, green and efficient protocol for synthesis of dihydropyrano[2,3-c]pyrazole derivatives is developed by a four component reaction of various benzaldehydes, ethyl acetoacetate, hydrazine hydrate and malononitrile in the presence of 3-methyl-1-(4-sulphonic acid)butylimidazolium hydrogen sulphate [(CH2)4SO3HMIM][HSO4], an acidic ionic liquid and as a catalyst, under solvent-free conditions. The key advantages of this process are high yields, shorter reaction times, easy work-up, purification of products by non-chromatographic method and the reusability of the catalyst.

  14. Preparation of different amides via Ritter reaction from alcohols and nitriles in the presence of silica-bonded N- propyl sulphamic acid (SBNPSA) under solvent-free conditions

    Indian Academy of Sciences (India)

    Maryam-Sadat Shakeri; Hassan Tajik; Khodabakhsh Niknam

    2012-09-01

    A number of methods have been proposed for the modification of the Ritter reaction. However, many of these methods involve the use of strongly acidic conditions, stoichiometric amounts of reagents, harsh reaction conditions and extended reaction times. Therefore, the development of mild, efficient, convenient and benign reagents for the Ritter reaction is desirable. In this research, we have developed a clean and environmentally friendly protocol for the synthesis of amides by using different benzylic or tertiary alcohols and different nitriles in the presence of silica-bonded N- propyl sulphamic acid (SBNPSA) as catalyst under solvent-free conditions in high yields.

  15. Quantitative structure-retardation factor relationship of protein amino acids in different solvent mixtures for normal-phase thin-layer chromatography.

    Science.gov (United States)

    Yousefinejad, Saeed; Honarasa, Fatemeh; Saeed, Negar

    2015-05-01

    A quantitative predictive/descriptive model was proposed for the retardation factors of protein amino acids in normal-phase thin-layer chromatography. The experimental retardation factors of 126 chromatographic mixtures (21 protein amino acids in different mobile phases) were used as the independent variable. The matrix of dependent variables of the model was built using structural descriptors of amino acids and empirical parameters of solvents of the applied mobile phases. After variable selection, a five-parametr model was proposed for the retardation factor of amino acids, which covered about 84 and 77% variance of data in training and cross-validation, respectively. The correlation coefficient of the external test set was 0.80, which shows the prediction potential of proposed model as well as its good applicability domain that was checked using a standardized residual-leverage plot. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Role of solvent/non-solvent ratio on microsphere formation using the solvent removal method.

    Science.gov (United States)

    Godbee, J; Scott, E; Pattamunuch, P; Chen, S; Mathiowitz, E

    2004-03-01

    The importance of good solvent concentration in the non-solvent mixture and the non-solvent viscosity on the ability to form microspheres using solvent removal process was investigated. The higher the viscosity of the polymer solutions, the higher the concentration of good solvent needed in the nonsolvent mixture to produce microspheres. This finding was due to faster precipitation of the polymer phase. Also, the addition of a model drug, fluorescein isothiocyanate conjugated-labelled bovine serum albumin, to the polymer solution (10% poly-L-lactic acid:poly(fumaric-co-sebacic) anhydride in methylene chloride) resulted in an overall lower polymer solution viscosity (15.5 cP with fluorescein isothiocyanate conjugated-labelled bovine serum albumin as compared with 18.25 cP for blank polymer at 25 degrees C). Additionally, the effect of good solvent concentration on non-solvent viscosity was evaluated, and the viscosity decreased as the concentration of good solvent increased. The effect of good solvent concentration on the non-solvent mixture on sphere formation was of great importance. Microspheres would not form when the good polymer solvent (methylene chloride) in the non-solvent phase was too low (below 175 ml for poly-L-lactic acid or 150 ml for poly(D,L-lactidco-glycolid)) or was replaced by another good solvent such as ethyl acetate, even though the same viscosity was achieved. It was shown that the concentration of the good solvent in the non-solvent mixture was more of a controlling factor than the viscosity of the non-solvent mixture in microsphere formation and the findings support the conclusion that diffusion is the main controlling parameter in solvent removal.

  17. Non-dispersive solvent extraction of p-toluic acid from purified terephthalic acid plant wastewater with p-xylene as extractant

    Institute of Scientific and Technical Information of China (English)

    Qing-ran KONG; You-wei CHENG; Li-jun WANG; Xi LI‡

    2016-01-01

    题目:对二甲苯非分散相溶剂萃取精对苯二甲酸工业废水中的对甲基苯甲酸  目的:采用对二甲苯为萃取剂,通过非分散相溶剂萃取(膜基萃取)同时回收利用精对苯二甲酸(PTA)工业废水中的对甲基苯甲酸和水。  创新点:1.采用非分散相溶剂萃取有效地实现了工业条件下 PTA 废水的净化和资源的回收利用;2.采用数学模拟优化工业萃取的操作参数。  方法:1.进行对二甲苯萃取实验,考察操作条件对萃取效率和萃余水杂质浓度的影响;2.通过数学模拟,建立膜萃取过程的数学模型,对操作参数与膜结构参数进行敏感性分析。  结论:1.非分散相溶剂萃取可以有效解决 PTA 工业废水的回收利用问题;2.质量传递的速率控制步骤是管程中的水相扩散;3.优化的工业操作条件为:中空纤维膜内径为200~250μm,萃取时间为50~60 s,水油两相体积比为9.0,萃取温度为318 K。%Non-dispersive solvent extraction (NDSE) with p-xylene as extractant was employed as a novel separation method to recover both p-toluic (PT) acid and water from purified terephthalic acid (PTA) wastewater. The mass transport behavior of PT acid from aqueous solution to p-xylene was investigated by experiments and numerical simulation. Experiments showed that NDSE is feasible and effective. Residual PT acid in the raffinate can be reduced to lower than the permitted limit of wastewater re-use (100 g/m3) with extraction time longer than 60 s in industrial conditions. A mathematical model of PT acid mass transport was developed to optimize the membrane module performance. The model was validated with the experimental results with relative errors of less than 6%. Numerical analysis for mass transfer through the lumen side, the porous membrane layer, and the shell side showed that PT acid transport in the aqueous solution is the rate determining step. The effects

  18. Impact of quality parameters on the recovery of putrescine and cadaverine in fish using methanol-hydrochloric acid solvent extraction.

    Science.gov (United States)

    Richard, Nicole L; Pivarnik, Lori F; Ellis, P Christopher; Lee, Chong M

    2011-01-01

    Methanol (MeOH) extraction by AOAC Official Method 996.07 has resulted in low amine recoveries in fresh fish tissue. Addition of 25% 0.4 M HCl to the 75% methanol-water extraction solvent resulted in higher recoveries of putrescine and cadaverine. Average putrescine recovery increased from 55 to 92% in flounder, scup, bluefish, and salmon; from 92 to 98% in mackerel; and from 83 to 107% in processed mackerel. Average cadaverine recovery increased from 57 to 95% in flounder, scup, bluefish, and salmon; from 91 to 97% in mackerel; and from 92 to 108% in processed mackerel. Fish stored on ice for 12 days also showed differences between background concentrations determined with the two solvents. However, the values decreased with storage time, indicating that degradation of the protein matrix may cause more comparable measurements between the two solvents. However, consistently higher putrescine and cadaverine measurements were determined using MeOH-HCl. Although significant differences in the extraction of amines from the high-fat fish tissue were not seen between MeOH and MeOH-HCl, it would be ideal to have one solvent for biogenic amine extraction. This study confirms that MeOH-HCl is a better solvent for complete extraction and recovery of putrescine and cadaverine in fresh and processed fish tissues.

  19. Two-Stage Separation of V(IV) and Al(III) by Crystallization and Solvent Extraction from Aluminum-Rich Sulfuric Acid Leaching Solution of Stone Coal

    Science.gov (United States)

    Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing; Liu, Hong

    2016-12-01

    To improve separation of V(IV) and Al(III) from aluminum-rich sulfuric acid leaching solution of stone coal, the two-stage separation by crystallization and solvent extraction methods have been developed. A co-extraction coefficient (k) was put forward to evaluate comprehensively co-extraction extent in different solutions. In the crystallization stage, 68.2% of aluminum can be removed from the solution. In the solvent extraction stage, vanadium was selectively extracted using di-2-ethylhexyl phosphoric acid/tri-n-butyl phosphate from the crystalline mother solution, followed by H2SO4 stripped efficiently. A V2O5 product with purity of 98.39% and only 0.10% Al was obtained after oxidation, precipitation, and calcination. Compared with vanadium extraction from solution without crystallization, the counter-current extraction stage of vanadium can be decreased from 6 to 3 and co-extraction coefficient (k) decreased from 2.51 to 0.58 with two-stage separation. It is suggested that the aluminum removal by crystallization can evidently weaken the influence of aluminum co-extraction on vanadium extraction and improve the selectivity of solvent extraction for vanadium.

  20. Co-precipitation of asiatic acid and poly(l-lactide) using rapid expansion of subcritical solutions into liquid solvents

    Energy Technology Data Exchange (ETDEWEB)

    Sane, Amporn, E-mail: amporn.s@ku.ac.th; Limtrakul, Jumras [Kasetsart University, NANOTEC Center of Excellence, National Nanotechnology Center (Thailand)

    2011-09-15

    Poly(l-lactide) (PLLA) nanoparticles loaded with asiatic acid (AA) were successfully produced by rapid expansion of a subcritical solution into an aqueous receiving solution containing a dispersing agent. A mixture of carbon dioxide (CO{sub 2}) and ethanol (EtOH) with a weight ratio of 1:1 was used as the solvent for AA and PLLA. Two surfactants, Pluronic F127 and sodium dodecyl sulfate were employed. The former was found to be more effective for stabilizing AA-loaded PLLA nanoparticles, as a rapid expansion into a 0.1 wt% Pluronic F127 solution produced a stable nanosuspension consisting mainly of well-dispersed, individual nanoparticles. The effects of rapid expansion-processing conditions-AA to PLLA weight ratio and pre-expansion temperature (T{sub pre})-on the size and morphology of composite nanoparticles, and the loading capacity and entrapment efficiency of AA in PLLA nanoparticles, were systematically investigated. It was found that AA-loaded PLLA nanoparticles with a size range of 30-100 nm were consistently fabricated by rapid expansion at T{sub pre} of 70-100 Degree-Sign C and AA to PLLA weight ratios of 1:2 and 1:4, and with a constant pre-expansion pressure of 330 bar. The T{sub pre} and AA to PLLA weight ratio had no significant effects on the size of the nanoparticles. The AA to PLLA weight ratio is a controlling parameter for both the loading capacity and the entrapment efficiency of AA in PLLA nanoparticles. The loading capacity and entrapment efficiency increased from 8-11 to 16-21 wt%, and 38-57 to 50-62 wt%, respectively, when the AA to PLLA weight ratio changed from 1:4 to 1:2. However, increasing the T{sub pre} from 70 to 100 Degree-Sign C decreased both the loading capacity and entrapment efficiency of AA in PLLA nanoparticles by {approx}20-30%.

  1. Evaluation of food grade solvents for lipid extraction and impact of storage temperature on fatty acid composition of edible seaweeds Laminaria digitata (Phaeophyceae) and Palmaria palmata (Rhodophyta).

    Science.gov (United States)

    Schmid, Matthias; Guihéneuf, Freddy; Stengel, Dagmar B

    2016-10-01

    This study evaluated the impact of different food- and non-food grade extraction solvents on yield and fatty acid composition of the lipid extracts of two seaweed species (Palmaria palmata and Laminaria digitata). The application of chloroform/methanol and three different food grade solvents (ethanol, hexane, ethanol/hexane) revealed significant differences in both, extraction yield and fatty acid composition. The extraction efficiency, in terms of yields of total fatty acids (TFA), was in the order: chloroform/methanol>ethanol>hexane>ethanol/hexane for both species. Highest levels of polyunsaturated fatty acids (PUFA) were achieved by the extraction with ethanol. Additionally the effect of storage temperature on the stability of PUFA in ground and freeze-dried seaweed biomass was investigated. Seaweed samples were stored for a total duration of 22months at three different temperatures (-20°C, 4°C and 20°C). Levels of TFA and PUFA were only stable after storage at -20°C for the two seaweed species.

  2. Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Sudipta Pathak

    2013-11-01

    Full Text Available A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products.

  3. The preparation of terephthalic acid by solvent-free oxidation of p-xylene with air over T(p-Cl)PPMnCl and Co(OAc)2

    Institute of Scientific and Technical Information of China (English)

    Yang Xiao; Xiao Yan Zhang; Qin Bo Wang; Ze Tan; Can Cheng Guo; Wei Deng; Zhi Gang Liu; He Fei Zhang

    2011-01-01

    An attempt has been made to prepare terephthalic acid (TPA) by solvent-free oxidation of p-xylene (PX) with air over tetra(p-chlorophenylporphinato)manganese chloride (T(p-Cl)PPMnCl) and cobalt acetate. The co-catalysis between T(p-Cl)PPMnCl and Co(OAc)2 has been discovered under solvent-free conditions. TPA yield could be increased significantly when T(p-Cl)PPMnCl and Co(OAc)2 were used together. The addition of T(p-Cl)PPMnCl into the reaction mixture over Co(OAc)2 significantly accelerated the rate-determining step of the oxidation process of PX to TPA. The effect of temperature on reaction was also investigated.

  4. 含氮类萃取剂对水-醋酸汽液平衡的影响%EFFECT OF NITROGEN-CONTAINING SOLVENTS ON VAPOR-LIQUID EQUILIBRIUM OF WATER -ACETIC ACID SYSTEM

    Institute of Scientific and Technical Information of China (English)

    胡兴兰; 周荣琪

    2004-01-01

    Acetic acid is a basic chemical and solvent in the production of many chemicals and intermediates. Acetic acid is usually diluted in these processes, so the concentration and purification of acetic acid from its aqueous solutions is an important technique in the chemical industry. Extractive distillation is a new

  5. Demonstration of a Universal Solvent Extraction Process for the Separation of Cesium and Strontium from Actual Acidic Tank Waste at the INEEL

    Energy Technology Data Exchange (ETDEWEB)

    Law, Jack Douglas; Herbst, Ronald Scott; Todd, Terry Allen; Brewer, Ken Neal; Romanovskiy, V.N.; Esimantovskiy, V.M.; Smirnov, I.V.; Babain, V.A.; Zaitsev, B.N.

    1999-09-01

    A universal solvent extraction process is being evaluated for the simultaneous separation of Cs, Sr, and the actinides from acidic high-activity tank waste at the Idaho National Engineering and Environmental Laboratory (INEEL) with the goal of minimizing the high-activity waste volume to be disposed in a deep geological repository. The universal solvent extraction process is being developed as a collaborative effort between the INEEL and the Khlopin Radium Institute in St. Petersburg, Russia. The process was recently demonstrated at the INEEL using actual radioactive, acidic tank waste in 24 stages of 2-cm diameter centrifugal contactors located in a shielded cell facility. With this testing, removal efficiencies of 99.95%, 99.985%, and 95.2% were obtained for 137 Cs, 90 Sr, and total alpha, respectively. This is sufficient to reduce the activities of 137 Cs and 90 Sr to below NRC Class A LLW requirements. The total alpha removal efficiency was not sufficient to reduce the activity of the tank waste to below NRC Class A non-TRU requirements. The lower than expected removal efficiency for the actinides is due to loading of the Ph2Bu2CMPO in the universal solvent exiting the actinide strip section and entering the wash section resulted in the recycle of the actinides back to the extraction section. This recycle of the actinides contributed to the low removal efficiency. Significant amounts of the Zr (>97.7%), Ba (>87%), Pb (>98.5%), Fe (6.9%), Mo (19%), and K (17%) were also removed from the feed with the universal solvent extraction flowsheet.

  6. Comparison of contact angle measurement and microbial adhesion to solvents for assaying electron donor-electron acceptor (acid-base) properties of bacterial surface.

    Science.gov (United States)

    Hamadi, Fatima; Latrache, Hassan

    2008-08-01

    The electron donor-electron acceptor (acid-base properties) of cell surfaces of a series of bacteria were determined by two methods, namely, Microbial Adhesion to Solvents (MATS) and Contact Angle Measurements (CAM) combined with equation of Van Oss. The efficiency of these two methods was then compared. Pseudomonas aeruginosa ATCC 27853, Bacillus subtilis ILP 142B, Staphylococcus aureus ATCC 25923 and four Escherichia coli strains including HB101, AL52, O128B12 and ATCC 25922, acid-base properties were examined under the two different conditions mentioned above. The results showed that the correlation between acid-base properties determined by MATS and CAM was very weak. We have also found that when the microbial cell surface was electron donor by CAM method, similar result was found by MATS, but the reverse was not always true. In contrast, a good correlation between the two methods was obtained when the four E. coli strains were examined.

  7. Penelitian pengaruh naphthenic oil dan HAF black terhadap sifat pampat tetap pada kompon lis kaca mobil

    Directory of Open Access Journals (Sweden)

    A Buchori

    1996-06-01

    Full Text Available The objective of the research is to know the influence of naphthenic oil and HAF black properties of the compression set by constant load and constant deflection rubber strip compound. Rubber strip compound is made from natural rubber (RSS and synthetic rubber (SBR 1502 with the addition of ingredient such as softener, activator, filler, anti oxidant, accelerator and vulcanizing agent. It should be carried out using base formula by varrying naphtenic oil 3; 5 and 7 parts and carbon black 45; 50 and 55 parts for 9 compounds, then it should be tested their physical properties, compression set by constant load and constant deflection. The test is actually able to fullfill the specification of SII 1999-86 “Lis karet kaca kendaraan bermotor”. The result of the test statistically prove that naphthenicc oil and HAF black influence the physical properties.

  8. Mathematical modeling of cadmium(II) solvent extraction from neutral and acidic chloride media using Cyanex 923 extractant as a metal carrier.

    Science.gov (United States)

    Leopold, A A; Coll, M T; Fortuny, A; Rathore, N S; Sastre, A M

    2010-10-15

    This paper describes experimental work and the mathematical modeling of solvent extraction of cadmium(II) from neutral and acidic aqueous chloride media with a Cyanex 923 extractant in Exxol D-100. Solvent extraction experiments were carried out to analyze the influence of variations in the composition of the aqueous and organic phases on the efficiency of cadmium(II) extraction. In neutral and acidic chloride conditions, the extraction of cadmium(II) by the organophosphorous extractant Cyanex 923 (L) is based on the solvation mechanism of neutral H(n)CdCl((2+n)) species and the formation of H(n)CdCl((2+n))L(q) complexes in the organic phase, where n=0, 1, 2 and q=1, 2. The mathematical model of cadmium(II) extraction was derived from the mass balances and chemical equilibria involved in the separation system. The model was computed with the Matlab software. The equilibrium parameters for metal extraction, i.e. the stability constants of the aqueous Cd-Cl complexes, the formation constants of the acidic Cd-Cl species and the metal equilibrium extraction constants, were proposed. The optimized constants were appropriate, as there was good agreement when the model was fitted to the experimental data for each of the experiments.

  9. Mathematical modeling of cadmium(II) solvent extraction from neutral and acidic chloride media using Cyanex 923 extractant as a metal carrier

    Energy Technology Data Exchange (ETDEWEB)

    Leopold, A.A., E-mail: agnieszka.leopold@upc.edu [Department of Chemical Engineering, Universitat Politecnica de Catalunya, EPSEVG, Av. Victor Balaguer s/n, 08800 Vilanova i la Geltru (Spain); Coll, M.T.; Fortuny, A.; Rathore, N.S. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, EPSEVG, Av. Victor Balaguer s/n, 08800 Vilanova i la Geltru (Spain); Sastre, A.M. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, ETSEIB, Av. Diagonal 647, 08028 Barcelona (Spain)

    2010-10-15

    This paper describes experimental work and the mathematical modeling of solvent extraction of cadmium(II) from neutral and acidic aqueous chloride media with a Cyanex 923 extractant in Exxol D-100. Solvent extraction experiments were carried out to analyze the influence of variations in the composition of the aqueous and organic phases on the efficiency of cadmium(II) extraction. In neutral and acidic chloride conditions, the extraction of cadmium(II) by the organophosphorous extractant Cyanex 923 (L) is based on the solvation mechanism of neutral H{sub n}CdCl{sub (2+n)} species and the formation of H{sub n}CdCl{sub (2+n)}L{sub q} complexes in the organic phase, where n = 0, 1, 2 and q = 1, 2. The mathematical model of cadmium(II) extraction was derived from the mass balances and chemical equilibria involved in the separation system. The model was computed with the Matlab software. The equilibrium parameters for metal extraction, i.e. the stability constants of the aqueous Cd-Cl complexes, the formation constants of the acidic Cd-Cl species and the metal equilibrium extraction constants, were proposed. The optimized constants were appropriate, as there was good agreement when the model was fitted to the experimental data for each of the experiments.

  10. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part II. Recovery of Ammonia from Sour Waters

    Energy Technology Data Exchange (ETDEWEB)

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, SUCCiOlC acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  11. A facile, green, one-pot synthesis of amidoalkyl naphthols under solvent-free conditions catalyzed by a carbon-based solid acid

    Institute of Scientific and Technical Information of China (English)

    Abolghasem Davoodnia; Rahil Mahjoobin; Niloofar Tavakoli-Hoseini

    2014-01-01

    An efficient, environmentally friendly procedure for the synthesis of amidoalkyl naphthols through the one-pot, three-component reaction of β-naphthol, aryl aldehydes, and acetamide in the presence of a carbon-based solid acid under thermal solvent-free conditions is described. The beneficial fea-tures of this new synthetic approach include short reaction time, high yields, clean reaction profiles, and a simple work-up procedure. Furthermore, the catalyst can be readily recycled and reused four times without obvious significant loss of activity. The structure of the catalyst was confirmed by Fourier transform infrared spectroscopy, N2 adsorption/desorption analysis, and X-ray diffraction.

  12. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  13. Impregnation of 12-tungstophosphoric acid on silica - part II: effect of different solvents on the impregnation and catalytic activity in methyl esterification of stearic acid; Impregnacao do acido 12-tungstofosforico em silica - parte II: efeito de diferentes solventes na impregnacao e atividade catalitica na esterificacao metilica de acido estearico

    Energy Technology Data Exchange (ETDEWEB)

    Scroccaro, Karine Isabel; Yamamoto, Carlos I., E-mail: karineisabel@yahoo.com.br [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Centro Politecnico. Departamento de Engenharia Quimica; Tanobe, Valcineide O. de A.; Oliveira, Alan Antonio de [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Departamento de Engenharia e Tecnologia Florestal; Wypych, Fernando [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Departamento de Quimica

    2014-04-15

    Materials obtained by the immobilization of 12-tungstophosphoric acid (PTA) on silica using the method of impregnation with excess solution in distinct solvents (aqueous HCl, methanol:H{sub 2}O, and acetonitrile) were evaluated for use as catalysts in the methyl esterification of stearic acid. Optimum conditions were established for the impregnation of 0.5 g (w/w) of PTA on amorphous silica, under stirring at 150 rpm for 24 h, using 20 mL of 0.1 mol L{sup -1} HCl as the solvent. After calcination at 200 deg C, high conversions were obtained under mild reaction conditions, resulting in high turnover numbers. The catalyst was evaluated in ten catalytic cycles of use, where the activity was reduced only slightly, attesting its stability and the possibility to apply it to industrial production of methylesters. (author)

  14. Acilação de Friedel-Crafts do 2-metoxinaftaleno usando o ácido dodecafosfotúngstico suportado em sílica (HPW/SiO2 como catalisador e acetonitrila como solvente Friedel-Crafts acylation of the 2-methoxynaphthalene using the silica-supported dodecatungstophosphoric acid (HPW/SiO2 as catalyst and acetonitrile as solvent

    Directory of Open Access Journals (Sweden)

    Gil Luciano Guedes dos Santos

    2010-01-01

    Full Text Available The synthesis of fine chemicals intermediates using Friedel-Crafts acylation is one of the most important methods in chemical technology. In this work, the acylation of 2-methoxynaphthalene with acetic anhydride using a silica-supported dodecatungstophosphoric acid catalyst (HPW/SiO2 and acetonitrila as solvent was studied, showing that this reaction is a feasible alternative to produce intermediaries to replace the current methods of production. The reactions using acetonitrile solvent showed yields greater than or equal to the reactions using traditional solvents such as nitrobenzene and dichloroethane. Finally, the modified Eley-Rideal mechanism was proposed to elucidate the experimental data obtained.

  15. Continuous Preparation of 1:1 Haloperidol-Maleic Acid Salt by a Novel Solvent-Free Method Using a Twin Screw Melt Extruder.

    Science.gov (United States)

    Lee, Hung Lin; Vasoya, Jaydip M; Cirqueira, Marilia de Lima; Yeh, Kuan Lin; Lee, Tu; Serajuddin, Abu T M

    2017-03-10

    Salts are generally prepared by acid-base reaction in relatively large volumes of organic solvents, followed by crystallization. In this study, the potential for preparing a pharmaceutical salt between haloperidol and maleic acid by a novel solvent-free method using a twin-screw melt extruder was investigated. The pH-solubility relationship between haloperidol and maleic acid in aqueous medium was first determined, which demonstrated that 1:1 salt formation between them was feasible (pHmax 4.8; salt solubility 4.7 mg/mL). Extrusion of a 1:1 mixture of haloperidol and maleic acid at the extruder barrel temperature of 60 °C resulted in the formation of a highly crystalline salt. The effects of operating temperature and screw configuration on salt formation were also investigated, and those two were identified as key processing parameters. Salts were also prepared by solution crystallization from ethyl acetate, liquid-assisted grinding, and heat-assisted grinding and compared with those obtained by melt extrusion by using DSC, PXRD, TGA, and optical microscopy. While similar salts were obtained by all methods, both melt extrusion and solution crystallization yielded highly crystalline materials with identical enthalpies of melting. During the pH-solubility study, a salt hydrate form was also identified, which, upon heating, converted to anhydrate similar to that obtained by other methods. There were previous reports of the formation of cocrystals, but not salts, by melt extrusion. (1)H NMR and single-crystal X-ray diffraction confirmed that a salt was indeed formed in the present study. The haloperidol-maleic acid salt obtained was nonhygroscopic in the moisture sorption study and converted to the hydrate form only upon mixing with water. Thus, we are reporting for the first time a relatively simple and solvent-free twin-screw melt extrusion method for the preparation of a pharmaceutical salt that provides material comparable to that obtained by solution

  16. Supramolecular synthons in designing low molecular mass gelling agents: L-amino acid methyl ester cinnamate salts and their anti-solvent-induced instant gelation.

    Science.gov (United States)

    Sahoo, Pathik; Kumar, D Krishna; Raghavan, Srinivasa R; Dastidar, Parthasarathi

    2011-04-04

    Easy access to a class of chiral gelators has been achieved by exploiting primary ammonium monocarboxylate (PAM), a supramolecular synthon. A combinatorial library comprising of 16 salts, derived from 5 L-amino acid methyl esters and 4 cinnamic acid derivatives, has been prepared and scanned for gelation. Remarkably, 14 out of 16 salts prepared (87.5 % of the salts) show moderate to good gelation abilities with various solvents, including commercial fuels, such as petrol. Anti-solvent induced instant gelation at room temperature has been achieved in all the gelator salts, indicating that the gelation process is indeed an aborted crystallization phenomenon. Rheology, optical and scanning electron microscopy, small angle neutron scattering, and X-ray powder diffraction have been used to characterize the gels. A structure-property correlation has been attempted, based on these data, in addition to the single-crystal structures of 5 gelator salts. Analysis of the FT-IR and (1)H NMR spectroscopy data reveals that some of these salts can be used as supramolecular containers for the slow release of certain pest sex pheromones. The present study clearly demonstrates the merit of crystal engineering and the supramolecular synthon approach in designing new materials with multiple properties.

  17. SOLVENT EXTRACTION OF URANIUM VALUES

    Science.gov (United States)

    Feder, H.M.; Ader, M.; Ross, L.E.

    1959-02-01

    A process is presented for extracting uranium salt from aqueous acidic solutions by organic solvent extraction. It consists in contacting the uranium bearing solution with a water immiscible dialkylacetamide having at least 8 carbon atoms in the molecule. Mentioned as a preferred extractant is dibutylacetamide. The organic solvent is usually used with a diluent such as kerosene or CCl/sub 4/.

  18. Upgrading of LCO by partial hydrogenation of aromatics and ring opening of naphthenes over bi-functional catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Calemma, Vincenzo; Giardino, Roberto; Ferrari, Marco [Eni R and M, Via Maritano 26, 20097 San Donato M.se (Italy)

    2010-07-15

    Available options to upgrade LCO to diesel fuel are: i) aromatic saturation (ASAT) ii) mild hydrocracking and iii) aromatic saturation followed by selective ring opening (SRO) of naphthenic structures. Although the above mentioned routes lead to significant product quality enhancement, they suffer from several disadvantages. Hydrocracking leads to significant yields in gasoline-range products, ASAT is characterized by a relatively high consumption of hydrogen with only limited improvement of product quality in terms of density and cetane properties, ASAT + SRO route leads to higher improvements of product quality but it requires a very high hydrogen consumption which strongly affects the economics of the process. An alternative upgrading route consists in partial polyaromatic compound saturation and selective opening of both naphthenic and benzo-naphthenic structures to produce less condensed naphthenic structures and alkyl-benzenes respectively. In this case the hydrogen needed to improve product quality at the same level, of cetane properties and density, is lower in comparison with ASAT. This paper reports the results obtained during a research program aimed at upgrading LCO via selective ring opening. The hydroconversion of a low sulfur hydrotreated LCO has been studied over iridium and platinum loaded on different supports. The results of this study indicate that the properties of products heavily depend on the characteristics of the support and the metal used. The data obtained with the Ir/amorphous silica-alumina (MSA) show the possibility to get a clear increase of CN and decrease of density in comparison with the mere aromatic saturation. The practical consequence of this result is the possibility of producing products with CN and density similar to products obtained by complete dearomatization but still containing a significant percentage of aromatic structures so allowing a consistent saving of hydrogen. (author)

  19. Regioselective ring opening of epoxides using NH4SCN/silica sulfuric acid: An efficient approach for the synthesis of β-hydroxy thiocyanate under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Ali R. Kiasat; Maryam Zayadi; Mehdi Fallah Mehrjardi

    2008-01-01

    Silica sulfuric acid was developed as a stable and efficient heterogeneous catalyst in organic synthesis. This solid acid catalyzed the regioselective ring opening of epoxides by thiocyanate anion to give thiocyanohydrins as key intermediates in agricultural and pharmaceutical chemistry in high yields under solvent-free conditions.

  20. Characterization of napthenic acids in oil sands process-affected waters using fluorescence technology

    Energy Technology Data Exchange (ETDEWEB)

    Brown, L.; Alostaz, M.; Ulrich, A. [Alberta Univ., Edmonton, AB (Canada). Dept. of Civil and Environmental Engineering

    2009-07-01

    Process-affected water from oil sands production plants presents a major environmental challenge to oil sands operators due to its toxicity to different organisms as well as its corrosiveness in refinery units. This abstract investigated the use of fluorescence excitation-emission matrices to detect and characterize changes in naphthenic acid in oil sands process-affected waters. Samples from oil sands production plants and storage ponds were tested. The study showed that oil sands naphthenic acids show characteristic fluorescence signatures when excited by ultraviolet light in the range of 260 to 350 mm. The signal was a unique attribute of the naphthenic acid molecule. Changes in the fluorescence signature can be used to determine chemical changes such as degradation or aging. It was concluded that the technology can be used as a non-invasive continuous water quality monitoring tool to increase process control in oil sands processing plants.

  1. Fermentation products of solvent tolerant marine bacterium Moraxella spp. MB1 and its biotechnological applications in salicylic acid bioconversion.

    Directory of Open Access Journals (Sweden)

    Solimabi Wahidullah

    Full Text Available As part of a proactive approach to environmental protection, emerging issues with potential impact on the environment is the subject of ongoing investigation. One emerging area of environmental research concerns pharmaceuticals like salicylic acid, which is the main metabolite of various analgesics including aspirin. It is a common component of sewage effluent and also an intermediate in the degradation pathway of various aromatic compounds which are introduced in the marine environment as pollutants. In this study, biotransformation products of salicylic acid by seaweed, Bryopsis plumosa, associated marine bacterium, Moraxella spp. MB1, have been investigated. Phenol, conjugates of phenol and hydroxy cinnamic acid derivatives (coumaroyl, caffeoyl, feruloyl and trihydroxy cinnamyl with salicylic acid (3-8 were identified as the bioconversion products by electrospray ionization mass spectrometry. These results show that the microorganism do not degrade phenolic acid but catalyses oxygen dependent transformations without ring cleavage. The degradation of salicylic acid is known to proceed either via gentisic acid pathway or catechol pathway but this is the first report of biotransformation of salicylic acid into cinnamates, without ring cleavage. Besides cinnamic acid derivatives (9-12, metabolites produced by the bacterium include antimicrobial indole (13 and β-carbolines, norharman (14, harman (15 and methyl derivative (16, which are beneficial to the host and the environment.

  2. Fermentation products of solvent tolerant marine bacterium Moraxella spp. MB1 and its biotechnological applications in salicylic acid bioconversion.

    Science.gov (United States)

    Wahidullah, Solimabi; Naik, Deepak N; Devi, Prabha

    2013-01-01

    As part of a proactive approach to environmental protection, emerging issues with potential impact on the environment is the subject of ongoing investigation. One emerging area of environmental research concerns pharmaceuticals like salicylic acid, which is the main metabolite of various analgesics including aspirin. It is a common component of sewage effluent and also an intermediate in the degradation pathway of various aromatic compounds which are introduced in the marine environment as pollutants. In this study, biotransformation products of salicylic acid by seaweed, Bryopsis plumosa, associated marine bacterium, Moraxella spp. MB1, have been investigated. Phenol, conjugates of phenol and hydroxy cinnamic acid derivatives (coumaroyl, caffeoyl, feruloyl and trihydroxy cinnamyl) with salicylic acid (3-8) were identified as the bioconversion products by electrospray ionization mass spectrometry. These results show that the microorganism do not degrade phenolic acid but catalyses oxygen dependent transformations without ring cleavage. The degradation of salicylic acid is known to proceed either via gentisic acid pathway or catechol pathway but this is the first report of biotransformation of salicylic acid into cinnamates, without ring cleavage. Besides cinnamic acid derivatives (9-12), metabolites produced by the bacterium include antimicrobial indole (13) and β-carbolines, norharman (14), harman (15) and methyl derivative (16), which are beneficial to the host and the environment.

  3. Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

    Directory of Open Access Journals (Sweden)

    Fatemeh Rajabi

    2016-07-01

    Full Text Available Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15 have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs.

  4. Nano-composite polymer gel electrolytes containing ortho-nitro benzoic acid: role of dielectric constant of solvent and fumed silica

    Science.gov (United States)

    Kumar, R.

    2015-03-01

    In this paper, nano-composite polymer gel electrolytes containing polymethylmethacrylate, dimethylacetamide, diethyl carbonate, fumed silica and ortho-nitro benzoic acid have been synthesized. Electrical conductivity, viscosity, pH and thermal behavior of these electrolytes have been studied. The effect of acid, polymer, fumed silica concentration on conductivity, pH and viscosity has been discussed. The effect of dielectric constant of solvent on conductivity behavior of composite polymer gel electrolytes has also been studied. Two maxima in conductivity behavior have been observed with fumed silica concentration for composite polymer gel electrolytes, which have been explained on the basis of double percolation threshold model. Maximum conductivity of 3.20 × 10-4 and 2.46 × 10-6 S/cm at room temperature has been observed for nano-composite polymer gel electrolytes containing 10 wt% polymethylmethacrylate in 1 M solution of o-nitro benzoic acid in dimethylacetamide and diethyl carbonate respectively. The intensity of first maximum observed in conductivity at low concentration of fumed silica has been found to decrease with the decrease in acid concentration for composite polymer gel electrolytes, while the intensity of second maximum at higher fumed silica concentration remains unaffected. The conductivity of composite gels does not show much change in the temperature range of 20-100 °C and also remains constant with time, making them suitable for use as electrolytes in various devices like fuel cells, proton batteries, electrochromic window applications etc.

  5. 酸性体系中钼的溶剂萃取研究进展%Research advances of molybdenum solvent extraction in acidic system

    Institute of Scientific and Technical Information of China (English)

    李波

    2013-01-01

    The acidic leaching process has been widely applied to the treatment of the materials bearing molyb-denum for the recovery of molybdenum. Moreover, there has been a growing concern on the separation of molybdenum from acidic leaching solutions by solvent extraction. Based on the review of the current research status on acidic, neutral and amine extraction agents that are used in the molybdenum extraction technique from the acid leaching solution, the extraction mechanisms of the various agents and their relative merits are analyzed, and the trend of further study is prospected as well.%目前酸浸工艺已广泛应用于各种含钼物料的处理,而由含钼酸浸溶液中萃取分离钼已愈来愈受到关注。文中在综述酸类萃取剂、中性萃取剂、胺类萃取剂从酸浸液中萃取分离钼工艺研究现状的基础上,对各类萃取剂萃钼机理及优缺点进行了分析,并指出了进一步研究的方向。

  6. Preparation of porous carboxymethyl chitosan grafted poly (acrylic acid) superabsorbent by solvent precipitation and its application as a hemostatic wound dressing

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yu, E-mail: cylsy@163.com [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Zhang, Yong [School of Life Science, Beijing Institute of Technology, Beijing 100081 (China); Wang, Fengju [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Meng, Weiwei; Yang, Xinlin [School of Life Science, Beijing Institute of Technology, Beijing 100081 (China); Li, Peng [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Jiang, Jianxin [State Key Laboratory of Trauma Burns and Combined Injury, The Third Military Medical University, Chongqing 400042 (China); Tan, Huimin [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Zheng, Yongfa [Guangdong Fuyang Biotechnology Co., Ltd., Heyuan, Guangdong 517000 (China)

    2016-06-01

    The volume phase transition of a hydrogel initiated by shrinking may result in complex patterns on its surface. Based on this unique property of hydrogel, we have developed a novel solvent precipitation method to prepare a kind of novel superabsorbent polymers with excellent hemostatic properties. A porous carboxymethyl chitosan grafted poly (acrylic acid) (CMCTS-g-PAA) superabsorbent polymer was prepared by precipitating CMCTS-g-PAA hydrogel with ethanol. Its potential application in hemostatic wound dressing was investigated. The results indicate that the modified superabsorbent polymer is non-cytotoxic. It showed a high swelling capacity and better hemostatic performance in the treatments of hemorrhage model of ear artery, arteria cruralis and spleen of the New Zealand white rabbit than the unmodified polymer and other commonly used clinic wound dressings. The hemostatic mechanism of the porous CMCTS-g-PAA polymer was also discussed. - Highlights: • The novel solvent precipitation method was developed to prepare the porous superabsorbent polymer. • The swelling rate was promoted and the harmful residual monomer was leached after modification. • The modified polymer showed good biological safety. • It showed good hemostasis to arterial hemorrhage model of the animal. • The hemostatic mechanism of the modified superabsorbent polymer was discussed.

  7. Synthesis, crystallographic, spectral, and spectrophotometric studies of proton transfer complex of 1,2-dimethylimidazole with 3,5-dinitrobenzoic acid in different polar solvents

    Science.gov (United States)

    Miyan, Lal; Zulkarnain; Ahmad, Afaq

    2017-04-01

    The molecular interaction between 1, 2-dimethylimidazole (DMI) and 3,5-dinitrobenzoic acid (DNBA) has been investigated in methanol at room temperature. The stoichiometry of the synthesized CT complex was found to be 1:1 using the straight line method of Benesi-Hildebrand equation. The structure of the resulting CT complex was isolating and characterized using X-ray crystallography, FTIR and 1H NMR spectroscopic techniques. The thermal composition and stability of the CT complex were analyzed using thermogravimetric and differential thermal analysis (TGA and DTA). UV-visible spectrophotometric technique was used to the determine the various important physical parameters such as formation constant (KCT), molar extinction coefficient (εCT), energy of interaction (ECT), ionization potential (ID), resonance energy (RN), free energy (ΔG°), oscillator strength (ƒ) and transition dipole moment (μN). The effect of polarity of the solvent and concentration of acceptor on these parameters have been investigated. The results indicate that charge transfer complex (CTC) is more stable in less polar solvent due to the high value of the formation constant. A polymeric network through hydrogen bonding interaction between neighboring moieties was observed. This has also been attributed to the formation of 1:1 type CT complex.

  8. Traceable atomic force microscopy of high-quality solvent-free crystals of [6,6]-phenyl-C61-butyric acid methyl ester

    Science.gov (United States)

    Lazzerini, Giovanni Mattia; Paternò, Giuseppe Maria; Tregnago, Giulia; Treat, Neil; Stingelin, Natalie; Yacoot, Andrew; Cacialli, Franco

    2016-02-01

    We report high-resolution, traceable atomic force microscopy measurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8 nm), was used to measure the crystals' height. The optical interferometer together with the stabilized laser provides traceability (via the laser wavelength) of the vertical measurements made with the atomic force microscope. We find that the crystals can conform to the surface topography, thanks to their height being significantly smaller compared to their lateral dimensions (namely, heights between about 50 nm and 140 nm, for the crystals analysed, vs. several tens of microns lateral dimensions). The vast majority of the crystals are flat, but an isolated, non-flat crystal provides insights into the growth mechanism and allows identification of "molecular terraces" whose height corresponds to one of the lattice constants of the single PCBM crystal (1.4 nm) as measured with X-ray diffraction.

  9. The effect of re-dissolution solvents and HPLC columns on the analysis of mycosporine-like amino acids in the eulittoral macroalgae Prasiola crispa and Porphyra umbilicalis

    Science.gov (United States)

    Karsten, Ulf; Escoubeyrou, Karine; Charles, François

    2009-09-01

    Many macroalgal species that are regularly exposed to high solar radiation such as the eulittoral green alga Prasiola crispa and the red alga Porphyra umbilicalis synthesize and accumulate high concentrations of mycosporine-like amino acids (MAAs) as UV-sunscreen compounds. These substances are typically extracted with a widely used standard protocol following quantification by various high performance liquid chromatography (HPLC) techniques. However, further preparation steps prior to HPLC analysis as well as different HPLC column types have not been systematically checked regarding separation quality and reproducibility. Therefore pure methanol, distilled water and HPLC eluent were evaluated as re-dissolution solvent for dried Prasiola and Porphyra extracts, which were subsequently analyzed on three reversed-phase C8 and C18 HPLC columns. The data indicate that distilled water and the HPLC eluent gave almost identical peak patterns and MAA contents on the C8 and C18 columns. In contrast, the application of the widely used methanol led to double peaks or even the loss of specific peaks as well as to a strong decline in total MAA amounts ranging from about 35% of the maximum in P. crispa to 80% of the maximum in P. umbilicalis. Consequently, methanol should be avoided as re-dissolution solvent for the HPLC sample preparation. An improved protocol for the MAA analysis in macroalgae in combination with a reliable C18 column is suggested.

  10. Hydrogen atom transfer from 1,n-alkanediamines to the cumyloxyl radical. Modulating C-H deactivation through acid-base interactions and solvent effects.

    Science.gov (United States)

    Milan, Michela; Salamone, Michela; Bietti, Massimo

    2014-06-20

    A time-resolved kinetic study on the effect of trifluoroacetic acid (TFA) on the hydrogen atom transfer (HAT) reactions from 1,n-alkanediamines (R2N(CH2)nNR2, R = H, CH3; n = 1-4), piperazine, and 1,4-dimethylpiperazine to the cumyloxyl radical (CumO(•)), has been carried out in MeCN and DMSO. Very strong deactivation of the α-C-H bonds has been observed following nitrogen protonation and the results obtained have been explained in terms of substrate basicity, of the distance between the two basic centers and of the solvent hydrogen bond acceptor ability. At [substrate] ≤ 1/2 [TFA] the substrates exist in the doubly protonated form HR2N(+)(CH2)nN(+)R2H, and no reaction with CumO(•) is observed. At 1/2 [TFA] [TFA], HAT occurs from the α-C-H bonds of R2N(CH2)nNR2, and the mesured kH values are very close to those obtained in the absence of TFA. Comparison between MeCN and DMSO clearly shows that in the monoprotonated diamines R2N(CH2)nN(+)R2H remote C-H deactivation can be modulated through solvent hydrogen bonding.

  11. Microchip electrophoresis with background electrolyte containing polyacrylic acid and high content organic solvent in cyclic olefin copolymer microchips for easily adsorbed dyes.

    Science.gov (United States)

    Wei, Xuan; Sun, Ping; Yang, Shenghong; Zhao, Lei; Wu, Jing; Li, Fengyun; Pu, Qiaosheng

    2016-07-29

    Plastic microchips can significantly reduce the fabrication cost but the adsorption of some analytes limits their application. In this work, background electrolyte containing ionic polymer and high content of organic solvent was adopted to eliminate the analyte adsorption and achieve highly efficient separation in microchip electrophoresis. Two dyes, rhodamine 6G (Rh6G) and rhodamine B (RhB) were used as the model analytes. By using methanol as the organic solvent and polyacrylic acid (PAA) as a multifunctional additive, successful separation of the two dyes within 75μm id. microchannels was realized. The role of PAA is multiple, including viscosity regulator, selectivity modifier and active additive for counteracting analyte adsorption on the microchannel surface. The number of theoretical plate of 7.0×10(5)/m was attained within an effective separation distance of 2cm using background electrolyte consisting 80% methanol, 0.36% PAA and 30mmol/L phosphate at pH 5.0. Under optimized conditions, relative standard deviations of Rh6G and RhB detection (n=5) were no more than 1.5% for migration time and 2.0% for peak area, respectively. The limit of detection (S/N=3) was 0.1nmol/L for Rh6G. The proposed technique was applied in the determination of both Rh6G and RhB in chilli powder and lipstick samples with satisfactory recoveries of 81.3-103.7%.

  12. Traceable atomic force microscopy of high-quality solvent-free crystals of [6,6]-phenyl-C{sub 61}-butyric acid methyl ester

    Energy Technology Data Exchange (ETDEWEB)

    Lazzerini, Giovanni Mattia; Yacoot, Andrew [National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW (United Kingdom); Paternò, Giuseppe Maria; Tregnago, Giulia; Cacialli, Franco [Department of Physics and Astronomy and London Centre for Nanotechnology, University College London, Gower Street, London WC1E 6BT (United Kingdom); Treat, Neil; Stingelin, Natalie [Department of Materials Science, Imperial College London, London SW7 2AZ (United Kingdom)

    2016-02-01

    We report high-resolution, traceable atomic force microscopy measurements of high-quality, solvent-free single crystals of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). These were grown by drop-casting PCBM solutions onto the spectrosil substrates and by removing the residual solvent in a vacuum. A home-built atomic force microscope featuring a plane mirror differential optical interferometer, fiber-fed from a frequency-stabilized laser (emitting at 632.8 nm), was used to measure the crystals' height. The optical interferometer together with the stabilized laser provides traceability (via the laser wavelength) of the vertical measurements made with the atomic force microscope. We find that the crystals can conform to the surface topography, thanks to their height being significantly smaller compared to their lateral dimensions (namely, heights between about 50 nm and 140 nm, for the crystals analysed, vs. several tens of microns lateral dimensions). The vast majority of the crystals are flat, but an isolated, non-flat crystal provides insights into the growth mechanism and allows identification of “molecular terraces” whose height corresponds to one of the lattice constants of the single PCBM crystal (1.4 nm) as measured with X-ray diffraction.

  13. The solvent-tolerant Pseudomonas putida S12 as host for the production of cinnamic acid from glucose

    NARCIS (Netherlands)

    Nijkamp, K.; Luijk, N. van; Bont, J.A.M. de; Wery, J.

    2005-01-01

    A Pseudomonas putida S12 strain was constructed that efficiently produced thefine chemical cinnamic acid from glucose or glycerol via the central metabolite phenylalanine. The gene encoding phenylalanine ammonia lyase from the yeast Rhodosporidium toruloides was introduced. Phenylalanine availabilit

  14. Penelitian pengaruh variasi china clay dan naphthenic oil terhadap perpanjangan tetap dan tegangan putus kompon karet untuk lis pintu almari es

    Directory of Open Access Journals (Sweden)

    A Buchori

    1997-12-01

    Full Text Available The aim of this research is to know the influence of filer china clay naphthenic oil to the physical properties of permanent set and tensile strength rubber compound for refrigerator gasket. It makes from natural rubber ( pale crepe and synthetic rubber (SBR 1502 as raw material with addition of ingredients such as : softener, activator, filler, antioxidant, accelerator, coloring and vulcanizing agent. It should be carried out using base formula by varying china clay : 30; 40 ; and 50 parts and naphthenic oil : 5,0 ; 7,5 and 10 parts for 9 compound then should be tested their physical properties permanent set and tensile strength. The result of the test statistically prove that china clay and naphthenic oil influence the physical properties for permanent set by china clay 30 parts and naphthenic oil 5 parts, the value 1,24%, for tensile strength by china clay 50 parts and naphthenic oil 5 parts, the value 102,6081 Kg/Cm2.

  15. Long-chain ethers as solvents can amplify the enantioselectivity of the Carica papaya lipase-catalyzed transesterification of 2-(substituted phenoxy)propanoic acid esters.

    Science.gov (United States)

    Miyazawa, Toshifumi; Iguchi, Wakana

    2013-10-01

    The enantioselectivity of the transesterification of the 2,2,2-trifluoroethyl esters of 2-(substituted phenoxy)propanoic acids, as catalyzed by the lipase from Carica papaya, was greatly improved by using long-chain ethers, such as di-n-hexyl ether, as solvents instead of the conventional diisopropyl ether. Thus, for example, the E value was enhanced from 21 [in diisopropyl ether (0.8 ml)] to 57 [in di-n-hexyl ether (0.8 ml)] in the reaction of 2,2,2-trifluoroethyl(RS)-2-phenoxypropanoate (0.1 mmol) with methanol (0.4 mmol) in the presence of the plant lipase preparation (10 mg); it was also improved from 13 (in diisopropyl ether) to 44 (in di-n-hexyl ether) in the reaction of 2,2,2-trifluoroethyl(RS)-2-(2-chlorophenoxy)propanoate with methanol under the same reaction conditions.

  16. Stereochemistry of Complex Marine Natural Products by Quantum Mechanical Calculations of NMR Chemical Shifts: Solvent and Conformational Effects on Okadaic Acid

    Directory of Open Access Journals (Sweden)

    Humberto J. Domínguez

    2014-01-01

    Full Text Available Marine organisms are an increasingly important source of novel metabolites, some of which have already inspired or become new drugs. In addition, many of these molecules show a high degree of novelty from a structural and/or pharmacological point of view. Structure determination is generally achieved by the use of a variety of spectroscopic methods, among which NMR (nuclear magnetic resonance plays a major role and determination of the stereochemical relationships within every new molecule is generally the most challenging part in structural determination. In this communication, we have chosen okadaic acid as a model compound to perform a computational chemistry study to predict 1H and 13C NMR chemical shifts. The effect of two different solvents and conformation on the ability of DFT (density functional theory calculations to predict the correct stereoisomer has been studied.

  17. Preparation of porous carboxymethyl chitosan grafted poly (acrylic acid) superabsorbent by solvent precipitation and its application as a hemostatic wound dressing.

    Science.gov (United States)

    Chen, Yu; Zhang, Yong; Wang, Fengju; Meng, Weiwei; Yang, Xinlin; Li, Peng; Jiang, Jianxin; Tan, Huimin; Zheng, Yongfa

    2016-06-01

    The volume phase transition of a hydrogel initiated by shrinking may result in complex patterns on its surface. Based on this unique property of hydrogel, we have developed a novel solvent precipitation method to prepare a kind of novel superabsorbent polymers with excellent hemostatic properties. A porous carboxymethyl chitosan grafted poly (acrylic acid) (CMCTS-g-PAA) superabsorbent polymer was prepared by precipitating CMCTS-g-PAA hydrogel with ethanol. Its potential application in hemostatic wound dressing was investigated. The results indicate that the modified superabsorbent polymer is non-cytotoxic. It showed a high swelling capacity and better hemostatic performance in the treatments of hemorrhage model of ear artery, arteria cruralis and spleen of the New Zealand white rabbit than the unmodified polymer and other commonly used clinic wound dressings. The hemostatic mechanism of the porous CMCTS-g-PAA polymer was also discussed.

  18. Photophysical properties and excited state intramolecular proton transfer in 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid in homogeneous solvents and micro-heterogeneous environments

    Energy Technology Data Exchange (ETDEWEB)

    Gashnga, Pynsakhiat Miki [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India); Singh, T. Sanjoy [Department of Chemistry, Assam University, Silchar 788011, Assam (India); Baul, Tushar S. Basu [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India); Mitra, Sivaprasad, E-mail: smitra@nehu.ac.in [Centre for Advanced Studies, Department of Chemistry, North-Eastern Hill University, Shillong 793022, Meghalaya (India)

    2014-04-15

    A systematic study on the photophysical properties and excited state intramolecular proton transfer (ESIPT) behavior of 2-hydroxy-5-[(E)-(4-methoxyphenyl)diazenyl]benzoic acid, is reported using steady-state and time-resolved fluorescence spectroscopy in homogeneous solvents as well as in different micro-heterogeneous environments. Depending on the nature of intramolecular hydrogen bond (IHB), the salicylic acid derivative may exist in two different ground state conformers (I and II). Structure I having IHB between the carbonyl oxygen and phenolic hydrogen can undergo ESIPT upon excitation as evidenced by largely Stokes-shifted fluorescence at ∼455 nm; whereas, normal fluorescence in the blue side of the spectrum (∼410 nm) is due to the spontaneous emission from conformer II. The results in homogeneous solvents were compared with those in bio-mimicking environments of β-cyclodextrin (CD) and surfactants. The intensity of the ESIPT fluorescence increases substantially upon encapsulation of the probe into the cyclodextrin as well as micellar nano-cavities. Detailed analysis of the spectroscopic data indicates that the probe forms 1:1 complex with CD in aqueous medium. Binding constant of the probe with the micelles as well as critical micelle concentration was obtained from the variation of fluorescence intensity on increasing concentration of different surfactants in aqueous medium. -- Highlights: • Steady state and time resolved fluorescence study on ESIPT in HMBA. • Dual fluorescence corresponding to the pro- and non-ESIPT structures. • Modulation of ESIPT fluorescence in micro-heterogeneous environments. • 1:1 stoichiometry for interaction with cyclodextrin. • Calculation of binding constant and other physico-chemical properties from fluorescence titration data in surfactants.

  19. IMIDAZOLIUM IONIC LIQUIDS AS DISSOLVING SOLVENTS FOR CHEMICAL-GRADE CELLULOSE IN THE DETERMINATION OF FATTY ACIDS USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY

    Directory of Open Access Journals (Sweden)

    Kessy F. Kilulya

    2011-06-01

    Full Text Available A quick, simple, and environmentally friendly sample preparation method for fatty acids analysis from chemical-grade cellulose was developed employing imidazolium based ionic liquids as solvents. A variety of imidazolium based ionic liquids were screened for their ability to dissolve chemical cellulose at different temperatures. Dissolution of chemical cellulose was observed to be dependent on the ionic liquids’ anions as well as temperature. The effect of ionic liquids on chemical cellulose was examined using FT-IR and TGA techniques, which showed no difference between the original and the regenerated cellulose except for the percentage mass residues in TGA profile which was high for regenerated cellulose, 15% compared to 8% of the original at 600 °C. Fatty acids extracted from cellulose were found to be predominant in the samples from different bleaching stages, with high levels in the oxygen delignification and low levels were observed in hypochlorite bleached samples. The number and levels of the identified fatty acids were observed to decrease with the bleaching sequence. The recoveries obtained using this method ranged from 90 to 107%.

  20. Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids%有机磷(膦)酸对碱土金属的萃取

    Institute of Scientific and Technical Information of China (English)

    许新; 朱屯

    2002-01-01

    Solvent extraction equilibria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester,di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent on the e/r value and hydration energy of the metal ions. The minor shift of the P-O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P-O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compounds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effect is explained by using IR spectra of the loaded organic phase.

  1. 菜籽预榨-浸出粕中植酸的提取%Extraction of phytic acid from prepress - solvent extracted rapeseed meal

    Institute of Scientific and Technical Information of China (English)

    鲍传稳; 张明辉; 刘晔

    2012-01-01

    为实现菜籽粕的综合开发利用,研究了一种从菜籽预榨-浸出粕中两步提取植酸的工艺.考察了酸洗pH、酸洗时间、碱提pH和碱提乙二胺四乙酸二钠(EDTA)浓度等对植酸提取的影响.将经过复合纤维素酶水解的菜籽粕在pH 5.0和50℃下酸洗3h获得酸洗液,然后用EDTA浓度0.1mol/L的碱性溶液在pH 12.0和50℃下碱提酸沉获得乳清液,经以上两步可将菜籽粕中的植酸基本提取完全.将提取液中的粗植酸经氢氧化钙沉淀并酸化,再经离子交换可获得纯度为69.96%、提取率为58.0%的植酸产品.%To realize fully utilization of rapeseed meal, a two - step process for extraction of phytic acid from prepress - solvent extracted rapeseed meal was established. The effects of key parameters on phytic acid extraction, including pH of acid solution, duration of acid solution, pH and ethylene diamine tetraace-tic acid(EDTA) concentration of alkaline solution for extraction were investigated. With an acid solution extracting step at pH 5.0 and 501 for 3 h and an alkaline solution extracting step at pH 12.0 and 50℃ with the supplement of 0.1 mol/L EDTA followed by acidic precipitation, the phytic acid in cellulase pre-treated rapeseed meal could be almost entirely extracted. The crude phytic acid in extracted solution was purified by calcium hydroxide precipitation and acidification, then it was treated with ion exchange to obtain a final product with purity of 69. 96% and extraction rate of 58.0%.

  2. Estudo da influência do solvente, carboidrato e ácido graxo na síntese enzimática de ésteres de açúcares Study of the influence of solvent, carbohydrate and fatty acid in the enzymatic synthesis of sugar esters by lipases

    OpenAIRE

    2005-01-01

    The aim of this work was to gain knowledge of enzymatic processes for the synthesis fatty acid esters of sugar, with the objective to develop an enzymatic process for the preparation of non-toxic biodegradable surface-active agents derived entirely from renewable resources. A wide range of data were collected for reaction conditions involving different sugars (glucose, fructose and sucrose), fatty acids (oleic, palmitic, lauric), solvents (hexane, heptane and t-butanol) and different sources ...

  3. Separation of middle rare earths by solvent extraction using 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant

    Institute of Scientific and Technical Information of China (English)

    Danilo; Fontana; Loris; Pietrelli

    2009-01-01

    The extraction of the trivalent middle rare earths from chloride media by kerosene solutions of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester as an extractant was studied. The separation factors between the elements using solution simulating wastes from NiMH spent batteries have been evaluated: the order of the extractive ability of extractant can be confirmed in ThGdEuSm.

  4. Solvent extraction of rare earth ions from nitrate media with new extractant di-(2,3-dimethylbutyl)-phosphinic acid

    Institute of Scientific and Technical Information of China (English)

    王俊莲; 陈广; 徐盛明; 尹祉力; 张覃

    2016-01-01

    As a relatively new extractant, di-(2,3-dimethylbutyl)-phosphinic acid (HYY-2) is more efficient to separate heavy rare earths Tm/Yb/Lu than Cyanex 272 and P507. In this paper, HYY-2 was synthesized in our lab, and the extraction equilibrium, ther-modynamics and stripping acidity for La, Gd and Y, which stood for light rare earth elements (REE), middle REE and heavy REE respectively, from nitrate media with this extractant were investigated. Meanwhile, extraction ability, capacity and stripping acidity of HYY-2 were investigated and compared with those of Cyanex 272 and P507. The separation performance for rare earth element cou-ples Gd/Eu and Er/Ywere also studied. Compared to Cyanex 272, it possessed higher extraction capacity; while compared with P507, it has lower stripping acidity. The maximumβGd/Eu 1.46 occurred at pHequilibrium=2.78 and the maximumβEr/Y was 1.47 when pHequilibrium= 2.01.

  5. Oxidation of Cyclohexene to "trans"-1,2-Cyclohexanediol Promoted by "p"-Toluenesulfonic Acid without Organic Solvents

    Science.gov (United States)

    Rosatella, Andreia A.; Afonso, Carlos A. M.; Branco, Lus C.

    2011-01-01

    This experiment describes a method for cyclohexene oxidation to "trans"-1,2-cyclohexanediol using "p"-toluenesulfonic acid ("p"-TsOH) as promoter and hydrogen peroxide as oxidant in a biphasic system. This method allows conversions up to 97.9% (monitored by [superscript 1]H NMR). "trans"-1,2-Cyclohexanediol was not easily separated from the…

  6. Two-dimensional gas chromatography and trilinear partial least squares for the quantitative analysis of aromatic and naphthene content in naphtha.

    Science.gov (United States)

    Prazen, B J; Johnson, K J; Weber, A; Synovec, R E

    2001-12-01

    Quantitative analysis of naphtha samples is demonstrated using comprehensive two-dimensional gas chromatography (GC x GC) and chemometrics. This work is aimed at providing a GC system for the quantitative and qualitative analysis of complex process streams for process monitoring and control. The high-speed GC x GC analysis of naphtha is accomplished through short GC columns, high carrier gas velocities, and partial chromatographic peak resolution followed by multivariate quantitative analysis. Six min GC x GC separations are analyzed with trilinear partial least squares (tri-PLS) to predict the aromatic and naphthene (cycloalkanes) content of naphtha samples. The 6-min GC x GC separation time is over 16 times faster than a single-GC-column standard method in which a single-column separation resolves the aromatic and naphthene compounds in naphtha and predicts the aromatic and naphthene percent concentrations through addition of the resolved signals. Acceptable quantitative precision is provided by GC x GC/tri-PLS.

  7. The chemistry of tetrameric acids in petroleum.

    Science.gov (United States)

    Sjöblom, Johan; Simon, Sébastien; Xu, Zhenghe

    2014-03-01

    This article reviews the properties of a novel class of molecules: the tetrameric acids. These molecules have brought a large interest in petroleum science since the discovery of the family of molecules named ARN in 2004. ARN, which is naturally present in oil, is responsible, by reaction with calcium ion, of the formation of calcium naphthenate deposits; organic deposits that cause irregularities in crude oil production and processing. In order to study the properties of ARN, a model tetrameric acid molecule mimicking some of its properties named BP-10 has been developed in 2008 by Nordgård and Sjöblom and has been extensively used since then. After presenting the experimental techniques used to study the tetrameric acids, this review describes in detail the structure, preparation, detection and the bulk and interfacial properties of tetrameric acids ARN and BP-10. Finally the prediction of the operational problems with calcium naphthenate precipitation in new fields is discussed.

  8. Diamex solvent regeneration studies

    Energy Technology Data Exchange (ETDEWEB)

    Nicol, C.; Cames, B.; Margot, L.; Ramain, L. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, DRRV, 30 - Marcoule (France)

    2000-07-01

    The CEA has undertaken the development of the DIAMEX process as the first step in the strategy aiming at recovering minor actinides which could then be transmuted or separately conditioned. The scientific feasibility of this process was demonstrated during counter current hot tests operated in 1993. Then experimental works were conducted, on one hand to optimise the extractant formula, on the other hand to improve the flowsheet. Reference extractant and flowsheet were then chosen, respectively in 1995 and 1996. The next step, still in progress, is the demonstration of the DIAMEX technical feasibility (in 2002); this means that the flowsheet should include solvent regeneration treatments. In this aim, degradation studies were performed to quantify main degradation products, and identify those which could be disturbing in the process. This paper deals with experimental studies performed with intend to propose a regeneration treatment, included in the flowsheet, so that the solvent could be recycled. It comprises: - Quantification of the main degradation products issued from radiolysis or hydrolysis, which are methyl octyl amine (MOA) and carboxylic acids; - Effects of these products on extracting and hydrodynamics performances of the process; - Study of methods able to remove mainly disturbing degradation products. Acidic scrubbing, which are performed in the scrubbing and stripping sections of the DIAMEX process, should allow the quantitative removal of methyl octyl amine. Then basic scrubbings, which were more especially studied, should eliminate at least 80% of carboxylic acids, and part of the cations remaining in the solvent. (authors)

  9. Recovery of rare earths from acid leach solutions of spent nickel-metal hydride batteries using solvent extraction

    Institute of Scientific and Technical Information of China (English)

    夏允; 肖连生; 田吉英; 李兆洋; 曾理

    2015-01-01

    The extraction of rare earths from acid leach solutions of spent nickel-metal hydride batteries using a primary amine ex-tractant of N1923 was studied. The effects of feed pH, temperature, agitation rate and time on the extraction of rare earths, as well as stripping agent composition and concentration, phase ratio on the stripping were investigated. In addition, the extraction isotherm was determined. The pilot plant test results showed that the extraction of rare earths reached 99.98% after a five-stage counter current ex-traction. The mixed rare earths oxalates with the 99.77% purity of rare earth elements and impurity content less than 0.05% were ob-tained by the addition of oxalic acids in loaded strip liquors. The extractant exhibited good selectivity of rare earths over base metals of iron, nickel, copper and manganese.

  10. Estimation of free energy barriers in the cytoplasmic and mitochondrial aspartate aminotransferase reactions probed by hydrogen-exchange kinetics of C alpha-labeled amino acids with solvent

    Energy Technology Data Exchange (ETDEWEB)

    Julin, D.A.; Wiesinger, H.; Toney, M.D.; Kirsch, J.F. (Univ. of California, Berkeley (USA))

    1989-05-02

    The existence of the postulated quinonoid intermediate in the cytoplasmic aspartate amino-transferase catalyzed transamination of aspartate to oxaloacetate was probed by determining the extent of transfer of tritium from the C alpha position of tritiated L-aspartate to pyridoxamine 5'-phosphate in single turnover experiments in which washout from the back-reaction was obviated by product trapping. The maximum amount of transferred tritium observed was 0.7%, consistent either with a mechanism in which a fraction of the net transamination reaction proceeds through a quinonoid intermediate or with a mechanism in which this intermediate is formed off the main reaction pathway. It is shown that transfer of labeled hydrogen from the amino acid to cofactor cannot be used to differentiate a stepwise from a concerted transamination mechanism. The amount of tritium transferred is a function of the rate constant for torsional equilibration about the epsilon-amino group of Lys-258, the presumptive abstractor of the C alpha proton; the relative rate constants for hydrogen exchange with solvent versus cofactor protonation; and the tritium isotope effect on this ratio. The free energy barriers facing the covalent intermediate between aldimine and keto acid product (i.e., ketimine and possibly quinonoid) were evaluated relatively by comparing the rates of C alpha-hydrogen exchange in starting amino acid with the rates of keto acid formation. The value of theta (= kexge/kprod) was found to be 2.6 for the reaction of cytoplasmic isozyme with aspartate and ca. 0.5 for that of the mitochondrial form with glutamate.

  11. Cation-exchange high-performance liquid chromatography: Separation of highly basic proteins using volatile acidic solvents

    NARCIS (Netherlands)

    Eijnden-van Raaij, A.J.M. van den; Koornneef, I.; Oostwaard, Th.M.J.; Laat, S.W. de; Zoelen, E.J.J. van

    1987-01-01

    The chromatographic behavior of a number of globular proteins was studied on a Bio-Sil TSK CM-2-SW weak cation exchange HPLC column under acidic conditions. A linear gradient of O-I M NH₄Ac in I M HOAc, inducing a convex pH gradient from 2.4-4.8, resulted in an excellent separation of highly basic p

  12. Ultrasound-assisted catalytic synthesis of acyclic imides in the presence of p-toluenesulfonic acid under solvent free conditions

    Directory of Open Access Journals (Sweden)

    Nasr-Esfahani Masoud

    2012-01-01

    Full Text Available A rapid and convenient preparation of acyclic imides by the reaction of aliphatic and aromatic nitriles with acyclic carboxylic anhydride in the presence of catalytic amounts of p-toluenesulfonic acid under thermal or ultrasonic conditions is reported. The advantages of this procedure are moderate reaction times, good to excellent yields, use of inexpensive and ecofriendly catalyst. The reaction of nitriles with aliphatic anhydrides proceeds in thermal conditions, while by the use of ultrasound irradiations these reactions get accelerated.

  13. Substituted ethan phosphonic acid esters as reagents for the separation of molybdenum from rhenium by solvent extraction.

    Science.gov (United States)

    Jordanov, N; Mareva, S; Borisov, G; Jordanov, B

    1968-02-01

    New esters of the ethan phosphonic acids have been synthesized and their extraction properties studied with respect to Mo(VI), Re(VII), Fe(III),Au(III),Tl(III) and Sb(V). A possibility is shown for the analytical separation of molybdenum from rhenium (beta = 700). The state of these new extraction agents in carbon tetrachloride solution, and the mechanism of the extraction processes, have been investigated by means of infrared spectra.

  14. Solvent extraction of nitric acid,uranium(VI) and thorium(IV) by N,N,N',N'-tetrahexylsuccinylamide

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    A new kind of diamideN,N,N',N'-tetrahexylsuccinylamide (THSA)wassynthesized,characterized and used for the extraction of HNO3,U(VI) and Th(IV)in a diluent composed of 0.5 volume fraction1,2,4-trimethy benzene(TMB) and 0.5 volume fraction kerosene(OK).Extraction distribution coefficients of U(VI) and Th(IV) as functionsof aqueous nitric acid concentration, extractant concentration,temperature and salting-out agent (LiNO3) have been studied, and it is found that THSA as an extractant is superior to TBP for extraction ofU(VI) and Th(IV).Back extraction was also studied.At low acidity, themain adduct of THSA and HNO3 is HNO3.THSA.THSA.(HNO3)2 and THSA.(HNO3)3 are also found at high acidity.The compositions of extracted species, apparent equilibrium constants and enthalpies ofextraction reactions have also been calculated.

  15. Magnetic Nanoparticle Immobilized N-Propylsulfamic Acid as a Recyclable and Efficient Nanocatalyst for the Synthesis of 2H-indazolo[2,1-b]phthalazine-triones in Solvent-Free Conditions: Comparison with Sulfamic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Rostami, Amin; Tahmasbi, Bahman; Yari, Ako [Univ. of Kurdistan, Sanandaj (Iran, Islamic Republic of)

    2013-05-15

    N-Propylsulfamic acid supported onto magnetic Fe{sub 3}O{sub 4} nanoparticles (MNPs-PSA) was used as an efficient and magnetically recoverable catalyst for synthesis of 2H-Indazolo[2,1-b]phthalazine-1,6,11(13H)-trione derivatives from the three-component, one-pot condensation reaction of phthalhydrazide, aromatic aldehydes and cyclic 1,3-diones, in good to excellent yields at 100 .deg. C under solvent-free conditions. The catalyst was easily separated with the assistance of an external magnetic field from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency. In order to compare, the synthesis of 2H-Indazolo[2,1-b]phthalazine-1,6,11(13H)-trione derivatives in the presence of catalytic amount of sulfamic acid (SA) under same reaction condition was also reported.

  16. Preparation of Solid Phase Microextraction (SPME) Probes through Polyaniline Multiwalled Carbon Nanotubes (PANI/MWCNTs) Coating for the Extraction of Palmitic Acid and Oleic Acid in Organic Solvents.

    Science.gov (United States)

    Khajeamiri, Alireza

    2012-01-01

    A fiber coating from polyaniline (PANI) was electrochemically prepared and employed for Solid phase micreoextraction (SPME). The PANI film was directly electrodeposited on the platinum wire surface using cyclic voltametry (CV) technique. The same method was applied for the preparation of SPME fiber coated by polyaniline multiwalled carbon nanotubes (PANI/MWCNTs) composite. The concentration of sulfuric acid for electropolymerization was 0.1 M in the presence of 0.045 M aniline in aqueous solution. For the electrodeposition of PANI/MWCNT composite, 4 μg/mL of MWCNTs was dispersed into the solution. Film coating was carried out on the platinum wire by repetitive cycling of potentials between 0 and 1.0 V at the scan rate of 0.05 V/s. The applicability of these coatings were assessed through employing a laboratory-made SPME injecting device and gas chromatography with mass spectrometry (GC-MS) for the extraction of palmitic acid and oleic acid from chloroform. The developed method proved to be simple and easy, offering high reproducibility. Both PANI coated and PANI/CNT coated probes had the ability to concentrate palmitic acid and oleic acid on their coating and produced strong signals in GC-MS chromatograms. In the meantime, PANI/CNT coated SPME probes produced signals which were stronger than those produced by PANI coated SPME probes. The amount of extracted palmitic acid and oleic acid from chloroform by the PANI/MWCNTs coating was about 6 and 12 times higher than the amount extracted by plane PANI SPME fibers respectively. It could be suggested that the composite material with CNTs has both an increased surface area and an elevated absorptive capacity which leads to this overall increase in extracted palmitic acid and oleic acid.

  17. Solvent extraction of La(III) with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (EHEHPA) by membrane dispersion micro-extractor

    Institute of Scientific and Technical Information of China (English)

    侯海龙; 王运东; 徐建鸿; 陈晋南

    2013-01-01

    The conventional rare earth solvent extraction equipments have many problems such as long mixing time, low processing capacity, large factory area occupation, high energy consumption and so on. In order to solve the problems, many types of equipments were brought out. In this work, studies were carried out on the La(III) extraction process with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (EHEHPA) by membrane dispersion micro-extractor. Equilibrium studies showed that the initial aqueous pH value 4.15 with the saponification rate 40%was the optimal operation condition. The effects of membrane dispersion micro-extractor operational conditions such as dispersion mode, bulk flow rate and organic phase flow rate on the extraction efficiency were studied. The results showed that when the organic solution was the dispersed phase, the extraction efficiency was higher than that of others. Increasing bulk flow ratio could enhance the extraction efficiency greatly. When the ratio of organic phase flow rate to that of aque-ous phase was 80:80, the extraction efficiency was over 95%. The effect of stripping phase acidity on the La(III) recovery was studied. The results showed that when the stripping phase pH was 2.0, organic phase flow rate to stripping phase flow rate was 20:80;the re-covery efficiency of La(III) can reach 82%.

  18. Synthesis of sn-2 docosahexaenoyl monoacylglycerol by mild enzymatic transesterification of docosahexaenoic acid ethyl ester and glycerol in a solvent-free system

    Directory of Open Access Journals (Sweden)

    Sonia Moreno-Perez

    2016-12-01

    Full Text Available The enzymatic transesterification of docosahexaenoic acid (DHA ethyl ester with glycerol was performed with several lipases in a solvent-free system and it involves the initial formation of sn-2 docosahexaenyl monoacylglyceride. This DHA derivative is highly relevant for improving the bioavailability of DHA and it has received increasing interest in the field of nutrition. Three commercial lipases, from Rhizomucor miehei (RML, Alcaligenes sp (QL, and Candida antarctica-fraction B (CALB were tested. In certain cases (CALB, using an excess of DHA ethyl ester and high temperatures the transesterification reaction continues to the formation of triacylglycerides, but in other cases, sn-2 monoacylglyceride (2-MG is the unique synthetic product even in the presence of high concentrations of DHA ethyl ester. At low temperatures (e.g. 37°C, RML derivatives synthesize only 2-MG in 15 min. These very mild conditions are very interesting for the thermal oxidative stability of the omega-3 fatty acid and for the thermal stability of the biocatalyst. Using Normal Phase HPLC-ELSD and accurate markers, the formation of the 2-MG was confirmed.

  19. Structure elucidation of C80, C81 and C82 isoprenoid tetraacids responsible for naphthenate deposition in crude oil production.

    Science.gov (United States)

    Lutnaes, Bjart F; Krane, Jostein; Smith, Ben E; Rowland, Steven J

    2007-06-21

    A series of C(80) isoprenoid 20-bis-16,16'-biphytanyl tetraacids has previously been found to be responsible for calcium naphthenate scaling in crude oil processing. This paper describes the structure elucidation by high-field NMR spectroscopy of the structures of the series of homologous C(80) tetraacids containing 4-8 five-membered rings. In addition, the structures of methyl-substituted C(81) and C(82) analogues containing 7 and 8 five-membered rings have been determined for the first time. The biosynthetic implications are discussed.

  20. Melamine trisulfonic acid: A new, efficient and recyclable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones in the absence of solvent

    Institute of Scientific and Technical Information of China (English)

    Farhad Shirini; Mohammad Ali Zolfigol; Jalal Albadi

    2011-01-01

    Melamine trisulfonic acid (MTSA) can be used as an efficient and recyclable catalyst for the promotion of the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones (DHPMs) in the absence of solvent. All reactions were performed at 80 ℃ in good to high yields.

  1. Comparative study of corn stover pretreated by dilute acid and cellulose solvent-based lignocellulose fractionation: Enzymatic hydrolysis, supramolecular structure, and substrate accessibility.

    Science.gov (United States)

    Zhu, Zhiguang; Sathitsuksanoh, Noppadon; Vinzant, Todd; Schell, Daniel J; McMillan, James D; Zhang, Y-H Percival

    2009-07-01

    Liberation of fermentable sugars from recalcitrant biomass is among the most costly steps for emerging cellulosic ethanol production. Here we compared two pretreatment methods (dilute acid, DA, and cellulose solvent and organic solvent lignocellulose fractionation, COSLIF) for corn stover. At a high cellulase loading [15 filter paper units (FPUs) or 12.3 mg cellulase per gram of glucan], glucan digestibilities of the corn stover pretreated by DA and COSLIF were 84% at hour 72 and 97% at hour 24, respectively. At a low cellulase loading (5 FPUs per gram of glucan), digestibility remained as high as 93% at hour 24 for the COSLIF-pretreated corn stover but reached only approximately 60% for the DA-pretreated biomass. Quantitative determinations of total substrate accessibility to cellulase (TSAC), cellulose accessibility to cellulase (CAC), and non-cellulose accessibility to cellulase (NCAC) based on adsorption of a non-hydrolytic recombinant protein TGC were measured for the first time. The COSLIF-pretreated corn stover had a CAC of 11.57 m(2)/g, nearly twice that of the DA-pretreated biomass (5.89 m(2)/g). These results, along with scanning electron microscopy images showing dramatic structural differences between the DA- and COSLIF-pretreated samples, suggest that COSLIF treatment disrupts microfibrillar structures within biomass while DA treatment mainly removes hemicellulose. Under the tested conditions COSLIF treatment breaks down lignocellulose structure more extensively than DA treatment, producing a more enzymatically reactive material with a higher CAC accompanied by faster hydrolysis rates and higher enzymatic digestibility.

  2. Zirconium phosphate nanoparticles as a remarkable solid acid catalyst for selective solvent-free alkylation of phenol

    Institute of Scientific and Technical Information of China (English)

    Abdol R. Hajipour; Hirbod Karimi

    2014-01-01

    A facile synthesis of α-zirconium phosphate (ZP) nanoparticles as an effective, eco-friendly, and recyclable solid acid catalyst is reported. Polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) were used as organic matrix as dispersing agents and served as a template for the nanoparticles. Hydrogen bonds between ZP and PVA or PVP, along the polymer chains, appear to play an im-portant role for improving the dispersion of in situ formed ZP. Following calcination of PVA/ZP or PVP/ZP, pure hexagonal ZP nanoparticles were obtained. The catalysts were characterized by ni-trogen sorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, Fouri-er transform infrared spectroscopy (FTIR), scanning electron microscopy, and transmission elec-tron microscopy. Pyridine-FTIR and temperature-programmed desorption of NH3 suggest the presence of Brönsted acid sites. The acidic properties of the catalyst were studied in Friedel-Crafts alkylation of phenol by tert-butanol, producing 2-tert-butylphenol, 4-tert-butylphenol, and 2,4-di-tert-butylphenol. The alkylation reaction was performed in the presence of catalysts P2O5/Al2O3, P2O5/SiO2, α-ZrP (prepared in the absence of the polymers), and various ionic liquids. The use of the hexagonal ZP nanoparticle catalyst afforded an excellent phenol conversion (86%) and selectivity towards 4-tert-butylphenol (83%) under optimized reaction conditions. The catalyst was easily recovered from the reaction mixture, regenerated, and reused at least four times without significant loss in the catalytic activity.

  3. Regeneration of high-quality silk fibroin fiber by wet spinning from CaCl2-formic acid solvent.

    Science.gov (United States)

    Zhang, Feng; Lu, Qiang; Yue, Xiaoxiao; Zuo, Baoqi; Qin, Mingde; Li, Fang; Kaplan, David L; Zhang, Xueguang

    2015-01-01

    Silks spun by silkworms and spiders feature outstanding mechanical properties despite being spun under benign conditions. The superior physical properties of silk are closely related to its complicated hierarchical structures constructed from nanoscale building blocks, such as nanocrystals and nanofibrils. Here, we report a novel silk dissolution behavior, which preserved nanofibrils in CaCl2-formic acid solution, that enables spinning of high-quality fibers with a hierarchical structure. This process is characterized by simplicity, high efficiency, low cost, environmental compatibility and large-scale industrialization potential, as well as having utility and potential for the recycling of silk waste and the production of silk-based functional materials.

  4. Solvent-induced chemical shifts of methoxyl nuclear resonance signals in chalcones by benzene and trifluoroacetic acid

    Science.gov (United States)

    Khurana, Shashi K.; Krishnamoorthy, V.; Parmar, Virinder S.

    The 1H NMR spectra of eight different methoxylated chalcones have separately been recorded, (1) in deuterated chloroform; (2) in a mixture (1:1) of deuterated chloroform and benzene; and (3) in a mixture of deuterated chloroform, benzene and trifluoroacetic acid (2:2:1) and the benzene induced and TFA induced shift values have been assigned to different methoxyl groups. These shift values can serve as a guide in determining the structures of natural or new chalcones. The steric, electronic and conformational factors are discussed to explain the shift values.

  5. Covalently anchored sulfonic acid on silica gel (SiO2-R-SO3H) as an efficient and reusable heterogeneous catalyst for the one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Gholam Hossein Mahdavinia; Mohammad A.Bigdeli; Yaser Saeidi Hayeniaz

    2009-01-01

    A highly efficient one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions catalyzed by sulfonic acid covalently anchored onto the surface of silica gel is reported.All types of aldehydes,including aromatic,unsaturated,and heterocyclic,are used.The silica gel/sulfonic acid catalyst (SiO2-R-SO3H) is completely heterogeneous and can be recycled.

  6. Mesostructured SBA-15-Pr-SO3H: An efficient solid acid catalyst for one-pot and solvent-free synthesis of 3,4-dihydro-2-pyridone derivatives

    Indian Academy of Sciences (India)

    Ghodsi Mohammadi Ziarani; Somayeh Mousavi; Negar Lashgari; Alireza Badiei

    2013-11-01

    3,4-Dihydro-2-pyridone derivatives have been prepared efficiently via a one-pot four-component reaction of benzaldehyde derivatives, Meldrum’s acid, methyl acetoacetate and ammonium acetate in the presence of sulphonic acid-functionalized ordered nanoporous SBA-15 as a nano heterogeneous catalyst under solvent-free conditions. This process is a simple, environmentally friendly, rapid and high yielding reaction.

  7. Effect of Solvent and Acid-Base on Palladium(ll)-catalyzed Dicarbonylation of Terminal Acetylenes: a General, Efficient andStereoselective Synthesis of Maleic Diesters and Maleic Anhydrides

    Institute of Scientific and Technical Information of China (English)

    JIANG, Huan-Feng; LI, JiN-Heng; CHEN, Ming-Cai

    2001-01-01

    The productions of maleic diesters and maleic anhydrises depend on the effect of solvint and acid-bade of solvent and acid-base in palladium-catalyzed dicarbonylation of terminal acetylenes. For primaryand secondary alcohol in benzene.only maleic diesters wereobtained stereospecifically from the sicabonylation ofacetylenes in the presence of PdCl2,and NaHCO3.For tERTIARy alcohols,maleic anhydrides were synthesized selectively.

  8. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C6 F5 )3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H2 splitting at the carbonyl carbon atom of (C6 F5 )3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C6 F5 )3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C6 F5 )3 B, as a catalyst, namely, 1) the step of H2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C6 F5 )3 B-ketone adducts in which (C6 F5 )3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C6 F5 )3 B-alkoxide intermediate giving the (C6 F5 )3 B-alcohol adduct, and 3) the SN 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Effect of temperature and solvent composition on acid dissociation equilibria, I: Sequenced (s)(s)pKa determination of compounds commonly used as buffers in high performance liquid chromatography coupled to mass spectroscopy detection.

    Science.gov (United States)

    Padró, Juan M; Acquaviva, Agustín; Tascon, Marcos; Gagliardi, Leonardo G; Castells, Cecilia B

    2012-05-06

    A new automated and rapid potentiometric method for determining the effect of organic-solvent composition on pK(a) has been developed. It is based on the measurements of pH values of buffer solutions of variable solvent compositions using a combined glass electrode. Additions of small volumes of one precisely thermostated solution into another, both containing exactly the same analytical concentrations of the buffer components, can produce continuous changes in the solvent composition. Two sequences of potential measurements, one of increasing and the other of decreasing solvent content, are sufficient to obtain the pK(a) values of the acidic compound within the complete solvent-composition range in about 2h. The experimental design, procedures, and calculations needed to convert the measured pH into the thermodynamic pK(a) values are thoroughly discussed. This rapid and automated method allows the systematic study of the effect of solvent compositions and temperatures on the pK(a). It has been applied to study the dissociation constants of two monoprotic acids: formic acid and triethylamine:HCl in acetonitrile/water mixtures within the range from 0 to 90% (v/v) at temperatures between 20°C and 60°C. These volatile compounds are frequently used to control the pH of the mobile phase in HPLC, especially in methods coupled to mass-spectrometry detection. The obtained pK(a) values are in excellent agreement with those previously reported. The results were fitted to empirical functions between pK(a) and temperature and composition. These equations, which can be used to estimate the pK(a) of these substances at any composition and temperature, would be highly useful in practical work during chromatographic method development.

  10. A novel digestion method based on a choline chloride–oxalic acid deep eutectic solvent for determining Cu, Fe, and Zn in fish samples

    Energy Technology Data Exchange (ETDEWEB)

    Habibi, Emadaldin [Department of Marine Chemistry, Faculty of Marine Science, Khorramshahr University of Marine Science and Technology, P.O. BOX 669, Khorramshahr (Iran, Islamic Republic of); Ghanemi, Kamal, E-mail: Kamal.ghanemi@kmsu.ac.ir [Department of Marine Chemistry, Faculty of Marine Science, Khorramshahr University of Marine Science and Technology, P.O. BOX 669, Khorramshahr (Iran, Islamic Republic of); Marine Science Research Institute, Khorramshahr University of Marine Science and Technology, Khorramshahr (Iran, Islamic Republic of); Fallah-Mehrjardi, Mehdi [Department of Marine Chemistry, Faculty of Marine Science, Khorramshahr University of Marine Science and Technology, P.O. BOX 669, Khorramshahr (Iran, Islamic Republic of); Marine Science Research Institute, Khorramshahr University of Marine Science and Technology, Khorramshahr (Iran, Islamic Republic of); Dadolahi-Sohrab, Ali [Department of Marine Environment, Faculty of marine natural resources, Khorramshahr University of Marine Science and Technology, Khorramshahr (Iran, Islamic Republic of)

    2013-01-31

    Highlights: ► A novel digestion method: lack of concentrated acids or oxidizing reagents. ► First report of using choline chloride–oxalic acid (ChCl–Ox) for digestion. ► Complete dissolution of biological samples in ChCl–Ox for solubilization metals. ► Extraction recoveries greater than 95%: validated by the fish protein CRM. ► Successfully applied in different fish tissues (Muscle, Liver, and Gills). -- Abstract: A novel and efficient digestion method based on choline chloride–oxalic acid (ChCl–Ox) deep eutectic solvent (DES) was developed for flame atomic absorption spectrometry (FAAS) determination of Cu, Zn, and Fe in biological fish samples. Key parameters that influence analyte recovery were investigated and optimized, using the fish protein certified reference material (CRM, DORM-3) throughout the procedure. In this method, 100 mg of the sample was dissolved in ChCl–Ox (1:2, molar ratio) at 100 °C for 45 min. Then, 5.0 mL HNO{sub 3} (1.0 M) was added. After centrifugation, the supernatant solution was filtered, diluted to a known volume, and analyzed by FAAS. Under optimized conditions, an excellent agreement between the obtained results and the certified values was observed, using Student's t-test (P = 0.05); the extraction recovery of the all elements was greater than 95.3%. The proposed method was successfully applied to the determination of analytes in different tissues (muscle, liver, and gills) having a broad concentration range in a marine fish sample. The reproducibility of the method was validated by analyzing all samples by our method in a different laboratory, using inductively coupled plasma optical emission spectrometry (ICP-OES). For comparison, a conventional acid digestion (CAD) method was also used for the determination of analytes in all studied samples. The simplicity of the proposed experimental procedure, high extraction efficiency, short analysis time, lack of concentrated acids and oxidizing agents, and the

  11. Development and optimization of a naphthoic acid-based ionic liquid as a "non-organic solvent microextraction" for the determination of tetracycline antibiotics in milk and chicken eggs.

    Science.gov (United States)

    Gao, Jiajia; Wang, Hui; Qu, Jingang; Wang, Huili; Wang, Xuedong

    2017-01-15

    In traditional ionic liquids (ILs)-based microextraction, ILs are often used as extraction and dispersive solvents; however, their functional effects are not fully utilized. Herein, we developed a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]) with strong acidity. It was used as a mixed dispersive solvent with conventional [C2MIM][BF4] in "functionalized ionic liquid-based non-organic solvent microextraction (FIL-NOSM)" for determination of tetracycline antibiotics (TCs) in milk and eggs. Utilization of [C4MIM][NPA] in FIL-NOSM method increased extraction recoveries (ERs) of TCs by more than 20% and eliminated the pH adjustment step because of its strong acidity. Under optimized conditions based on central composite design, the ERs of four TCs were 94.1-102.1%, and the limitsofdetection were 0.08-1.12μgkg(-1) in milk and egg samples. This proposed method provides high extraction efficiency, less pretreatment time and requires non-organic solvents for determination of trace TC concentrations in complex animal-based food matrices.

  12. Modeling of solvent extraction equilibrium of Cu(II from sulphuric Acid solution with MOC-55TD

    Directory of Open Access Journals (Sweden)

    Alguacil, F. J.

    1999-06-01

    Full Text Available The extraction of Cu(II from acidic sulphate aqueous solutions using the commercial MOC-55TD extractant is studied. A predictive model, which consists in a set of non-linear mass action and mass balance equations is proposed. The model was solved using a tailor-made equation-solving program. The extraction of copper can be described by the formation of CuR2 species (log Kext= 0.717 ± 0.03 in the organic phase. The copper equilibrium isotherm was also obtained at 20°C.

    Se estudia la extracción de Cu(II de disoluciones acuosas acidas, en medio sulfato, mediante la oxima comercial MOC-55TD. Se propone un modelo para predecir la extracción del metal; este modelo consiste en una serie de ecuaciones no lineales de acción de masas y balance de masas. El modelo se resolvió empleando un programa de ordenador específicamente definido para este tipo de equilibrios. La extracción de cobre se describe por la formación de la especie CuR2 (log Kext= 0,717 ± 0,03 en la fase orgánica. Se ha obtenido la isoterma de extracción de cobre a 20 °C.

  13. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    Science.gov (United States)

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin

    2016-07-20

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

  14. Testing the nature of reaction coordinate describing interaction of H2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-09-01

    Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)3 adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H—H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C(carbonyl) and a number of Lewis basic solvent molecules—i.e., the concerted C(carbonyl)⋯H2⋯solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via "computational experimentation" employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

  15. Kinetics, reactivity, initial-transition state analysis and thermodynamic parameters of base-catalyzed hydrolysis of coumalic acid in solvents with different polarities

    Directory of Open Access Journals (Sweden)

    Ezz A. Abu-Gharib

    2017-02-01

    Full Text Available Base-catalyzed hydrolysis of coumalic acid (COU in binary aqueous-methanol and aqueous-acetone mixtures has been studied kinetically at a temperature range from 283 to 313 K. Moreover, the change in the activation energy barrier of COU from water to water–methanol and water–acetone mixtures is estimated from the kinetic data. Solvent effects on reactivity trends have been analyzed into initial and transition state components by using transfer chemical potentials of the reactants and kinetic data. The transfer chemical potentials δmμθ for COU− anion are derived from solubility data from its calcium, cerium and lanthanum salts. The decrease in rate constant of the base hydrolysis reaction of COU as the percentage of methanol or acetone increases is dominated by transition state (TS. The base hydrolysis reaction of COU follows a rate law with kobs = k2[OH−] and the reaction mechanism was suggested. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

  16. Preparation of methacrylic acid copolymer S nano-fibers using a solvent-based electrospinning method and their application in pharmaceutical formulations.

    Science.gov (United States)

    Hamori, Mami; Shimizu, Yuki; Yoshida, Kaori; Fukushima, Keizo; Sugioka, Nobuyuki; Nishimura, Asako; Naruhashi, Kazumasa; Shibata, Nobuhito

    2015-01-01

    In this study, we applied an electrospinning (ES) method, which is mainly employed in the textile industry, to the field of pharmaceuticals. We developed and modified an ES instrument and then utilized it to produce methacrylic acid copolymer S (MAC) nano-fibers to prepare tablets. By attaching a conductor rod made from stainless steel to the central part of the nano-fiber-collection plate of the ES apparatus, a MAC nano-fiber sheet could be produced effectively. In addition, we studied various operating conditions for this new ES method, including needle gauge, voltage between the electrodes, distance between the needle and nano-fiber-collection plate and the flow rate of MAC polymer solution, but these had no significant effect on the diameter of MAC nano-fibers. On the other hand, the viscosity (concentration) of MAC polymer solution and permittivity of solvent used to dilute MAC were closely related to the mean diameter of the nano-fibers. Tableting of MAC nano-fibers was performed using a tableting machine without lubricants, and addition of Tween 20 to the tablets enabled regulation of the release profile of a water-soluble drug. The modified ES method reported here is a useful technique for the controlled-release of drugs and has wide-ranging potential for pharmaceutical applications.

  17. Solvent effects on the formation of nanoparticles and multilayered coatings based on hydrogen-bonded interpolymer complexes of poly(acrylic acid) with homo- and copolymers of N-vinyl pyrrolidone.

    Science.gov (United States)

    Zhunuspayev, Daulet E; Mun, Grigoriy A; Hole, Patrick; Khutoryanskiy, Vitaliy V

    2008-12-02

    The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition.

  18. Polymer supported sulphanilic acid: A highly efficient and recyclable green heterogeneous catalyst for the construction of 4,5-dihydropyrano[3,2-c]chromenes under solvent-free conditions

    Indian Academy of Sciences (India)

    Jashmin P Patel; Jemin R Avalani; Dipak K Raval

    2013-05-01

    Polystyrene divinylbenzene supported sulphanilic acid was prepared, characterized and tested as an acidic catalyst in multicomponent organic synthesis. This is the first report focusing on the development of one-pot solvent-free synthesis of 4,5- dihydropyrano [3,2-c]chromenes under acidic conditions. It proved to be a versatile catalyst for microwave-assisted synthesis of 4,5-dihydropyrano[3,2-c]chromenes. This methodology is mild, high yielding, green and the catalyst could be easily recycled for several times.

  19. KRISTALISASI PELARUT SUHU RENDAH PADA PEMBUATAN FRAKSI KAYA VITAMIN E MENGANDUNG TOKOTRIENOL DARI DISTILAT ASAM LEMAK MINYAK SAWIT [Low Temperature Solvent Crystallizationin Tocotrienol Containing Vitamin E Rich Fraction Preparation from Palm Fatty Acid Distillate

    Directory of Open Access Journals (Sweden)

    Kgs Ahmadi1*,

    2011-12-01

    Full Text Available Palm Fatty Acid Distillate (PFAD is a by-product of physical refining of CPO (Crude Palm Oil in deodorization process. PFAD is a potential source of natural vitamin E, that besides tocopherol, also contains tocotrienol. Both have functions as antioxidant and vitamin. This research studied a method for obtaining vitamin E rich fraction that contained tocotrienol by low temperature hexane solvent crystallization. The elucidation factors were ratio of solvent to unsaponifiable fraction of PFAD(5:1, 6:1, and 7:1 and crystallization temperature (-20, -10, and 0°C. The experiment was conducted in factorial completely randomized design. The research showed that PFAD contains high tocotrienol. Low temperature solvent crystallization of unsaponifiable fraction gave 33.88% increase ofvitamin E concentration compared to control. Temperature and ratio of solvent to unsaponifiable fraction affected enrichment of vitamin E in PFAD. Later, saponification increased vitamin E content in unsaponifiable fraction of PFAD. Enrichment of tocopherol was higher than that of tocotrienol, supposed as a result of improper separation process in crystallization stage. Modulation of Vitamin E concentration during saponification of PFAD increased antioxidant activity compared to unsaponifiable fraction. The best result was achieved at ratio of solvent to unsaponifiable fraction of 6:1 and crystallization temperature of -10°C.

  20. Effect of temperature and solvent composition on acid dissociation equilibria, I: Sequenced {sup s}{sub s}pK{sub a} determination of compounds commonly used as buffers in high performance liquid chromatography coupled to mass spectroscopy detection

    Energy Technology Data Exchange (ETDEWEB)

    Padro, Juan M.; Acquaviva, Agustin; Tascon, Marcos [Laboratorio de Separaciones Analiticas, Division Quimica Analitica, Universidad Nacional de La Plata y CIDEPINT, 47 y 115, (1900) La Plata (Argentina); Gagliardi, Leonardo G., E-mail: leogagliardi@quimica.unlp.edu.ar [Laboratorio de Separaciones Analiticas, Division Quimica Analitica, Universidad Nacional de La Plata y CIDEPINT, 47 y 115, (1900) La Plata (Argentina); Castells, Cecilia B., E-mail: castells@isis.unlp.edu.ar [Laboratorio de Separaciones Analiticas, Division Quimica Analitica, Universidad Nacional de La Plata y CIDEPINT, 47 y 115, (1900) La Plata (Argentina)

    2012-05-06

    Highlights: Black-Right-Pointing-Pointer We developed a rapid potentiometric method for sequential pK{sub a} determinations. Black-Right-Pointing-Pointer We measured pK{sub a} of buffers from 0 to 90% (v/v) acetonitrile/water and from 20 to 60 Degree-Sign C. Black-Right-Pointing-Pointer Sequences of 42 pK{sub a}-data spanned over a wide solvent composition range needed 2 h. Black-Right-Pointing-Pointer We measured pK{sub a} of formic acid and triethylamine/HCl in up to 90% (v/v) acetonitrile. Black-Right-Pointing-Pointer The high-throughput method was applied to obtain pK{sub a} of two common buffers in LC/MS. - Abstract: A new automated and rapid potentiometric method for determining the effect of organic-solvent composition on pK{sub a} has been developed. It is based on the measurements of pH values of buffer solutions of variable solvent compositions using a combined glass electrode. Additions of small volumes of one precisely thermostated solution into another, both containing exactly the same analytical concentrations of the buffer components, can produce continuous changes in the solvent composition. Two sequences of potential measurements, one of increasing and the other of decreasing solvent content, are sufficient to obtain the pK{sub a} values of the acidic compound within the complete solvent-composition range in about 2 h. The experimental design, procedures, and calculations needed to convert the measured pH into the thermodynamic pK{sub a} values are thoroughly discussed. This rapid and automated method allows the systematic study of the effect of solvent compositions and temperatures on the pK{sub a}. It has been applied to study the dissociation constants of two monoprotic acids: formic acid and triethylamine:HCl in acetonitrile/water mixtures within the range from 0 to 90% (v/v) at temperatures between 20 Degree-Sign C and 60 Degree-Sign C. These volatile compounds are frequently used to control the pH of the mobile phase in HPLC, especially in

  1. Microwave-assisted Synthesis of Modified Polyaspartic Acid in Solvent%微波溶剂法合成天冬氨酸-谷氨酸共聚物研究

    Institute of Scientific and Technical Information of China (English)

    张玉玲; 黄君礼; 程志辉; 杨士林

    2007-01-01

    Polyaspartic acid (PASP) is suitable for the inhibition of scale deposition from water.To enhance its inhibition efficiency, PASP was modified by reacting aspartic acid (Asp) with glutamic acid (Glu) to provide Asp-Glu copolymer under microwave irradiation.The influence of reaction parameters on conversion, molecular weight and inhibition of CaCOa precipitation was investigated Infra-red.(IR),1H nuclear magnetic resonance (1H NMR) and 13C nuclear magnetic resonance (13C NMR) spectroscopies were used to characterize the copolymer.The results show that copolymerization of aspartic acid and glutamic acid is catalyzed by a small amount of phosphorous acid (H3PO4) in solvent, the product conversion is 98.05% under the following conditions: the molar ratio of glutamic acid to reactant [Glu/(Asp+Glu)] is 0.3 and that of catalyst (Cat) to reactant [Cat/(Glu+Asp)] is 0.05 (0.65ml H3PO4), the volume of solvent dimethylformamide is 16ml, the microwave power used is 720W and the reaction for 3 rnin.The weight average molecular weight of copolymer synthesized under these conditions is 2709 and the inhibition rate for CaCO3 is 97.75%.

  2. Study on the Technology of Detoxification of Rapeseed Meal by Acid Solvent%酸溶液对菜籽粕脱毒工艺探讨

    Institute of Scientific and Technical Information of China (English)

    兰文菊; 彭密军; 彭胜; 吕强; 张琳杰; 张昌伟

    2012-01-01

    菜籽粕是一种植物蛋白资源,富含氨基酸、矿物元素、维生素等多种常规营养成分,但须脱毒方能用于饲料.试验以菜籽粕为研究对象,采用单因素和正交试验确定了酸溶液对菜籽粕脱毒的最佳工艺参数,即硫酸浓度4%;液固比为20:1 (mL/g),60℃下浸提60 min,提取1次.经硫酸溶液脱毒后菜籽粕中植酸、单宁、硫代葡萄糖苷、异硫氰酸酯和噁唑烷硫酮的脱除率分别为92.16%、90.45%、93.37%、90.85%和88.97%,符合饲料级要求,脱毒后其蛋白质含量提高.%Rapeseed meal is a kind of vegetable protein resources. There are a variety of conventional nutrients in it such as amino acid, vitamin, mineral elements, ect. ,yet it must be de - toxificated before it is added into feed. The technologies of de - toxification of rapeseed meal were confirmed by single factors and orthogonal experiment- The optimum parameters were as follows:sulphuric acid(4% )as de -toxification solvent,liquid -solid ratio 20:1(mL/g), 60 min,60 ℃. Under these conditions, the de -toxificated rate of phytic acid, tannin, glucosinolate, isothiocyanate (ITC)and oxazolidine(OZT)were 92.16% ,90.45% ,93. 37% ,90. 85% and 88. 97% Respectively which fulfil feed level guideline. The nutrition in detoxified rapeseed meal was increased.

  3. Solvent-induced O-H vibration red-shifts of oxygen-acids in hydrogen-bonded O-H···base complexes.

    Science.gov (United States)

    Keinan, Sharon; Pines, Dina; Kiefer, Philip M; Hynes, James T; Pines, Ehud

    2015-01-22

    Infrared spectroscopy has been used to characterize the solvent effect on the OH stretching vibrations νOH of phenol, 1-naphthol, 2-naphthol, 1-hydroxypyrene, and ethanol. We distinguish the dielectric (nonspecific) effect of the solvent on ΔνOH, the observed red-shifts in νOH, from the much larger red-shift caused by direct hydrogen (H)-bonding interactions with the solvents. To isolate the solvent dielectric constant ε effect on νOH, the OH oscillator was also studied when it is already H-bonded with an invariant oxygen base, dimethyl sulfoxide. We find that ΔνOH depends importantly on ΔPA, the difference between the proton affinities of the conjugate base of the proton donor and the proton acceptor. For a given H-bonded complex, νOH tends to vary inversely with ε, exhibiting different slopes for polar and nonpolar solvents, i.e., solvents comprising molecules with and without a permanent dipole moment, respectively. We use a two-state valence-bond-based theory to analyze our experimental data. This demonstrates that the OH oscillator acquires a more ionic-like character in the vibrational excited state, i.e., charge transfer; this results in a stronger H-bond in a more anharmonic potential for the OH vibration. The theory distinguishes between nonpolar and polar solvents and successfully accounts for the observed 1/ε and ΔPA variations.

  4. Solvent extraction bis (the 2- ethylhexyl) phosphoric acid catecholamine structural property quantitative correlation; Bisu (2-echiruhekishiru) rinsan wo mochiita katekoru amin rui no yobai chushutsu to teiryoteki kozo bussho sokan

    Energy Technology Data Exchange (ETDEWEB)

    Yoshizuka, Kazuharu [Saga University, Saga (Japan); Fujimoto, Yuko; Owatari, Keisuke; Inoue, Katsutoshi

    1999-03-05

    As a basic research of separation and refinement of catecholamine (CA) by solvent extraction method which is chemical messenger of central neuron in the internal, it was extracted from dopamine (DA), adrenalin (Ad) and in hydrochloric acid aqueous solution of noradrenaline (NA). Then, each solution of chloroform. Hexane and toluene of bis (the 2 - ethylhexyl) phosphoric acid (D2EHPA) was used in respect of the stripping. All CA is CA by D2EHPA in mechanism of ion exchange: It was clarified that it was extracted as D2EHPA=1:4 complex and the extraction equilibrium constant was obtained. In addition, the consideration by molecule modeling considering the solvent effect of continuous medium types using semi-experience molecular orbital method by quantitative structural property correlation (QSPR) was carried out on got extraction equilibrium constant. (translated by NEDO)

  5. Cooperative Reinforcement of Ionic Liquid and Reactive Solvent on Enzymatic Synthesis of Caffeic Acid Phenethyl Ester as an In Vitro Inhibitor of Plant Pathogenic Bacteria

    Directory of Open Access Journals (Sweden)

    Yan Xu

    2017-01-01

    Full Text Available It is widely believed that lipases in ionic liquids (ILs possess higher enzyme activity, stability and selectivity; however, reaction equilibrium is always limited by product inhibition, and the product is difficult to separate from non-volatile ILs using distillation. To solve this problem, using trialkylphosphine oxide (TOPO as a complexing agent, a novel biphase of reactive solvent and IL was firstly reported for caffeic acid phenethyl ester (CAPE production from methyl caffeate (MC and 2-phenylethanol (PE catalyzed by lipase via transesterification. The effects of the reaction parameters and their action mechanism were investigated, and the inhibition of CAPE against bacterial wilt pathogen Ralstonia solanacearum was firstly measured. The MC conversion of 98.83% ± 0.76% and CAPE yield of 96.29% ± 0.07% were obtained by response surface methodology in the 25 g/L TOPO-cyclohexane/[Bmim][Tf2N] (1:1, v/v; the complex stoichiometry calculation and FTIR spectrum confirmed that the reversible hydrogen-bond complexation between TOPO and caffeates significantly enhances the cooperative effect of two phases on the lipase-catalyzed reaction. The temperature was reduced by 14 °C; the MC concentration increased by 3.33-fold; the ratio of catalyst to donor decreased by 4.5-fold; and Km decreased 1.08-fold. The EC50 of CAPE against R. solanacearum was 0.17–0.75 mg/mL, suggesting that CAPE is a potential in vitro inhibitor of plant pathogenic bacteria.

  6. Influence of imidazolium based green solvents on volume phase transition temperature of crosslinked poly(N-isopropylacrylamide-co-acrylic acid) hydrogel.

    Science.gov (United States)

    Chang, Chi-Jung; Reddy, P Madhusudhana; Hsieh, Shih-Rong; Huang, Hsin-Chun

    2015-01-28

    The volume phase transition temperature (VPTT) of crosslinked poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAM-co-AA) hydrogel in water in the presence of five imidazolium based ionic liquids (ILs) was studied. The VPTT of PNIPAM-co-AA hydrogel can be modulated to different extents by the addition of different amounts of ILs. The modulations in VPTT values can be attributed to the IL-induced alterations in hydrophobic, hydrophilic and hydrogen bonding interactions of PNIPAM-co-AA hydrogel with the neighboring solvent and molecular chains. The influence of ILs having a common cation, 1-butyl-3-methylimidazolium cation ([Bmim]) and different anions, such as iodide (I-), tetrafluoroborate (BF4-), chloride (Cl-), acetate (CH3COO-) and hydrogen sulfate (HSO4-), on the phase transition of PNIPAM-co-AA hydrogel was monitored by the aid of differential scanning calorimetry (DSC), dynamic light scattering (DLS) and Fourier transform infrared (FT-IR) spectroscopy. Furthermore, the interfacial properties between aqueous IL and polymer surface were scrutinized with the help of contact angle (CA) measurements. The overall specific ranking of ILs in preserving the hydration layer around the PNIPAM-co-AA hydrogel in water was [Bmim][I]>[Bmim][BF4]>[Bmim][Cl]>[Bmim][Ac]>[Bmim][HSO4]. The trend of these ILs followed the well-known Hofmeister series. Interestingly, the PNIPAM-co-AA hydrogel in water shows abnormal salting-out property in the presence of [Bmim][BF4] at higher concentration and this abnormal behavior can be explained based on the lack of sufficient binding sites on the macromolecule for higher number of [Bmim][BF4] at a higher concentration.

  7. 酸性加压浸出液中钼的萃取分离%Molybdenum Solvent Extraction Technology From Acid Pressure Leaching Solution

    Institute of Scientific and Technical Information of China (English)

    邹小平; 张邦胜; 张磊; 王海北

    2014-01-01

    研究了从酸性加压浸出液中采用溶剂萃取法提取钼工艺,考察了萃取剂浓度、改质剂浓度、萃取相比、萃取时间等对钼萃取率的影响。试验结果表明,在有机相组成25%N235+5%异辛醇+磺化煤油,O/A=3/1,混合时间3 min的条件下,钼的萃取率可达到98%以上;负载有机相采用20%的氨水反萃,O/A=1/3,在两级逆流萃取的条件下钼反萃率超过98%。%The technology of extracting molybodenum from acid pressure leaching solution adopting solvent extraction method was researched. The effects of extractant concentration, modification agent concentration, phase ratio and extraction time on the extraction rate of Mo were investigated. The tests result showed that the extraction ratio of Mo could reach above 98% at the condition of the organic phase containing 20%N235, 5%Isooctanol and Kerosene with O/A of 1/3, and the mixing time of 3 min. When the loaded organic reagent was stripped with 20% ammonia, the stripping ratio of Mo was more than 98% after two-stage stripping with O/A of 3/1.

  8. Study of antioxidant property of a thiosphosphorated compound derived from cashew nut shell liquid in hydrogenated naphthenics oils

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, A.A.S.; Carneiro, E.A. [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Engenharia Quimica]. E-mail: adasanders@gmail.com; Rios, M.A.S.; Hiluy Filho, J.J.; Carioca, J.O.B.; Barros, G.G.; Mazzetto, S.E. [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Parque de Desenvolvimento Tecnologico

    2008-01-15

    The present work shows the aspects related to the synthesis and thermogravimetric analysis of thiophosphorated and phosphorated compounds from hydrogenated cardanol. Studies on thermal-oxidative stability were investigated, using a classical thermoanalytical-thermogravimetric method (TG/DTG) in an air atmosphere. Its use as an antioxidant additive in hydrogenated naphthenic NH10, NH20 and NH140 oils was evaluated. The addition of 1.2% synthesized compounds to the oils has improved their thermal-oxidative stability by 5-15 deg C. The occurrence of major thermal degradation events at higher temperatures (T{sub max}) in additivated oils is a good indication of the antioxidant properties of the thiophosphorated and phosphorated cardanol compounds antioxidant properties. (author)

  9. Study of antioxidant property of a thiosphorated compound derived from cashew nut shell liquid in hydrogenated naphthenics oils

    Directory of Open Access Journals (Sweden)

    A. A. S. Lopes

    2008-03-01

    Full Text Available The present work shows the aspects related to the synthesis and thermogravimetric analysis of thiophosphorated and phosphorated compounds from hydrogenated cardanol. Studies on thermal-oxidative stability were investigated, using a classical thermoanalytical-thermogravimetric method (TG/DTG in an air atmosphere. Its use as an antioxidant additive in hydrogenated naphthenic NH10, NH20 and NH140 oils was evaluated. The addition of 1.2% synthesized compounds to the oils has improved their thermal-oxidative stability by 5-15ºC. The occurrence of major thermal degradation events at higher temperatures (Tmax in additivated oils is a good indication of the antioxidant properties of the thiophosphorated and phosphorated cardanol compounds antioxidant properties.

  10. KSF supported 10-molybdo-2-vanadophosphoric acid as an efficient and reusable catalyst for one-pot synthesis of 2,4,5-trisubstituted imidazole derivatives under solvent-free condition

    Institute of Scientific and Technical Information of China (English)

    Laxmikant D. Chavan; Sunil G. Shankarwar

    2015-01-01

    The one-pot three-component cyclocondensation has been developed involving the reaction of benzil with an aromatic aldehydes and ammonium acetate under thermal solvent-free conditions in the presence of a KSF supported 10-molybdo-2-vanadophosphoric acid catalyst. 10-Molybdo-2-vanadophosphoric acid was immobilized on KSF with a 20% loading, which showed the highest catalytic activity. The catalyst was fully characterized using FT-IR spectroscopy, thermal analysis, XRD and SEM analysis techniques. There are several distinct advantages to this protocol, including high yields, short reaction time, operational simplicity and a recyclable catalyst with a facile work-up procedure.

  11. Estudo da influência do solvente, carboidrato e ácido graxo na síntese enzimática de ésteres de açúcares Study of the influence of solvent, carbohydrate and fatty acid in the enzymatic synthesis of sugar esters by lipases

    Directory of Open Access Journals (Sweden)

    Ariela V. de Paula

    2005-10-01

    Full Text Available The aim of this work was to gain knowledge of enzymatic processes for the synthesis fatty acid esters of sugar, with the objective to develop an enzymatic process for the preparation of non-toxic biodegradable surface-active agents derived entirely from renewable resources. A wide range of data were collected for reaction conditions involving different sugars (glucose, fructose and sucrose, fatty acids (oleic, palmitic, lauric, solvents (hexane, heptane and t-butanol and different sources of lipases in both free and immobilized forms. As a solvent t-butanol provided the best conditions to create a catalytic liquid phase in which the reaction occurs. Sugars were preferentially esterified in the following order: fructose > glucose > sucrose, depending on the enzyme preparation. For fructose no influence was found concerning de acyl donor and similar rates were achieved for all tested fatty acids. Ester synthesis was maximized for substrates containing fructose, lauric or oleic acids, t-butanol and lipase from porcine pancreas immobilized on polysiloxane-polyvinyl alcohol particles. Under such conditions molar conversions were higher than 50%.

  12. The chemistry of nonaqueous solvents v.4 solution phenomena and aprotic solvents

    CERN Document Server

    Lagowski, J J

    1976-01-01

    The Chemistry of Nonaqueous Solvents, Volume IV: Solution Phenomena and Aprotic Solvents focuses on the chemistry of nonaqueous solvents, with emphasis on solution phenomena and aprotic solvents such as tetramethylurea, inorganic acid chlorides, cyclic carbonates, and sulfolane. This book is organized into seven chapters and begins with an overview of the theory of electrical conductivity and elementary experimental considerations, along with some of the interesting research on nonaqueous solvents. It then turns to a discussion on hydrogen bonding phenomena in nonaqueous systems as probed

  13. PURIFICATION OF COBALT ANOLYTE USING THE NOVEL SOLVENT EXTRACTION SYSTEM

    Institute of Scientific and Technical Information of China (English)

    Y.F. Shen; W.Y. Xue; W. Y. Niu

    2003-01-01

    In present research, a novel extractant system (D2EHPA + naphthenic acid +pyridine-ester) was used to purify cobalt anolyte and a simulated industrial produc-tion were carried out. This novel extraction system can extract Cu and/or Ni againstCo from chloride medium solutions at pH range of 2.5-4.5. About 2g/l nickel and0.2g/l copper were removed from the cobalt chloride anolyte containing about 100g/lcobalt and 200g/l chloride ions respectively, the raffinate contains nickel and copperless than 0.03g/l and 0. 0003g/l respectively and can be used to electrolyze high-puritycobalt. About 5.5t cobalt anolyte was purified in the simulation industrial experimentand kilogram quantities of cobalt of 99.98% purity and about 95% recovery have beenproduced.

  14. Cerebral metabolic and circulatory effects of 1,1,1-trichloroethane, a neurotoxic industrial solvent. 2. Tissue concentrations of labile phosphates, glycolytic metabolites, citric acid cycle intermediates, amino acids, and cyclic nucleotides.

    Science.gov (United States)

    Folbergrová, J; Hougaard, K; Westerberg, E; Siesjö, B K

    1984-01-01

    In order to obtain information on the mechanisms of neurotoxicity of 1,1,1-trichloroethane, rats maintained artificially ventilated on N2O:O2 (70:30) were exposed to a concentration of 1,1,1-trichloroethane of 8000 ppm, 43.7 mg L-1, that induces moderate ataxia in awake, spontaneously breathing animals. After 5 and 60 min of exposure, as well as after a 60-min recovery period following 60 min of exposure, the brain was frozen in situ and cortical tissue was assayed for phosphocreatine (PCr), + ATP, ADP, AMP, glycogen, glucose, pyruvate, lactate, citric acid cycle intermediates, associated amino acids, and cyclic nucleotides; in addition, purine nucleotides, nucleosides, and bases were assayed by HPLC techniques. Exposure of animals to 1,1,1-trichloroethane failed to alter blood glucose, lactate, and pyruvate concentrations. However, the solvent induced highly significant increases in tissue lactate and pyruvate concentrations that were also reflected in cisternal CSF. Associated with these changes were increases in all citric acid cycle intermediates except succinate, an increase in alanine concentration, and a rise in the glutamate/aspartate ratio. After 5 min, a small decrease in glycogen concentration also occurred. All these changes were reversed when the exposure was terminated. No changes were observed in tissue concentrations of purine nucleotides, nucleosides, and bases except for a small reduction of ATP concentration after 60 min of exposure, still noticeable after 60 min of recovery. Apart from a small reduction in cAMP concentration after 5 min of exposure, cyclic nucleotide concentrations did not change.

  15. Solvent and H/D isotope effects on the proton transfer pathways in heteroconjugated hydrogen-bonded phenol-carboxylic acid anions observed by combined UV-vis and NMR spectroscopy.

    Science.gov (United States)

    Koeppe, Benjamin; Guo, Jing; Tolstoy, Peter M; Denisov, Gleb S; Limbach, Hans-Heinrich

    2013-05-22

    Heteroconjugated hydrogen-bonded anions A···H···X(-) of phenols (AH) and carboxylic/inorganic acids (HX) dissolved in CD2Cl2 and CDF3/CDF2Cl have been studied by combined low-temperature UV-vis and (1)H/(13)C NMR spectroscopy (UVNMR). The systems constitute small molecular models of hydrogen-bonded cofactors in proteins such as the photoactive yellow protein (PYP). Thus, the phenols studied include the PYP cofactor 4-hydroxycinnamic acid methyl thioester, and the more acidic 4-nitrophenol and 2-chloro-4-nitrophenol which mimic electronically excited cofactor states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate the proton transfer pathways in a qualitative way. Dual absorption bands of the phenolic moiety indicate a double-well situation for the shortest OHO hydrogen bonds studied. Surprisingly, when the solvent polarity is low the carboxylates are protonated whereas the proton shifts toward the phenolic oxygens when the polarity is increased. This finding indicates that because of stronger ion-dipole interactions small anions are stabilized at high solvent polarity and large anions exhibiting delocalized charges at low solvent polarities. It also explains the large acidity difference of phenols and carboxylic acids in water, and the observation that this difference is strongly reduced in the interior of proteins when both partners form mutual hydrogen bonds.

  16. Predicting the Solubility of Pharmaceutical Cocrystals in Solvent/Anti-Solvent Mixtures

    Directory of Open Access Journals (Sweden)

    Linda Lange

    2016-05-01

    Full Text Available In this work, the solubilities of pharmaceutical cocrystals in solvent/anti-solvent systems were predicted using PC-SAFT in order to increase the efficiency of cocrystal formation processes. Modeling results and experimental data were compared for the cocrystal system nicotinamide/succinic acid (2:1 in the solvent/anti-solvent mixtures ethanol/water, ethanol/acetonitrile and ethanol/ethyl acetate at 298.15 K and in the ethanol/ethyl acetate mixture also at 310.15 K. The solubility of the investigated cocrystal slightly increased when adding small amounts of anti-solvent to the solvent, but drastically decreased for high anti-solvent amounts. Furthermore, the solubilities of nicotinamide, succinic acid and the cocrystal in the considered solvent/anti-solvent mixtures showed strong deviations from ideal-solution behavior. However, by accounting for the thermodynamic non-ideality of the components, PC-SAFT is able to predict the solubilities in all above-mentioned solvent/anti-solvent systems in good agreement with the experimental data.

  17. 从废钒催化剂酸浸液中萃取钒%Solvent Extraction of Vanadium From Acidic Leaching Solution of Waste Catalyst

    Institute of Scientific and Technical Information of China (English)

    郝喜才; 姬学亮

    2014-01-01

    Solvent extraction of vanadium from acidic leaching solution of waste catalyst containing vanadium using TOA as extractant was researched . The optimum process parameters were determined .The results show that using the 10% TOA + 4% decanol+ 86% sulfonated kerosene as extraction agent ,at the conditions of aqueous phase pH of 2 .5 ,the volume ratio between organic phase and aqueous phase of 1∶3 ,contact time of 2 .5 min ,holding time of 5 min ,single stage extraction of vanadium is up to 95 .2% .Using 0 .6 mol/L Na2 CO3 solution and be two stages back‐extraction ,the 99% of vanadium in organic phase was stripped .The stripping liquid can be directly precipitated vanadium .Calcining the precipitate can acquire V2 O5 product with GB3283 -1987 metallurgical grade 99 standard .The extraction raffinate is centralized processing .The process is simple and has remarkable comprehensive benefit .%研究了用TOA作萃取剂从废钒催化剂酸浸液中萃取钒,考察了各影响因素对钒萃取率的影响,确定了最佳萃取参数。试验结果表明:用10% TOA+4%癸醇+86%磺化煤油作萃取剂,在水相pH=2.5、有机相与水相体积比(V o ∶V a )=1∶3、萃取时间2.5 min、静置时间5 min条件下,钒的单级萃取率高达95.2%;用0.6 mol/L Na2 CO3溶液进行2级反萃取,钒的反萃取率在99%以上;反萃取液可直接沉淀钒,产品V2 O5质量达到GB3283—1987冶金99级标准。萃余液可集中处理。该工艺简单,综合效益显著。

  18. A new procedure combining GC-MS with accelerated solvent extraction for the analysis of phthalic acid esters in contaminated soils

    Institute of Scientific and Technical Information of China (English)

    Tingting MA; Ying TENG; Peter CHRISTIE; Yongming LUO; Yongshan CHEN; Mao YE

    2013-01-01

    An optimized procedure based on gas chromatography-mass spectrometry (GC-MS) combined with accelerated solvent extraction (ASE) is developed for the analysis of six phthalic acid esters (PAEs), which are priority soil pollutants nominated by United States Environmental Protection Agency (USEPA). Quantification of PAEs in soil employs ultrasonic extraction (UE) (USEPA 3550) and ASE (USEPA 3545), followed by clean up procedures involving three different chromatography columns and two combined elution methods. GC-MS conditions under selected ion monitoring (SIM) mode are described and quality assurance and quality control (QA/ QC) criteria with high accuracy and sensitivity for target analytes were achieved. Method reliability is assured with the use of an isotopically labeled PAE, di-n-butyl phthalate-d4 (DnBP-D4), as a surrogate, and benzyl benzoate (BB) as an internal standard, and with the analysis of certified reference materials (CRM). QA/QC for the developed procedure was tested in four PAE-spiked soils and one PAE-contaminated soil. The four spiked soils were originated from typical Chinese agricultural fields and the contaminated soil was obtained from an electronic waste dismantling area. Instrument detection limits (IDLs) for the six PAEs ranged 0.10-0.31 μg·L-1 and method detection limits (MDLs) of the four spiked soils varied from a range of 20-70 μg· kg -1 to a range of 90-290 μg· kg-1. Lineal-iVy of response between 20 μg· L-1 and 2mg.L~ was also established and the correlation coefficients (R) were a11〉0.998. Spiked soil matrix showed relative recovery rates between 75 and 120% for the six target compounds and about 93% for the surrogate substance. The developed procedure is anticipated to be highly applicable for field surveys of soil PAE pollution in China.

  19. Poly(4-vinylpyridinium) perchlorate as an efficient solid acid catalyst for the chemoselective preparation of 1,1-diacetates from aldehydes under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Nader Ghaffari Khaligh

    2014-01-01

    Poly(4-vinylpyridinium) perchlorate has been used as a supported, recyclable, environmental-ly-benign catalyst for the formation of acylals from aliphatic and aromatic aldehydes in good to excellent yields under solvent-free conditions. Notably, the reaction conditions were tolerant of ketones. This methodology offers several distinct advantages, including its operational simplicity and high product yield, as well as being green in terms of avoiding the use of toxic catalysts and solvents. Furthermore, the catalyst can be recovered and reused several times without any loss in its activity.

  20. Fatty acid alkyl esters as solvents: An evaluation of the kauri-butanol value. Comparison to hydrocarbons, dimethyl diesters and other oxygenates

    Science.gov (United States)

    Esters, most commonly methyl esters, of vegetable oils or animal fats or other lipid feedstocks have found increasing use as an alternative diesel fuel known as biodiesel. However, biodiesel also has good solvent properties, a feature rendered additionally attractive by its biodegradability, low tox...

  1. SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .1. SOLUBILITY OF CYCLOHEXENE IN AQUEOUS SULFOLANE MIXTURES

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1992-01-01

    The solubility of cyclohexene in different water-sulfolane mixtures was measured between 313 and 413 K. The results demonstrate a sharp increase of the solubility of cyclohexene with increasing percentages of sulfolane in the solvent mixture. Without sulfolane the increase of the solubility with tem

  2. Miscellaneous hydrocarbon solvents.

    Science.gov (United States)

    Bebarta, Vikhyat; DeWitt, Christopher

    2004-08-01

    The solvents discussed in this article are common solvents not categorized as halogenated, aromatic, or botanical. The solvents discussed are categorized into two groups: hydrocarbon mixtures and single agents. The hydrocarbon mixtures discussed are Stoddard solvent, naphtha, and kerosene. The remaining solvents described are n-hexane, methyl n-butyl ketone, dimethylformamide, dimethyl sulfoxide, and butyl mercaptans. Effects common to this group of agents and their unique effects are characterized. Treatment of exposures and toxic effects of these solvents is described, and physiochemical properties and occupational exposure levels are listed.

  3. Obtention of Samarium and Gadolinium concentrates by solvent extraction using mono-2-ethylhexyl ester of 2-ethylhexyl phosphonic acid; Obtencao de concentrados de samario e gadolinio via extracao por solventes com o ester mono-2-etilhexil do acido 2-etilhexilfosfonico

    Energy Technology Data Exchange (ETDEWEB)

    Miranda Junior, Pedro

    1996-07-01

    The rare earth chlorides solution employed in this study, which is constituted by medium and heavy fractions, is derived from monazite processing accomplished by NUCLEMON-Mineroquimica (SP). This solution shows an acidity about 1.18 M and 189 g/L of rare earth oxides, containing as main constituents: Sm(34.55%), Gd(23.85%), Dy (6.82%), and Y (24.45%). It was used, as organic phase, 2-ethylhexyl phosphonic acid, mono-2-ethylhexylester diluted to 1 M in isododecane. (author)

  4. Measurement and Correlation for Solubility of Adipic Acid in Several Solvents%己二酸在几种有机溶剂中溶解度的测定与关联

    Institute of Scientific and Technical Information of China (English)

    樊丽华; 马沛生; 相政乐

    2007-01-01

    Using a laser detecting system, solubility data were measured for adipic acid dissolved in six pure solvents, namely, cyclohexanone, cyclohexanol, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide at the temperature range from 293.15K to 353.15K. All these data were regressed by λh, NRTL,Wilson, and the modified Wilson models. For the study of six, λh, NRTL, and the modified Wilson models were found to provide an accurate mathematical representation of the experimental results, with overall average absolute relative deviations between measured and calculated values as 1.74%, 2.06%, and 3.06%, respectively. The resultsshowed that the λh model is the most suitable for description of the solid-liquid equilibrium containing adipic acid.

  5. Solvent resistant nanofiltration membranes

    OpenAIRE

    Dutczak, S.M.

    2011-01-01

    This thesis describes preparation and characterization of membranes for organic solvent filtration (OSF). The main aim was developing membranes for solvent resistant nanofiltration (SRNF) with molecular weight cut-off below 500 g mol-1.

  6. Solvents in novolak synthesis

    Science.gov (United States)

    Sobodacha, Chet J.; Lynch, Thomas J.; Durham, Dana L.; Paradis, Valerie R.

    1993-09-01

    Novolac resins may be prepared with or without a solvent present. We have found that solvent power greatly affects the properties of the finished resin and thus gives the resist chemist another variable with which to `fine-tune' resist properties. Using designed experiments, we investigated the effect of solvent power, as measured by Hansen's Solubility Parameters, of a number of solvents and solvent mixtures on the final properties of the novolac resin. We found that the relative molecular weight (RMW) and dissolution rate of a novolac resin can be varied by selection of a solvent or solvent mixture with the appropriate polarity and hydrogen- bonding characteristics. The solvent polarity and hydrogen-bonding characteristics may affect the stability of the cresol/formaldehyde transition state, thus causing the observed changes in RMW and dissolution rate.

  7. Nano-Fe3O4 encapsulated-silica particles bearing sulfonic acid groups as an efficient, eco-friendly and magnetically recoverable catalyst for synthesis of various xanthene derivatives under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Firouzeh Nemati

    2017-01-01

    Full Text Available This report describes an efficient method for the synthesis of 1,8-dioxo-octahydroxanthene, 14H-dibenzo[a,j]xanthene, 12-aryl-tetrahydrobenzo[a]xanthenes-11-one and 13-aryl-5H-dibenzo[b,i]xanthene-5,7,12,14(13H-tetraone derivatives in the presence of a catalytic amount of nano-iron oxide encapsulated silica particles bearing sulfonic acid groups. Results present an efficient, environmentally friendly and magnetically recoverable catalyst under solvent-free conditions at 110–130 °C.

  8. A green ultrasonic-assisted liquid-liquid microextraction based on deep eutectic solvent for the HPLC-UV determination of ferulic, caffeic and cinnamic acid from olive, almond, sesame and cinnamon oil.

    Science.gov (United States)

    Khezeli, Tahere; Daneshfar, Ali; Sahraei, Reza

    2016-04-01

    A simple, inexpensive and sensitive ultrasonic-assisted liquid-liquid microextraction method based on deep eutectic solvent (UALLME-DES) was used for the extraction of three phenolic acids (ferulic, caffeic and cinnamic) from vegetable oils. In a typical experiment, deep eutectic solvent as green extraction solvent was added to n-hexane (as a typical oil medium) containing target analytes. Subsequently, the extraction was accelerated by sonication. After the extraction, phase separation (DES rich phase/n-hexane phase) was performed by centrifugation. DES rich phase (lower phase) was withdrawn by a micro-syringe and submitted to isocratic reverse-phase HPLC with UV detection. Under optimum conditions obtained by response surface methodology (RSM) and desirability function (DF), the method has good linear calibration ranges (between 1.30 and 1000 µg L(-1)), coefficients of determination (r(2)>0.9949) and low limits of detection (between 0.39 and 0.63 µg L(-1)). This procedure was successfully applied to the determination of target analytes in olive, almond, sesame and cinnamon oil samples. The relative mean recoveries ranged from 94.7% to 104.6%. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Comparison of ambient solvent extraction methods for the analysis of fatty acids in non-starch lipids of flour and starch

    Science.gov (United States)

    Bahrami, Niloufar; Yonekura, Lina; Linforth, Robert; Carvalho da Silva, Margarida; Hill, Sandra; Penson, Simon; Chope, Gemma; Fisk, Ian Denis

    2014-01-01

    BACKGROUND Lipids are minor components of flours, but are major determinants of baking properties and end-product quality. To the best of our knowledge, there is no single solvent system currently known that efficiently extracts all non-starch lipids from all flours without the risk of chemical, mechanical or thermal damage. This paper compares nine ambient solvent systems (monophasic and biphasic) with varying polarities: Bligh and Dyer (BD); modified Bligh and Dyer using HCl (BDHCL); modified BD using NaCl (BDNaCl); methanol–chloroform–hexane (3:2:1, v/v); Hara and Radin (hexane–isopropanol, 3:2, v/v); water-saturated n-butanol; chloroform; methanol and hexane for their ability to extract total non-starch lipids (separated by lipid classes) from wheat flour (Triticum aestivum L.). Seven ambient extraction protocols were further compared for their ability to extract total non-starch lipids from three alternative samples: barley flour (Hordeum vulgare L.), maize starch (Zea mays L.) and tapioca starch (Manihot esculenta Crantz). RESULTS For wheat flour the original BD method and those containing HCl or NaCl tended to extract the maximum lipid and a significant correlation between lipid extraction yield (especially the glycolipids and phospholipids) and the polarity of the solvent was observed. For the wider range of samples BD and BD HCl repeatedly offered the maximum extraction yield and using pooled standardized (by sample) data from all flours, total non-starch lipid extraction yield was positively correlated with solvent polarity (r = 0.5682, P lipid yields in the starches when compared to the flour samples, which is due to the differences in lipid profiles between the two sample types (flours and starches). PMID:24132804

  10. 酸溶剂对葛根淀粉/壳聚糖复合可食膜性能的影响%Effects of acid solvents on properties of kudzu starch/chitosan composite edible films

    Institute of Scientific and Technical Information of China (English)

    钟宇; 李云飞

    2012-01-01

    In order to evaluate the effects of acid solvents on antibacterial, physical and mechanical properties of composite edible films, the kudzu starch-chitosan composite film-forming solutions were prepared by tape casting with mass fraction 1% of acetic acid, lactic acid and malic acid as solvents. For the film, 0.5g/L of ascorbic acid as the active additive, 0.6g/L of glycerol as the plasticizer and 0.1 g/L of Tween 20 as the surfactant were added into the solutions. It was found that there was certain surface activity for film-forming solution, and acid solvent had no obvious impact on the surface tension of each solution. The types of acid solvents had obvious impact on the performance of composite films, in which the film with acetic-acid solvent had best mechanic strength, the mean tensile strength and puncture strength were 5.73 MPa and 8.63 N, respectively, and its solubility was the smallest, which was about 34%. The film made from lactic acid solution displayed the greatest flexible property, which mean elongation and puncture distance were 71.5% and 6.05 mm, respectively. The composite film using malic acid as solvent showed the best antibacterial activity against escherichia coli and staphylococcus aureus, which were 98.9% and 81.2%, respectively, and its water-tightness was best, which the water vapor permibility was 4.82×10-11 g/(m·s·Pa). So different acid solvents can be selected to prepare films according to different requirements. The study results can provide theoretical references for the application of edible films.%为了考察壳聚糖酸溶剂对葛根淀粉/壳聚糖复合可食膜抗菌、物理和机械性能的影响,该文选择质量分数为1%的乙酸、乳酸、苹果酸为溶剂,配制质量体积比2g/L的葛根淀粉-壳聚糖复合膜液,以0.5g/L的抗坏血酸为活性添加剂,0.6g/L的丙三醇为增塑剂,0.1g/L的吐温20为表面活性剂,采用流延法制备可食性复合膜.结果表明:复合膜液具有一定的表

  11. Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

    Institute of Scientific and Technical Information of China (English)

    Yaghoub Sarrafi; Manijeh Mohadeszadeh; Kamal Alimohammadi

    2009-01-01

    Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method axe high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection.

  12. Solvent abuse: a review.

    Science.gov (United States)

    Barnes, G E

    1979-01-01

    The literature on solvent abuse is reviewed. Methods of use, symptoms of use, and effects of long-term solvent abuse are discussed. Several surveys on solvent use are summarized. The highest prevalence of solvent abuse seems to occur in native peoples undergoing periods of cultural change. Environmental conditions which are postulated as leading to psychological vulnerability and solvent abuse include: low social assets, parental drug use, peer and sibling influence, and acculturative stress. Solvent abuse seems to provide a pharmacological way out of a stressful environment for people who feel helpless to improve their situation in other ways. Methods of intervention that have been proposed for dealing with solvent abuse are discussed. Methods of intervention thus far employed generally have not been evaluated in any systematic fashion. Suggestions for future research are provided.

  13. Cross-aldol Condensation of Cycloalkanones and Aromatic Aldehydes in the Presence of Nanoporous Silica-based Sulfonic Acid (SiO2-Pr-SO3H) under Solvent Free Conditions

    Institute of Scientific and Technical Information of China (English)

    MOHAMMADI ZIARANI Ghodsi; BADIEI Alireza; ABBASI Alireza; FARAHANI Zahra

    2009-01-01

    The aromatic aldehydes underwent cross aldol condensation with cycloalkanones in the presence of a catalytic amount of nanoporous silica-based sulfonic acid (SiO2-Pr-SO3H) under solvent-free conditions to afford the corresponding a,a'-bis(substituted benzylidene)cycloalkanones in excellent yields with short reaction time without any side reactions.This method is very general,simple and environmentally friendly in contrast with other existing methods.SiO2-Pr-SO3H was proved to be an efficient heterogeneous solid acid catalyst,which could be easily handled and removed from the reaction mixture by simple filtration,and also recovered and reused without loss of reactivity.

  14. HOPE--a new fixing technique enables preservation and extraction of high molecular weight DNA and RNA of > 20 kb from paraffin-embedded tissues. Hepes-Glutamic acid buffer mediated Organic solvent Protection Effect.

    Science.gov (United States)

    Wiedorn, Klaus Hermann; Olert, Jürgen; Stacy, Robin A P; Goldmann, Torsten; Kühl, Heike; Matthus, Jutta; Vollmer, Ekkehard; Bosse, Alexander

    2002-01-01

    The growing number of molecular pathologic tools that are currently available require material with good long term preservation of morphology, nucleic acids, and antigenic structures. However, pathologic investigations of tissues done at a molecular level are often hampered by the fixatives in use. We thus endeavored to design a new fixing system, including subsequent paraffin-embedding and sectioning, that makes complete pathologic analyses possible, with special consideration of immunohistochemistry (IHC), in situ hybridization (ISH), and molecular pathology. The optimized HOPE (Hepes-Glutamic acid buffer mediated Organic solvent Protection Effect) fixing technique allows us to preserve and extract high molecular weight DNA and RNA of > 20 kbp suitable for downstream applications, such as PCR and RT-PCR from HOPE-fixed, paraffin-embedded tissues that are up to 5 years old. This technique will most probably lead to new impacts on molecular pathology.

  15. Chemical reactions in solvents and melts

    CERN Document Server

    Charlot, G

    1969-01-01

    Chemical Reactions in Solvents and Melts discusses the use of organic and inorganic compounds as well as of melts as solvents. This book examines the applications in organic and inorganic chemistry as well as in electrochemistry. Organized into two parts encompassing 15 chapters, this book begins with an overview of the general properties and the different types of reactions, including acid-base reactions, complex formation reactions, and oxidation-reduction reactions. This text then describes the properties of inert and active solvents. Other chapters consider the proton transfer reactions in

  16. Use of a (Quantitative) Structure-Activity Relationship [(Q)SAR] model to predict the toxicity of naphthenic acids

    DEFF Research Database (Denmark)

    Frank, Richard; Sanderson, Hans; Kavanagh, Richard

    2010-01-01

    -Activity Relationship ((Q)SAR) model to accurately predict the toxicity of NA-like surrogates was investigated.  The USEPA’s ECOSAR model predicted the toxicity of NA-like surrogates with acceptable accuracy in comparison to observed toxicity values from Vibrio fischeri and Daphnia magna assays, indicating...... that the model has potential to serve as a prioritization tool for identifying NA structures likely to have an increased toxicity.  Investigating NAs of equal MW, the ECOSAR model predicted increased toxic potency for NAs containing fewer carbon rings.  Furthermore, NA structures with a linear grouping of carbon...

  17. Determination of acid number in oils by standard curve method with green solvents%绿色溶剂—标准曲线法测定油品酸值

    Institute of Scientific and Technical Information of China (English)

    陆克平

    2013-01-01

    提出了一种直接pH测定油品酸值的免滴定方法.这种方法基于水/醇为主体的溶剂,内含有机碱性试剂,能4mim内完全萃取油品中酸性物质,用pH复合电极直接测定油品酸值.溶剂组成为体积比1:1的异丙醇和水,内含0.05~0.20mol/L的N-甲基二乙醇胺(MDEA)和0.02mol/L硝酸钾,预调至pH 11.30±0.05.确定了标准曲线区间,可测定0.007 mg KOH/g以上油品酸值.本方法耗时少,操作简便,具有不使用有毒试剂,室温下萃取与检测以及无需空白试验的特点,已在日常分析中应用,结果令人满意.%A direct pH-metric method for determination of acid number in some petroleum oils has been developed, based on water-isopropanol solvents with organic alkaline reagent. In just 4 min, it is able to completely and rapidly extract the sum of acids from an oil test portion into the special reagent in the iso-propanol-water phase by combination glass pH electrode measurement without titration. The reagent consisting of N-Methyldiethanolamine(MDEA) and potassium nitrate(KNOs) dissolved in water(H2O) and isopropanol (2-PrOH)with the initial conditional pH 11. 30±0. 05 [0. 05-0. 20 mol/L MDEA and 0. 02 mol/L KNO3 in the mixture of 50 % H2 O + 50 % 2-PrOH]. The limit of quantitation was 0. 007 mg(KOH)/g. The advantages of the method include absence of toxic solvents, extraction and inspection of acid number at room temperature, and no need for preliminary neutralization of acid admixtures in a solvent.

  18. Microwave-assisted solvent extraction and analysis of shikimic acid from plant tissues Extração por solvente assistida por micro-ondas e análise do ácido chiquímico dos tecidos de plantas

    Directory of Open Access Journals (Sweden)

    M.B Matallo

    2009-12-01

    Full Text Available A better method for determination of shikimate in plant tissues is needed to monitor exposure of plants to the herbicide glyphosate [N-(phosphonomethylglycine] and to screen the plant kingdom for high levels of this valuable phytochemical precursor to the pharmaceutical oseltamivir. A simple, rapid, and efficient method using microwave-assisted extraction (MWAE with water as the extraction solvent was developed for the determination of shikimic acid in plant tissues. High performance liquid chromatography was used for the separation of shikimic acid, and chromatographic data were acquired using photodiode array detection. This MWAE technique was successful in recovering shikimic acid from a series of fortified plant tissues at more than 90% efficiency with an interference-free chromatogram. This allowed the use of lower amounts of reagents and organic solvents, reducing the use of toxic and/or hazardous chemicals, as compared to currently used methodologies. The method was used to determine the level of endogenous shikimic acid in several species of Brachiaria and sugarcane (Saccharum officinarum and on B. decumbens and soybean (Glycine max after treatment with glyphosate. The method was sensitive, rapid and reliable in all cases.Um método melhor para a determinação do chiquimato em tecidos de plantas é necessário para monitorar a exposição destas ao herbicida glyphosate N-(fosfonometilglicina] e selecionar o gênero da planta para altos níveis desse valioso precursor fitoquímico ao fármaco oseltamivir. Um método simples, rápido e eficiente, que usa a extração assistida por micro-ondas (MWAE com água como solvente de extração, foi desenvolvido para a determinação do ácido chiquímico em tecidos de plantas. Foi empregada cromatografia líquida de alto desempenho para a separação do ácido chiquímico, e os dados cromatográficos foram obtidos utilizando arranjo de fotodiodo. Essa técnica de MWAE obteve sucesso na recupera

  19. Solvent-Free Polymerization of L-Aspartic Acid in the Presence of D-Sorbitol to Obtain Water Soluble or Network Copolymers

    Science.gov (United States)

    L-aspartic acid was thermally polymerized in the presence of D-sorbitol with the goal of synthesizing new, higher molecular weight water soluble and absorbent copolymers. No reaction occurred when aspartic acid alone was heated at 170 or 200 degrees C. In contrast, heating sorbitol and aspartic ac...

  20. Influence of Solvent-Solvent and Solute-Solvent Interaction Properties on Solvent-Mediated Potential

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shi-Qi

    2005-01-01

    A recently proposed universal calculational recipe for solvent-mediated potential is applied to calculate excess potential of mean force between two large Lennard-Jones (LJ) or hard core attractive Yukawa particles immersed in small LJ solvent bath at supercritical state. Comparison between the present prediction with a hypernetted chain approximation adopted for solute-solute correlation at infinitely dilute limit and existing simulation data shows high accuracy for the region with large separation, and qualitative reliability for the solute particle contact region. The calculational simplicity of the present recipe allows for a detailed investigation on the effect of the solute-solvent and solvent-solvent interaction details on the excess potential of mean force. The resultant conclusion is that gathering of solvent particles near a solute particle leads to repulsive excess PMF, while depletion of solvent particles away from the solute particle leads to attractive excess PMF, and minor change of the solvent-solvent interaction range has large influence on the excess PMF.

  1. Thermal conductivity and electrical properties of hybrid SiO2-graphene naphthenic mineral oil nanofluid as potential transformer oil

    Science.gov (United States)

    Qing, Soo Hui; Rashmi, W.; Khalid, M.; Gupta, T. C. S. M.; Nabipoor, M.; Taghi Hajibeigy, Mohammad

    2017-01-01

    Hybrid SiO2-graphene nanoparticles were synthesised by sol gel centrifugation technique under four different pH levels ranging from 9 to 12. Stability, thermal conductivity, viscosity and electrical conductivity of hybrid SiO2-graphene and pure graphene dispersed in naphthenic oil were investigated. Nanofluids were synthesied at three different nanoparticle concentrations (0.01, 0.04 and 0.08 wt%) while the temperature was varied from 20 °C to 100 °C. Field emission scanning electron microscopy (FESEM), x-ray spectroscopy and Fourier transform infrared (FTIR) spectrometer show successful coating of SiO2 on graphene surface. The growth units and size distribution of SiO2 nanoparticles increased with pH level. Moreover, the presence of SiO2 improved the dispersion behaviour of the nanofluid as confirmed by visual observation and UV–Vis studies. Zeta potential measurements show the hybrid nanofluids at pH 11 are most stable due to its optimum amount and size of SiO2 coated on graphene surface while at pH 12 shows least stability due to precipitation. The presence of SiO2 on graphene further enhanced the thermal conductivity by 80% at pH 9. Also, the viscosity of hybrid nanofluids was higher than pure graphene based nanofluids due to increase in density and particle size. Moreover, the addition of hybrid SiO2-graphene nanoparticles significantly reduced the electrical conductivity enhancement of base fluid from 557% to 97%.

  2. A Novel Aqueous Two Phase System Composed of a Thermo-Separating Polymer and an Organic Solvent for Purification of Thermo-Acidic Amylase Enzyme from Red Pitaya (Hylocereus polyrhizus Peel

    Directory of Open Access Journals (Sweden)

    Mehrnoush Amid

    2014-05-01

    Full Text Available The purification of thermo-acidic amylase enzyme from red pitaya (Hylocereus polyrhizus peel for the first time was investigated using a novel aqueous two-phase system (ATPS consisting of a thermo-separating copolymer and an organic solvent. The effectiveness of different parameters such as molecular weight of the thermo-separating ethylene oxide-propylene oxide (EOPO copolymer and type and concentration of organic solvent on the partitioning behavior of amylase was investigated. In addition, the effects of phase components, volume ratio (VR, pH and crude load of purification factor and yield of amylase were evaluated to achieve the optimum partition conditions of the enzyme. In the novel ATPS method, the enzyme was satisfactorily partitioned into the polymer-rich top phase in the system composed of 30% (w/w EOPO 2500 and 15% (w/w 2-propanol, at a volume ratio of 1.94 and with a crude load scale of 25% (w/w at pH 5.0. Recovery and recycling of components was also measured in each successive step of the ATPS process. The enzyme was successfully recovered by the method with a high purification factor of 14.3 and yield of 96.6% and copolymer was also recovered and recycled at a rate above 97%, making the method was more economical than the traditional ATPS method.

  3. A novel aqueous two phase system composed of a thermo-separating polymer and an organic solvent for purification of thermo-acidic amylase enzyme from red pitaya (Hylocereus polyrhizus) peel.

    Science.gov (United States)

    Amid, Mehrnoush; Manap, Yazid; Zohdi, Nor Khanani

    2014-05-22

    The purification of thermo-acidic amylase enzyme from red pitaya (Hylocereus polyrhizus) peel for the first time was investigated using a novel aqueous two-phase system (ATPS) consisting of a thermo-separating copolymer and an organic solvent. The effectiveness of different parameters such as molecular weight of the thermo-separating ethylene oxide-propylene oxide (EOPO) copolymer and type and concentration of organic solvent on the partitioning behavior of amylase was investigated. In addition, the effects of phase components, volume ratio (VR), pH and crude load of purification factor and yield of amylase were evaluated to achieve the optimum partition conditions of the enzyme. In the novel ATPS method, the enzyme was satisfactorily partitioned into the polymer-rich top phase in the system composed of 30% (w/w) EOPO 2500 and 15% (w/w) 2-propanol, at a volume ratio of 1.94 and with a crude load scale of 25% (w/w) at pH 5.0. Recovery and recycling of components was also measured in each successive step of the ATPS process. The enzyme was successfully recovered by the method with a high purification factor of 14.3 and yield of 96.6% and copolymer was also recovered and recycled at a rate above 97%, making the method was more economical than the traditional ATPS method.

  4. Solvent Extraction and Characterization of Neutral Lipids in Oocystis sp.

    Directory of Open Access Journals (Sweden)

    Renil eAnthony

    2015-01-01

    Full Text Available Microalgae are a favorable feedstock for bioproducts and biofuels due to their high oil content, fast growth rates and low resource demands. Solvent lipid extraction efficiency from microalgae is dependent on algal strain and the extraction solvent. Four non-polar extraction solvents were evaluated for the recovery of neutral cellular lipids from microalgae Oocystis sp. (UTEX LB2396. Methylene chloride, hexane, diethyl ether, and cyclohexane were selected as the extraction solvents. All solvent extracts contained hexadecanoic acid, linoleic acid and linolenic acid; accounting for 70% of total lipid content with a proportional wt% composition of the three fatty acids, except for the hexane extracts that showed only hexadecanoic acid and linoleic acid. While not statistically differentiated, methylene chloride proved to be the most effective solvent for Oocystis sp. among the four solvents tested with a total average neutral lipid recovery of 0.25% of dry weight followed by diethyl ether (0.18%, cyclohexane (0.14% and hexane (0.11%. This research presents a simple methodology to optimize the selection of lipid specific extraction solvents for the microalgal strain selected.

  5. Solvent-resistant microporous polymide membranes

    Science.gov (United States)

    Miller, Warren K.; McCray, Scott B.; Friesen, Dwayne T.

    1998-01-01

    An asymmetric microporous membrane with exceptional solvent resistance and highly desirable permeability is disclosed. The membrane is made by a solution-casting or solution-spinning process from a copolyamic acid comprising the condensation reaction product in a solvent of at least three reactants selected from certain diamines and dianhydrides and post-treated to imidize and in some cases cross-link the copolyamic acid. The membrane is useful as an uncoated membrane for ultrafiltration, microfiltration, and membrane contactor applications, or may be used as a support for a permselective coating to form a composite membrane useful in gas separations, reverse osmosis, nanofiltration, pervaporation, or vapor permeation.

  6. Organic Solvent Tolerant Lipases and Applications

    Directory of Open Access Journals (Sweden)

    Shivika Sharma

    2014-01-01

    Full Text Available Lipases are a group of enzymes naturally endowed with the property of performing reactions in aqueous as well as organic solvents. The esterification reactions using lipase(s could be performed in water-restricted organic media as organic solvent(s not only improve(s the solubility of substrate and reactant in reaction mixture but also permit(s the reaction in the reverse direction, and often it is easy to recover the product in organic phase in two-phase equilibrium systems. The use of organic solvent tolerant lipase in organic media has exhibited many advantages: increased activity and stability, regiospecificity and stereoselectivity, higher solubility of substrate, ease of products recovery, and ability to shift the reaction equilibrium toward synthetic direction. Therefore the search for organic solvent tolerant enzymes has been an extensive area of research. A variety of fatty acid esters are now being produced commercially using immobilized lipase in nonaqueous solvents. This review describes the organic tolerance and industrial application of lipases. The main emphasis is to study the nature of organic solvent tolerant lipases. Also, the potential industrial applications that make lipases the biocatalysts of choice for the present and future have been presented.

  7. Alternative Green Solvents Project

    Science.gov (United States)

    Maloney, Phillip R.

    2012-01-01

    Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

  8. Stability of the Caustic-Side Solvent Extraction (CSSX) Process Solvent: Effect of High Nitrite on Solvent Nitration

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.V.

    2002-06-26

    The purpose of this investigation was to determine whether nitrated organic compounds could be formed during operation of the Caustic-Side Solvent Extraction (CSSX) process, and whether such compounds would present a safety concern. The CSSX process was developed to remove cesium from alkaline high-level salt waste stored at the US Department of Energy Savannah River Site (SRS). The solvent is composed of the cesium extractant calix[4]arene-bis-(4-tert-octylbenzo-crown-6) (BOBCalixC6), a fluorinated alcohol phase modifier, tri-n-octylamine (TOA), and an isoparaffinic diluent (Iospar{reg_sign}). During the CSSX process, the solvent is expected to be exposed to high concentrations of nitrate and nitrite dissolved in the alkaline waste feed. The solvent will also be exposed to dilute (50 mM) nitric acid solutions containing low concentrations of nitrite during scrubbing, followed by stripping with 1 mM nitric acid. The solvent is expected to last for one year of plant operation, and the temperatures the solvent may experience during the process could range from as low as 15 C to as high as 35 C. Excursions from standard process conditions could result in the solvent experiencing higher temperatures, as well as concentrations of nitrate, nitrite, and most importantly nitric acid, that exceed normal operating conditions. Accordingly, conditions may exist where nitration reactions involving the solvent components, possibly leading to other chemical reactions stemming from nitration reactions, could occur. To model such nitration reactions, the solvent was exposed to the types of nitrate- and nitrite-containing solutions that might be expected to be encountered during the process (even under off-normal conditions), as a function of time, temperature, and concentration of nitrate, nitrite, and nitric acid. The experiments conducted as part of this report were designed to examine the more specific effect that high nitrite concentrations could have on forming nitrated

  9. The Effect of the Synergism of Magnetic Field & Solvents on the Crystallization of Glutamic Acid%磁场-溶剂协同作用对谷氨酸结晶过程的影响

    Institute of Scientific and Technical Information of China (English)

    罗文波; 王弘; 于淑娟; 高大维

    2001-01-01

    研究了磁场-溶剂协同作用对谷氨酸结晶过程的影响及磁场作用下谷氨酸过饱和溶液表面张力、电导率的变化,并对磁场促进谷氨酸结晶的作用机理进行了探讨,提出了一种利用磁场-溶剂协同作用制备谷氨酸晶种的新方法.研究结果表明,磁场对谷氨酸结晶有促进作用,磁场-溶剂协同作用加速了晶体的成核过程,生成的晶粒均匀,结晶率高.%This paper studies the effect of the synergism of magnetic fieldand solvents on the crystallization of glutamic acid and the effects of magnetic field on surface tension and conductivity of glutamic acid supersaturated solution. The mechanism of the encouragement of magnetic field on the crystallization is discussed too, thus a new method to produce the crystal seeds by the synergism is presented. It is shown that the speed of crystallization of glutamic acid is hastened by magnetic field. The crystal seeds got by the method have the advantage of well-distributed crystal size and integrated, purity crystallization.

  10. Solvent extraction of uranium(VI) and thorium(IV) in nitric acid solution by N,N,N‘,N’—tetrabutyladipicamide

    Institute of Scientific and Technical Information of China (English)

    WangYou-Shao; BaoBo-Rong; 等

    1997-01-01

    N,N,N'N'-tetrabutyladipicamide(TBAA) has been synthesized,and applied to the extraction of U(VI) and Th(IV) from nitric acid solutions in a diluent composed of 0.50 volume fraction 1,2,4-trimethyl benzene (TMA) and 0.50 volume fraction kerosene(OK),The effects of the aueous nitric acid concentration,extractant concentration,slating-out agent (LiNO3) and temperature on extraction ability of TBAA for U(VI) and Th(IV) have been studied.Back Extraction of U(VI) and Th (IV) from organic phases were performed by dilute nitric acid.The compositions of extracted complexes,equilibrium constants and enthalpies of extraction reactions have also been estimated.The IR spectra of extraction of U(VI) and Th(IV) have been studied.

  11. Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride

    Science.gov (United States)

    Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.

    2017-03-01

    Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.

  12. Molecular dynamics simulations of the free and inhibitor-bound cruzain systems in aqueous solvent: insights on the inhibition mechanism in acidic pH.

    Science.gov (United States)

    Hoelz, L V B; Leal, V F; Rodrigues, C R; Pascutti, P G; Albuquerque, M G; Muri, E M F; Dias, L R S

    2016-09-01

    The major cysteine protease of Trypanosoma cruzi, cruzain (CRZ), has been described as a therapeutic target for Chagas' disease, which affects millions of people worldwide. Thus, a series of CRZ inhibitors has been studied, including a new competitive inhibitor, Nequimed176 (NEQ176). Nevertheless, the structural and dynamic basis for CRZ inhibition remains unclear. Hoping to contribute to this ever-growing understanding of timescale dynamics in the CRZ inhibition mechanism, we have performed the first study using 100 ns of molecular dynamics (MD) simulations of two CRZ systems in an aqueous solvent under pH 5.5: CRZ in the apo form (ligand free) and CRZ complexed to NEQ176. According to the MD simulations, the enzyme adopts an open conformation in the apo form and a closed conformation in the NEQ176-CRZ complex. We also suggest that this closed conformation is related to the hydrogen-bonding interactions between NEQ176 and CRZ, which occurs through key residues, mainly Gly66, Met68, Asn69, and Leu160. In addition, the cross-correlation analysis shows evidence of the correlated motions among Ala110-Asp140, Leu160-Gly189, and Glu190-Gly215 subdomains, as well as, the movements related to Ala1-Thr59 and Asp60-Pro90 regions seem to be crucial for CRZ activity.

  13. Effect of f-electron configurations on the adsorption of trivalent f-elements on tertiary pyridine resin in hydrochloric acid/alcohol mixed solvents

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, Atsushi; Suzuki, Tatsuya; Aida, Masao; Ohtake, Kouhei; Fujii, Yasuhiko; Itoh, Keisuke; Hara, Mitsuo; Mitsugashira, Toshiaki

    2004-07-14

    The separation of trivalent actinides (An) from lanthanides (Ln) is difficult because of their chemical similarities although it is necessary for various fields such as nuclear fuel-cycle process. In the present study, it was observed that the trivalent An (Am{sup 3+}, Cm{sup 3+} and Cf{sup 3+}) were adsorbed on tertiary pyridine type resins far more strongly than the Ln in HCl (LiCl solution)/methanol mixed solvents and the An were separated from the Ln by using a single separation process. On the other hand, the Dowex 1 x 8 showed no adsorption in the same conditions. Therefore, there is a possibility that the adsorption of An and Ln cations is caused by the complexation of the cations with the tertiary pyridine groups of the resins, not by the ionic interaction. There seems to be some relationship between the distribution coefficients (K{sub d}) of trivalent f-elements (i.e. An and Ln) and the f-electron configurations of their cations, and their ionic size.

  14. Thermodynamic modelling of the absorption of acid gas in mixed solvent (water-di-ethanolamine-methanol); Modelisation thermodynamique de l'absorption des gaz acides dans un solvant mixte (eau-diethanolamine-methanol)

    Energy Technology Data Exchange (ETDEWEB)

    Habchi tounsi, K.N.

    2003-10-01

    This work is related to the development of new processes about gas sweetening with mixed solvent coupling a chemical one (aqueous solution of di-ethanolamine) and a physical one (Methanol). These systems are electrolyte solutions constituted by ions and molecular species related each others by chemical reactions. This work is also relevant to the problematic of solvent mixtures (water-methanol). In a first stage we focus our interest over the measurement of original data covering a large experimental interval: five compositions in condition of pressures and temperatures up to 30 and 120 deg C respectively. In a second stage the simultaneous representation of chemical and phase equilibrium was successfully realised. The non stoichiometric method is used for the determination of chemical equilibrium. The heterogeneous method (Peng Robinson + NRTL electrolyte) is used for the representation of vapour liquid equilibrium. (author)

  15. Boric acid as a mild and efficient catalyst for one-pot synthesis of 1-amidoalkyl-2-naphthols under solvent-free conditions

    Indian Academy of Sciences (India)

    Aziz Shahrisa; Somayeh Esmati; Mahdi Gholamhosseini Nazari

    2012-07-01

    An efficient green chemistry method has been developed for the synthesis of 1-amidoalkyl-2-naphthol derivatives via a one-pot three-component condensation of 2-naphthol, aldehydes and amide in the presence of boric acid as a mild catalyst.

  16. Miscibility of poly(lactic acid) and poly(ethylene oxide) solvent polymer blends and nanofibers made by solution blow spinning

    Science.gov (United States)

    The miscibility of blends of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) was studied in polymer solutions by dilute solution viscometry and in solution blow spun nanofibers by microscopy (SEM, TEM) and by thermal and spectral analysis. Three blends of PLA and PEO were solution blended in...

  17. Lipase catalyzed esterification of glycidol in nonaqueous solvents: solvent effects on enzymatic activity.

    Science.gov (United States)

    Martins, J F; de Sampaio, T C; de Carvalho, I B; Barreiros, S

    1994-06-05

    We studied the effect of organic solvents on the kinetics of porcine pancreatic lipase (pp) for the resolution of racemic glycidol through esterification with butyric acid. We quantified ppl hydration by measuring water sorption isotherms for the enzyme in the solvents/mixtures tested. The determination of initial rates as a function of enzyme hydration revealed that the enzyme exhibits maximum apparent activity in the solvents/mixtures at the same water content (9% to 11% w/w) within the associated experimental error. The maximum initial rates are different in all the media and correlate well with the logarithm of the molar solubility of water in the media, higher initial rates being observed in the solvents/mixtures with lower water solubilities. The data for the mixtures indicate that ppl apparent activity responds to bulk property of the solvent. Measurements of enzyme particle sizes in five of the solvents, as function of enzyme hydration, revealed that mean particle sizes increased with enzyme hydration in all the solvents, differences between solvents being more pronounced at enzyme hydration levels close to 10%. At this hydration level, solvents having a higher water content lead to lower reaction rates; these are the solvents where the mean enzyme particle sizes are greater. Calculation of the observable modulus indicates there are no internal diffusion limitations. The observed correlation between changes in initial rates and changes in external surface area of the enzyme particles suggests that interfacial activation of ppl is only effective at the external surface of the particles. Data obtained for the mixtures indicate that ppl enantioselectivity depends on specific solvent-enzyme interactions. We make reference to ppl hydration and activity in supercritical carbon dioxide.

  18. Modeling post-combustion CO2 capture with amine solvents

    OpenAIRE

    Léonard, Grégoire; Heyen, Georges

    2010-01-01

    In order to avoid the emission of large amounts of greenhouse gas, CO2 capture in fossil fuel power plants and subsequent underground CO2 sequestration is studied. The capture occurs by reactive CO2 absorption into chemical solvent systems at moderate temperature (~50°C) followed by solvent regeneration at higher temperature (~120°C). So far, the most employed solvent for acid gas capture is monoethanolamine (MEA). One main drawback of this technology is the high energy consumption necessary ...

  19. Solvent effect modelling of isocyanuric products synthesis by chemometric methods

    OpenAIRE

    Havet, Jean-Louis; Billiau-Loreau, Myriam; Porte, Catherine; Delacroix, Alain

    2002-01-01

    Chemometric tools were used to generate the modelling of solvent e¡ects on the N-alkylation of an isocyanuric acid salt. The method proceeded from a central composite design applied on the Carlson solvent classification using principal components analysis. The selectivity of the reaction was studied from the production of different substituted isocyanuric derivatives. Response graphs were obtained for each compound and used to devise a strategy for solvent selection. The prediction models wer...

  20. Correlation between aggregation and extracting properties in solvent extraction systems: extraction of actinides (III) and lanthanides (III) by a malonamide in non acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Meridiano, Y.; Berthon, L.; Lagrave, S.; Crozes, X.; Sorel, C.; Testard, F.; Zemb, T. [CEA Marcoule, DEN/DRCP/SCPS/LCSE, 30207Bagnols sur Ceze (France)

    2008-07-01

    The organic phases of the DIAMEX (Diamide Extraction) process, allowing the co-extraction of actinides(III) and lanthanides(III) from high level radioactive wastes using a malonamide extractant molecule (DMDOHEMA) diluted in alkanes, are investigated. The aim of this study is to establish a link between different structures/organizations of diamide extractants and their extracting properties towards An(III) and Ln(III) cations. It is demonstrated that diamide, which are amphiphilic molecules, are organized in different structures (monomers, reverse micelles, lamellar phases..). This study deals with the effect of the composition of the extracting system on the extracting and aggregation properties of the DMDOHEMA solutions. The effects of the extractant (DMDOHEMA diluted in n-heptane) and metal concentrations (for a given extractant concentration) from a LiNO{sub 3} aqueous phase are investigated at two scales: at the supra-molecular scale by characterizing the aggregation by vapor-pressure osmometry (VPO) and small angle neutron and X-ray scattering (SANS and SAXS) experiments, and at the molecular scale by quantifying the extracted solutes (metal nitrate and water) and by determining the stoichiometries of the extracted complexes by electro-spray mass spectrometry (ESI-MS). The extraction equilibria can then be modeled by two approaches: a classical approach in solvent extraction based on mass action laws to determine extraction equilibria and their associated thermodynamic constants, and a physical chemical approach which consists in considering the extracted ions as adsorbed on a specific available surface of the extractant molecule. Thus, the extraction equilibrium can be considered as a sum of Langmuir isotherms corresponding to the different states of aggregation. The resulting constants are representative of both extraction efficiency and organic phase structure. (authors)

  1. Use of stirred tanks for studying matrix effects caused by inorganic acids, easily ionized elements and organic solvents in inductively coupled plasma atomic emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Paredes, Eduardo [Departamento de Quimica Analitica, Nutricion y Bromatologia, University of Alicante, 03080 Alicante (Spain); Maestre, Salvador E. [Departamento de Quimica Analitica, Nutricion y Bromatologia, University of Alicante, 03080 Alicante (Spain); Todoli, Jose L. [Departamento de Quimica Analitica, Nutricion y Bromatologia, University of Alicante, 03080 Alicante (Spain)]. E-mail: jose.todoli@ua.es

    2006-03-15

    A stirred tank was used for the first time to elucidate the mechanism responsible for inductively coupled plasma atomic emission spectroscopy (ICP-AES) matrix effects caused by inorganic, acids and easily ionized elements (EIEs), as well as organic, ethanol and acetic acid, compounds. In order to gradually increase the matrix concentration, a matrix solution was introduced inside a stirred container (tank) initially filled with an aqueous multielement standard. PolyTetraFluoroEthylene (PTFE) tubing was used to deliver the resulting solution to the liquid sample introduction system. Matrix concentration ranged from 0 to 2 mol l{sup -1} in the case of inorganic acids (i.e., nitric, sulfuric, hydrochloric and a mixture of them), from 0 to about 2500 mg l{sup -1} for EIEs (i.e., sodium, calcium and mixtures of both) and from 0% to 15%, w/w for organic compounds. Up to 40-50 different solutions were prepared and measured in a period of time shorter than 6-7 min. This investigation was carried out in terms of emission intensity and tertiary aerosols characteristics. The experimental setup used in the present work allowed to thoroughly study the effect of matrix concentration on analytical signal. Generally speaking, the experiments concerning tertiary aerosol characterization revealed that, in the case of inorganic acids and EIEs, the mechanism responsible for changes in aerosol characteristics was the droplet fission. In contrast, for organic matrices it was found that the interference was caused by a change in both aerosol transport and plasma thermal characteristics. The extent of the interferences caused by organic as well as inorganic compounds was compared for a set of 14 emission lines through a wide range of matrix concentrations. With a stirred tank, it is possible to choose an efficient internal standard for any given matrix composition. The time required to complete this procedure was shorter than 7 min.

  2. Advanced integrated solvent extraction systems

    Energy Technology Data Exchange (ETDEWEB)

    Horwitz, E.P.; Dietz, M.L.; Leonard, R.A. [Argonne National Lab., IL (United States)

    1997-10-01

    Advanced integrated solvent extraction systems are a series of novel solvent extraction (SX) processes that will remove and recover all of the major radioisotopes from acidic-dissolved sludge or other acidic high-level wastes. The major focus of this effort during the last 2 years has been the development of a combined cesium-strontium extraction/recovery process, the Combined CSEX-SREX Process. The Combined CSEX-SREX Process relies on a mixture of a strontium-selective macrocyclic polyether and a novel cesium-selective extractant based on dibenzo 18-crown-6. The process offers several potential advantages over possible alternatives in a chemical processing scheme for high-level waste treatment. First, if the process is applied as the first step in chemical pretreatment, the radiation level for all subsequent processing steps (e.g., transuranic extraction/recovery, or TRUEX) will be significantly reduced. Thus, less costly shielding would be required. The second advantage of the Combined CSEX-SREX Process is that the recovered Cs-Sr fraction is non-transuranic, and therefore will decay to low-level waste after only a few hundred years. Finally, combining individual processes into a single process will reduce the amount of equipment required to pretreat the waste and therefore reduce the size and cost of the waste processing facility. In an ongoing collaboration with Lockheed Martin Idaho Technology Company (LMITCO), the authors have successfully tested various segments of the Advanced Integrated Solvent Extraction Systems. Eichrom Industries, Inc. (Darien, IL) synthesizes and markets the Sr extractant and can supply the Cs extractant on a limited basis. Plans are under way to perform a test of the Combined CSEX-SREX Process with real waste at LMITCO in the near future.

  3. Supercritical solvent coal extraction

    Science.gov (United States)

    Compton, L. E. (Inventor)

    1984-01-01

    Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

  4. D2EHPA对高浓度盐酸介质中钛的萃取%Solvent extraction of tetravalent thitanium from high concentration of acidic chloride solutions by D2EHPA

    Institute of Scientific and Technical Information of China (English)

    毛雪华; 刘代俊

    2012-01-01

    研究了D2 EHPA对盐酸介质中钛的萃取和反萃性能.研究结果表明:萃取液中钛以TiOCl2·2 D2 EHPA的形式存在.钛萃取率随无机相中氯离子浓度和有机相中萃取剂浓度的增加而增加.D2EHPA对钛的饱和承载量为8.98 g/100 g D2EHPA.红外光谱研究进一步表明了Ti-D2EHPA螯合物的性质.在0.5-12 moL/dm3的盐酸介质中,D2EHPA对钛的萃取率随盐酸介质浓度的增加而增加,而对铁、铝、钙、镁无萃取性能.以7% H2O2 +3 mol/dm3 H2SO4为反萃剂,有机相中的钛可实现一次完全反萃.%The solvent extraction and stripping of titanium(IV) from acidic chloride solutions by D2EHPA(di-2-ethylhexyl phosphoric acid) in kerosene has been investigated. The solvent extraction results show that the dissolved titanium is present as TiOCl2 ·D2EHPA. The extractability of titanium ( IV ) increases with the increase of the total chloride concentration in the aqueous phase and the extractant concentration in the organic phase. The loading capacity of D2EHPA for titanium( IV) is 8. 98 g/100 g D2EHPA. IR spectroscopy is used to study the extracted complex in order to further clarify the nature of extracted complex. The results show that,the extractability of titanium( IV) increases when the concentration of hydrochloric acid aqueous solution increases from 0.5 mol'dm" to 12 mol o dm . On the other hand, iron ( III) , aluminum ( HI) , calcium ( II ) and magnesium ( II ) are not extracted under the same experimental conditions. Titanium( IV) can be completely stripped from the metal loaded organic phase with 7% H2O2 in 3 mol-dm H2SO4 as the stripping agent.

  5. Computer-Aided Solvent Screening for Biocatalysis

    DEFF Research Database (Denmark)

    Abildskov, Jens; Leeuwen, M.B. van; Boeriu, C.G.;

    2013-01-01

    . Esterification of acrylic acid with octanol is also addressed. Solvents are screened and candidates identified, confirming existing experimental results. Although the examples involve lipases, the method is quite general, so there seems to be no preclusion against application to other biocatalysts....

  6. Cleaning without chlorinated solvents

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.M.; Simandl, R.F.

    1994-12-31

    Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92%. The program has been a twofold effort. Vapor degreasers used in batch cleaning-operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting and bonding. Cleaning ability was determined using techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes and swelling of epoxies.

  7. 有机介质中沉淀聚合制备聚丙烯酸微凝胶及其性能%Preparation and Properties of Polyacrylic Acid Microgel by Precipitation Polymerization in Organic Solvent

    Institute of Scientific and Technical Information of China (English)

    王飞俊; 邵自强; 杨萌; 王文俊; 李永红

    2012-01-01

    Polyacrylic acid(PAA) microgels were prepared by precipitation polymerization of acrylic acid in different organic solvent and their properties were analyzed by scanning electron microscope(SEM),rheometer and UV spectrophotometer.The results show that cyclohexane is the appropriate solvent;the pH value of PAA microgel reaches the minimum when the mass fraction of PAA is 0.7%;PAA microgel solution is a kind of pseudoplastic fluid,its viscosity does not vary with the temperature,and reaches the maximum viscosity with pH value of 7,while the microgel changes into the macro gel;the higher the crosslinking degree,the more greatly the viscosity changes with pH value.%选用不同有机溶剂体系为分散介质,通过丙烯酸的沉淀聚合制备了聚丙烯酸(PAA)微凝胶,并用扫描电镜(SEM)、流变仪和紫外分光光度计对其性能进行了测试。结果表明,环己烷是合适的溶剂;PAA微凝胶的pH值在质量分数为0.7%时最低;PAA微凝胶水溶液为假塑性流体,黏度不随温度而变化,且pH为7时,溶液黏度最大,此时,PAA已从微凝胶转变成宏观凝胶;交联程度越高,黏度随pH变化越大。

  8. Solvent selection methodology for pharmaceutical processes: Solvent swap

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Kumar Tula, Anjan; Gani, Rafiqul

    2016-01-01

    A method for the selection of appropriate solvents for the solvent swap task in pharmaceutical processes has been developed. This solvent swap method is based on the solvent selection method of Gani et al. (2006) and considers additional selection criteria such as boiling point difference, volati...

  9. 苯甲酸溶解度的测定及关联%Measurement and Correlation of Solubilities of Benzoic Acid in Different Solvents

    Institute of Scientific and Technical Information of China (English)

    刘江刍鸟; 李殿卿; 刘大壮; 陈忠民; 田洪河

    2001-01-01

    Using a laser monitoring observation technique,the solubilities of benzoic acid in trichloromethane,N,N-dimethylformamide,N,N-dimethylacetamide and N-Methyl-2-pyrrolidonewere,which has never been seen in literatures before,are determined by the synthetic method.To verify the reliability of the experimental method,the solubility of benzoic acid in water was measured before the experiments,which shows excellent consistency with the literature data.By means of Apelblat's solubility model to correlate the experimental results,the calculated solubilities show good agreement with the experimental values.%为了回收、提纯PTA氧化残渣中的苯甲酸,采用激光监视技术由合成法测定了鲜见文献报道的苯甲酸在氯仿、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的溶解度.为了验证测定方法的可靠性,事先测定了苯甲酸在水、醋酸中的溶解度,与已有文献数据相比,一致性较好.用Apelblat等人提出的溶解度模型对实验数据进行关联,计算的溶解度与实验值符合良好.

  10. Solvent extraction-separation of La(III), Eu(III) and Er(III) ions from aqueous chloride medium using carbamoyl-carboxylic acid extractants

    Institute of Scientific and Technical Information of China (English)

    Reyhaneh Safarbali; Mohammad Reza Yaftian; Abbasali Zamani

    2016-01-01

    N,N-dibutyldiglycol amic acid (HLI) and N,N-dioctyldiglycol amic acid (HLI) were synthesized and characterized by con-ventional spectroscopic methods. These molecules were examined as extractants for extraction-separation of La(III), Eu(III) and Er(III), as representative ions of light, middle and heavy rare earths, from aqueous chloride solutions. The analysis of the extraction equilibria revealed that the extracted species of lanthanum and europium ions by both of the extractants had a 1:3 metal to ligand ratio. It was suggested that erbium ions were extracted into the organic phase via the formation of Er(LI or I)2Cl complexes. The effect of the organic diluents on the extraction-separation efficiency of the studied rare earths by HLI and HLI was investigated by comparing the results obtained in dichloromethane and carbon tetrachloride. Regardless to the diluent used, the order of selectivity presented by the investigated extractants was Er(III)>Eu(III)>La(III). It is noteworthy that, a significant enhancement in separation of the studied rare earths by the extractants was achieved in their competitive extraction experiments with respect to that obtained in single component extraction experiments. Applicability of the extractants for the removal of rare earth ions from spent Ni-MH batteries was tested by removal of La(III), Eu(III) and Er(III) ions from simulated leach solution of such batteries.

  11. First principles pKa calculations on carboxylic acids using the SMD solvation model: effect of thermodynamic cycle, model chemistry, and explicit solvent molecules.

    Science.gov (United States)

    Sutton, Catherine C R; Franks, George V; da Silva, Gabriel

    2012-10-04

    Aqueous pK(a) values are calculated from first principles for a set of carboxylic acids using the SMD solvation model with various model chemistries, thermodynamic cycles, and treatments of explicit solvation. In all, 108 unique theoretical protocols are examined. The direct (D) and water proton exchange (PX) cycles are trialled along with a new approach, termed the semidirect (SD) cycle. The SD thermodynamic cycle offers some improvements over the D and PX schemes, as it bypasses the gas-phase heterolytic bond dissociation calculation required in the conventional D approach while also avoiding an aqueous OH(-) calculation required by the PX method when using water as the reference acid. With all three cycles, the recommended model chemistry employs M05-2X/cc-pVTZ Gibbs energies of solvation with a single discrete water molecule and a high-level composite method for the gas-phase reaction energies. With the SD cycle, these calculations result in a mean unsigned error of less than 1 pK(a) units, with respective mean signed error and maximum unsigned error of less than 0.5 and 2 pK(a) units. Similar results are obtained with the D and PX cycles, and further improvement is required in both the gas and aqueous phase ab initio energy calculations before we can truly discriminate between the thermodynamic cycles investigated here.

  12. Lipase-catalyzed preparation of diacylglycerol-enriched oil from high-acid rice bran oil in solvent-free system.

    Science.gov (United States)

    Song, Zhihua; Liu, Yuanfa; Jin, Qingzhe; Li, Lei; Wang, Xingguo; Huang, Jianhua; Liu, Ruijie

    2012-09-01

    The ability of immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) to catalyze the reaction of high-acid rice bran oil (RBO) and monoglyceride (MG) for diacylglycerol-enriched rice bran oil (RBO-DG) preparation was investigated. The effects of substrate ratio, reaction temperature, time, and enzyme load on the respective content of free fatty acid (FFA) and DG in the final RBO-DG products was investigated. Enzyme screening on the reaction was also investigated. Response surface methodology (RSM) was used to optimize the effects of the reaction temperature (50-70 °C), the enzyme load (2-6 %; relative to the weight of total substrates), and the reaction time (4-8 h) on the respective content of FFA and DG. Validation of the RSM model was verified by the good agreement between the experimental and the predicted values. The optimum preparation conditions were as follows: MG/RBO, 0.25; temperature, 56 °C; enzyme load, 4.77 %; and reaction time, 5.75 h. Under the suggested conditions, the respective content of FFA and DG was 0.28 and 27.98 %, respectively. Repeated reaction tests indicated that Lipozyme RM IM could be used nine times under the optimum conditions with 90 % of its original catalytic activity still retained.

  13. Report on the analysis of common beverages spiked with gamma-hydroxybutyric acid (GHB) and gamma-butyrolactone (GBL) using NMR and the PURGE solvent-suppression technique.

    Science.gov (United States)

    Lesar, Casey T; Decatur, John; Lukasiewicz, Elaan; Champeil, Elise

    2011-10-10

    In forensic evidence, the identification and quantitation of gamma-hydroxybutyric acid (GHB) in "spiked" beverages is challenging. In this report, we present the analysis of common alcoholic beverages found in clubs and bars spiked with gamma-hydroxybutyric acid (GHB) and gamma-butyrolactone (GBL). Our analysis of the spiked beverages consisted of using (1)H NMR with a water suppression method called Presaturation Utilizing Relaxation Gradients and Echoes (PURGE). The following beverages were analyzed: water, 10% ethanol in water, vodka-cranberry juice, rum and coke, gin and tonic, whisky and diet coke, white wine, red wine, and beer. The PURGE method allowed for the direct identification and quantitation of both compounds in all beverages except red and white wine where small interferences prevented accurate quantitation. The NMR method presented in this paper utilizes PURGE water suppression. Thanks to the use of a capillary internal standard, the method is fast, non-destructive, sensitive and requires no sample preparation which could disrupt the equilibrium between GHB and GBL.

  14. Accurate Three States Model for Amino Acids with Two Chemically Coupled Titrating Sites in Explicit Solvent Atomistic Constant pH Simulations and pKa Calculations.

    Science.gov (United States)

    Dobrev, Plamen; Donnini, Serena; Groenhof, Gerrit; Grubmüller, Helmut

    2017-01-10

    Correct protonation of titratable groups in biomolecules is crucial for their accurate description by molecular dynamics simulations. In the context of constant pH simulations, an additional protonation degree of freedom is introduced for each titratable site, allowing the protonation state to change dynamically with changing structure or electrostatics. Here, we extend previous approaches for an accurate description of chemically coupled titrating sites. A second reaction coordinate is used to switch between two tautomeric states of an amino acid with chemically coupled titratable sites, such as aspartate (Asp), glutamate (Glu), and histidine (His). To this aim, we test a scheme involving three protonation states. To facilitate charge neutrality as required for periodic boundary conditions and Particle Mesh Ewald (PME) electrostatics, titration of each respective amino acid is coupled to a "water" molecule that is charged in the opposite direction. Additionally, a force field modification for Amber99sb is introduced and tested for the description of carboxyl group protonation. Our three states model is tested by titration simulations of Asp, Glu, and His, yielding a good agreement, reproducing the correct geometry of the groups in their different protonation forms. We further show that the ion concentration change due to the neutralizing "water" molecules does not significantly affect the protonation free energies of the titratable groups, suggesting that the three states model provides a good description of biomolecular dynamics at constant pH.

  15. Biofiltration of solvent vapors from air

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Young-sook.

    1993-01-01

    For various industrial solvent vapors, biofiltration promises to offer a cost-effective emission control technology. Exploiting the full potential of this technology will help attain the goals of the Clean Air Act Amendments of 1990. Concentrating on large volumes of volatile industrial solvents, stable multicomponent microbial enrichments capable of growing a mineral medium with solvent vapors as their only source of carbon and energy were obtained from soil and sewage sludge. These consortia were immobilized on an optimized porous solid support (ground peat moss and perlite). The biofilter material was packed in glass columns connected to an array of pumps and flow meters that allowed the independent variation of superficial velocity and solvent vapor concentrations. In various experiments, single solvents, such as methanol, butanol, acetonitrile, hexane and nitrobenzene, and solvent mixtures, such as benzene-toluene-xylene (BTX) and chlorobenzene-o-dichlorobenzene (CB/DCB) were biofiltered with rates ranging from 15 to334 g solvent removed per m[sup 3] filter volume /h. Pressure drops were low to moderate (0-10 mmHg/m) and with periodic replacement of moisture, the biofiltration activity could be maintained for a period of several months. The experimental data on methanol biofiltration were subjected to mathematical analysis and modeling by the group of Dr. Baltzis at NJIT for a better understanding and a possible scale up of solvent vapor biofilters. In the case of chlorobenzenes and nitrobenzene, the biofilter columns had to be operated with water recirculation in a trickling filter mode. To prevent inactivation of the trickling filter by acidity during CB/DCB removal, pH control was necessary, and the removal rate of CB/DCB was strongly influenced by the flow rate of the recyling water. Nitrobenzene removal in a trickling filter did not require pH control, since the nitro group was reduced and volatilized as ammonia.

  16. Purex process solvent: literature review

    Energy Technology Data Exchange (ETDEWEB)

    Geier, R.G.

    1979-10-01

    This document summarizes the data on Purex process solvent presently published in a variety of sources. Extracts from these various sources are presented herein and contain the work done, the salient results obtained, and the original, unaltered conclusions of the author of each paper. Three major areas are addressed: solvent stability, solvent quality testing, and solvent treatment processes. 34 references, 44 tables.

  17. Spectroscopic characterization of charge transfer complexes of 2,3-diaminopyridine with chloranilic acid and dihydroxy-p-benzoquinone in polar solvent.

    Science.gov (United States)

    Al-Ahmary, Khairia M

    2014-01-03

    Charge transfer (CT) complexes formed between 2,3-aminopyridine (2,3-DAP) as electron donor with the π-electron acceptors chloranilic acid (CHA) and dihydroxy-p-benzoquinone (DHBQ) were investigated spectrophotometrically in ethanol. Minimum-maximum absorbance method has been used for estimating the formation constants of the charge transfer reactions (KCT). Job's method of continuous variation and photometric titration studies were used to detect the stoichiometric ratios of the formed complexes and they showed that 1:1 complexes were produced. The molar extinction coefficient (ε), oscillator strength (f), dipole moment (μ), charge transfer energy (ECT), ionization potential (IP) and the dissociation energy (W) of the formed complexes were estimated, they reached acceptable values suggesting the stability of the formed CT-complexes. The solid CT-complexes were synthesized and characterized by elemental analyses, (1)H NMR and FTIR spectroscopies where the formed complexes included proton and electron transfer.

  18. Conversion of , '-dichlorodiazene dioxides using levulinic acid under solvent-free conditions to -chloroketones through a three-step domino process

    Indian Academy of Sciences (India)

    B C Vimala; Gopalpur Nagendrappa

    2009-11-01

    -Chloroketones find numerous synthetic uses. We have developed a simple method of preparation of these compounds starting from alkenes adopting the Green Chemistry principle of solventfree reaction. The procedure involves addition of NOCl generated in situ by the reaction of AcOH-HCl (3 : 1) with amyl nitrite to alkenes and treating the -chloronitroso compounds obtained as dimers with levulinic acid in presence of a few drops of 6N HCl, the latter being a three-step domino reaction, in which the first is dissociation of dimer to monomer, the second is tautomerisation of the nitroso function to oxime followed by deoximation in the third step. The yields are excellent. Since the starting compounds are readily available alkenes and the reaction is carried out under mild conditions leading to excellent yields of highly useful -chloroketones, the procedure has the potential of wide application.

  19. Compound forming extractants, solvating solvents and inert solvents IUPAC chemical data series

    CERN Document Server

    Marcus, Y; Kertes, A S

    2013-01-01

    Equilibrium Constants of Liquid-Liquid Distribution Reactions, Part III: Compound Forming Extractants, Solvating Solvents, and Inert Solvents focuses on the compilation of equilibrium constants of various compounds, such as acids, ions, salts, and aqueous solutions. The manuscript presents tables that show the distribution reactions of carboxylic and sulfonic acid extractants and their dimerization and other reactions in the organic phase and extraction reactions of metal ions from aqueous solutions. The book also states that the inorganic anions in these solutions are irrelevant, since they d

  20. Safe battery solvents

    Science.gov (United States)

    Harrup, Mason K.; Delmastro, Joseph R.; Stewart, Frederick F.; Luther, Thomas A.

    2007-10-23

    An ion transporting solvent maintains very low vapor pressure, contains flame retarding elements, and is nontoxic. The solvent in combination with common battery electrolyte salts can be used to replace the current carbonate electrolyte solution, creating a safer battery. It can also be used in combination with polymer gels or solid polymer electrolytes to produce polymer batteries with enhanced conductivity characteristics. The solvents may comprise a class of cyclic and acyclic low molecular weight phosphazenes compounds, comprising repeating phosphorus and nitrogen units forming a core backbone and ion-carrying pendent groups bound to the phosphorus. In preferred embodiments, the cyclic phosphazene comprises at least 3 phosphorus and nitrogen units, and the pendent groups are polyethers, polythioethers, polyether/polythioethers or any combination thereof, and/or other groups preferably comprising other atoms from Group 6B of the periodic table of elements.

  1. Effect of replacing solvent-extracted canola meal with high-oil traditional canola, high-oleic acid canola, or high-erucic acid rapeseed meals on rumen fermentation, digestibility, milk production, and milk fatty acid composition in lactating dairy cows.

    Science.gov (United States)

    Hristov, A N; Domitrovich, C; Wachter, A; Cassidy, T; Lee, C; Shingfield, K J; Kairenius, P; Davis, J; Brown, J

    2011-08-01

    The objective of this experiment was to investigate the effects of replacing conventional, solvent-extracted canola meal (control; CTRL) with high oil content; conventional, mechanically extracted canola meal (CMEC); high-oleic, low polyunsaturated fatty acid (FA) canola meal (HOLL); and high-erucic acid, low-glucosinolate rapeseed meal (RPS) on rumen function, digestibility, milk production, and milk FA composition in lactating dairy cows. The experimental design was a replicated 4×4 Latin square with 8 lactating dairy cows. Four of the cows were ruminally cannulated. All oilseed meals were included at approximately 12 to 13% of dietary dry matter (DM). Crude protein and fat concentrations (% of DM) of the meals were 43 and 3.1%, 32.8 and 16.1%, 45.2 and 13.7%, and 34.3 and 17.9% for CTRL, CMEC, HOLL, and RPS, respectively. All diets were formulated to supply net energy of lactation in excess of requirements. The CMEC and RPS diets were predicted to be about 1% deficient in metabolizable protein. Relative to the CTRL, inclusion of high-oil seed meals in the diet lowered ruminal acetate concentration and the molar acetate:propionate ratio and decreased DM intake. Milk yield generally followed DM intake and was lower for CMEC and RPS than the CTRL. Treatments had no effect on milk composition, other than an increase in milk urea nitrogen concentration for HOLL. Fat-corrected milk (3.5%) feed efficiency was increased by HOLL and RPS compared with CTRL. Urinary urea nitrogen losses were increased by HOLL, which, as a consequence, increased the ammonia-emitting potential of manure. The ratio of milk N-to-N intake was greater for CMEC and RPS. Replacing solvent-extracted canola meal with the high-oil meal decreased milk fat 12:0, 14:0, 16:0, and total saturated FA content and enhanced cis-9 18:1 and total monounsaturated FA concentrations. Relative to the CTRL, canola increased total trans FA in milk, whereas inclusion of HOLL in the diet increased trans-11 18:1 and

  2. Ultrasonic Velocity, Viscosity and Refractive Index Investigation on Interacting Blend Solutions of PAA (Poly Acrylic Acid) and PVA (Poly Vinyl Alcohol) in Solvent DMSO (Di methyl Sulphoxide)

    Science.gov (United States)

    Nagamani, Chakrala

    2010-11-01

    The present study provides a great insight into the major new research areas like Plasma research (which is yielding a greater understanding of the universe) and Nano Technology Research (which provides many practical uses like Drug Delivery System). The Ultrasonic Velocities, Viscosities and Refractive indices of Poly (Acrylic Acid) and Poly (Vinyl Alcohol) blends in DMSO solutions have been measured over a wide range of composition, concentration and at different temperatures. The variation of Ultrasonic Velocity, derived acoustical parameters, adiabatic compressibility, acoustic impedance, Rao number, molar compressibility and relaxation strength with composition of blend solution was found not linear. This non-linearity has been attributed to incompatibility in conformity with the earlier findings. This behavior was confirmed by Viscometric and interaction parameters studies, as well as by investigation of Refractive index studies. These investigations offer an entirely new and simple approach to the study of the compatibility of polymer blends which is in general obtained by sophisticated techniques of thermal dynamic mechanical and electron microscopic analysis.

  3. Steryl and stanyl esters of fatty acids by solvent-free esterification and transesterification in vacuo using lipases from Rhizomucor miehei, Candida antarctica, and Carica papaya.

    Science.gov (United States)

    Weber, N; Weitkamp, P; Mukherjee, K D

    2001-11-01

    Sitostanol has been converted in high to near-quantitative extent to the corresponding long-chain acyl esters via esterification with oleic acid or transesterification with methyl oleate or trioleoylglycerol using immobilized lipases from Rhizomucor miehei (Lipozyme IM) and Candida antarctica (lipase B, Novozym 435) as biocatalysts in vacuo (20-40 mbar) at 80 degrees C, whereas the conversion was markedly lower at 60 and 40 degrees C. Corresponding conversions observed with papaya (Carica papaya) latex lipase were generally lower. High conversion rates observed in transesterification of sitostanol with methyl oleate at 80 degrees C using Lipozyme IM were retained even after 10 repeated uses of the biocatalyst. Saturated sterols such as sitostanol and 5alpha-cholestan-3beta-ol were the preferred substrates as compared to Delta(5)-unsaturated cholesterol in transesterification reactions with methyl oleate using Lipozyme IM. Transesterification of cholesterol with dimethyl 1,8-octanedioate using Lipozyme IM in vacuo yielded methylcholesteryl 1,8-octanedioate (75%) and dicholesteryl 1,8-octanedioate (5%). However, transesterification of cholesterol with diethyl carbonate and that of oleyl alcohol with ethylcholesteryl carbonate, both catalyzed by Lipozyme IM, gave ethylcholesteryl carbonate and oleylcholesteryl carbonate, respectively, in low yield (20%). Moreover, cholesterol was transesterified with ethyl dihydrocinnamate using Lipozyme IM to give cholesteryl dihydrocinnamate in moderate yield (56%), whereas the corresponding reaction of lanosterol gave lanosteryl oleate in low yield (14%).

  4. Solubility of PdI/sub 2/ in nitrate and perchlorate solutions. [For use in spent fuels processing; solvents are water, nitric acid, calcium nitrate, and sodium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Horner, D.E.; Mailen, J.C.; Bigelow, H.R.

    1976-01-01

    This paper reports the solubilities of PdI/sub 2/ as measured in nitric acid by a tracer technique and in water, calcium nitrate, and sodium perchlorate solutions by a specific ion electrode technique. The tracer technique measures all the soluble iodine species, whereas the specific ion electrode measures only simple iodide ions (I/sup -/). When compared on the basis of ionic strength, the values obtained in the nitrate solutions by the two methods were in reasonable agreement. The solubilities in perchlorate solution were much higher than in nitrate, possibly because of ionic equilibria involving Pd/sup 4 +/, but this was not resolved in this work. The activity product constant, K/sub ap(PdI/sub 2/)/ = (2.5 +- 0.4) x 10/sup -23/ (25/sup 0/C), was calculated from PdI/sub 2/ solubility in water. With this value and the standard electrode potentials from the literature, the free energy of formation for PdI/sub 2/ was calculated to be --13.6 kcal/mol.

  5. Influence of solvent composition on the solid phase at equilibrium with saturated solutions of quinolones in different solvent mixtures.

    Science.gov (United States)

    Romero, Susana; Bustamante, Pilar; Escalera, Begoña; Mura, Paola; Cirri, Marzia

    2004-06-29

    The dissolution profiles and solubilities of three quinolonic drugs (oxolinic, pipemidic, and nalidixic acids) in different solvent mixtures were studied. The behavior of the solid phase, during solubility experiments was in-depth investigated with the aim of detecting possible crystalline modifications, such as polymorphic transitions or solvate formations, that might modify drug stability and/or solubility properties. In order to test the influence of both the nature and polarity of the co-solvents, aqueous and non-aqueous binary mixtures have been prepared by using Lewis base (dioxane and ethyl acetate) and amphiprotic co-solvents (ethanol and water). Differential scanning calorimetry (DSC), hot stage microscopy, IR spectroscopy and X-ray powder diffraction were used in combination with solubility and dissolution studies to characterize and investigate the solid state properties of the original powders and the corresponding ones at equilibrium with the different pure solvents and solvent mixtures examined. The solid phases of nalidixic and oxolinic acids did not show any change after equilibration with the various pure solvents or binary solvent mixtures, regardless the chemical nature of the examined solvents. On the contrary, in the case of pipemidic acid, the different analytical techniques used to characterize the drug solid state enabled identification of a solvated form at equilibrium with pure dioxane and a trihydrated form in aqueous mixtures of water with both ethanol (amphiprotic) or dioxane (Lewis base) in a concentration range from 10 to 100% water. Copyright 2004 Elsevier B.V.

  6. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    COWLEY, W.L.

    1999-05-13

    This report provides the basis for closing the organic solvent safety issue. Sufficient information is presented to conclude that risk posed by an organic solvent fire is within risk evaluation guidelines. This report updates information contained in Analysis of Consequences of Postulated Solvent Fires in Hanford Site Waste Tanks. WHC-SD-WM-CN-032. Rev. 0A (Cowley et al. 1996). However, this document will not replace Cowley et al (1996) as the primary reference for the Basis for Interim Operation (BIO) until the recently submitted BIO amendment (Hanson 1999) is approved by the US Department of Energy. This conclusion depends on the use of controls for preventing vehicle fuel fires and for limiting the use of flame cutting in areas where hot metal can fall on the waste surface.The required controls are given in the Tank Waste Remediation System Technical Safety Requirements (Noorani 1997b). This is a significant change from the conclusions presented in Revision 0 of this report. Revision 0 of this calcnote concluded that some organic solvent fire scenarios exceeded risk evaluation guidelines, even with controls imposed.

  7. Organic solvent topical report

    Energy Technology Data Exchange (ETDEWEB)

    Cowley, W.L.

    1998-04-30

    This report is the technical basis for the accident and consequence analyses used in the Hanford Tank Farms Basis for Interim Operation. The report also contains the scientific and engineering information and reference material needed to understand the organic solvent safety issue. This report includes comments received from the Chemical Reactions Subcommittee of the Tank Advisory Panel.

  8. Otoneurologic disturbances caused by solvent pollution.

    Science.gov (United States)

    Odkvist, L M; Möller, C; Thuomas, K A

    1992-06-01

    Subjects exposed to industrial solvents may experience vertigo and nausea. Solvents are usually volatile hydrocarbon compounds, which are important parts of everyday life in a modern society. They may also cause neurastenia, personality changes, and reduced intellectual capacity. The syndrome that may develop was formerly named psycho-organic syndrome (POS), but in modern terminology it is called chronic toxic encephalopathy (CTE). The syndrome develops slowly, and during the first years no pathological findings will be found using various test batteries. Somewhat later, when the syndrome still might be reversible, psychometric, auditory, and otoneurologic testing may well unveil disturbances within the posterior fossa structures. Animal experiments suggest one site of effect for solvents to be within the cerebellum and brainstem regions with close relationship to the gamma-amino-butyric acid (GABA) transmission. In the otoneurologic test battery, visual suppression and smooth pursuit are of extreme value, as are some auditory tests such as discrimination of interrupted speech and cortical response audiometry using frequency glides as stimuli. Dynamic posturography and magnetic resonance imaging (MRI) have recently proved valuable in the diagnosis. Research is needed concerning the most efficient test battery for early detection of solvent-induced lesions. During further research it is important to unveil other toxic agents, like heavy metals and alcohol, and their damage to the central nervous system and to make comparisons between these substances and the lesions caused by hydrocarbon solvents.

  9. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    Science.gov (United States)

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively.

  10. Study on Accelerated Solvent Extraction of Free Fatty Acids in Marine Sediments%加速溶剂萃取技术提取海洋沉积物中游离态脂肪酸的方法研究

    Institute of Scientific and Technical Information of China (English)

    李小琳; 贺行良; 李凤; 张媛媛; 陈立雷; 张培玉

    2014-01-01

    脂肪酸是沉积物中含量最丰富的脂类标记物之一,其存在形式主要有游离态脂肪酸和结合态脂肪酸。游离态脂肪酸可由溶剂直接提取,结合态脂肪酸是在已提取出游离态脂肪酸的沉积物残渣中加入酸碱加热后再用溶剂提取。加速溶剂萃取技术(ASE )因成本低和操作毒性小,在脂肪酸研究中得到了广泛的应用。本文采集东海近海海域沉积物作为研究样本,由于其中游离态脂肪酸含量丰富,而结合态脂肪酸含量过低,测定结果精密度差,难以作为方法研究对象,因此主要针对游离态脂肪酸应用ASE 法进行提取,研究了各种实验条件,包括萃取剂、萃取温度、静态萃取时间和循环次数的选择与优化。分析结果表明,甲醇-二氯甲烷(V/V,1∶3)更适合作为萃取剂;随着萃取温度、静态萃取时间、循环次数的增加,不同类型脂肪酸的提取效率各不相同,以涵盖碳原子数最多为先决条件,以脂肪酸的萃取效率最大化为依据,确定了ASE的实验条件是:萃取温度110℃,静态提取时间10 min,循环3次。用这种处理方法5次测定沉积物样品中大部分游离态脂肪酸的精密度为3.3%~19.0%,其替代物回收率为72.2%~104.6%。该方法应用于分析实际海洋沉积物样品,相比于传统的索氏提取法,流程简单,极大地提高了工作效率。%Fatty acids are one of the most abundant lipid markers in marine sediments,whose primary occurrence forms are free fatty acids and conjugated fatty acid.Free fatty acid can be extracted directly by solvent,and conjugated fatty acid is extracted from leftover sediment residue after free fatty acid has been extracted,through adding acid or alkali,and then extracting after being heated.Accelerated Solven Extraction (ASE)is a very popular method in the study of fatty acids due to its low cost and low toxicity

  11. Determination of residual organic solvent acetic acid in Omeprazole Magnesium by HPLC%HPLC 法测定奥美拉唑镁原料药中醋酸的残留量

    Institute of Scientific and Technical Information of China (English)

    李菊平; 刘效平; 金永亮

    2015-01-01

    目的:建立高效液相色谱法测定奥美拉唑镁原料药中有机溶剂醋酸含量。方法以色谱柱:以 X -Bridge TM C18(4.6 mm ×250 mm,5μm)为分离柱,采用等度洗脱,检测波长:210 nm。结果线性关系良好,方法精密度,重复性均符合要求。冰醋酸检测浓度线性范围为0.01~0.06 mg·mL -1(r =0.999994),低、中、高浓度平均回收率(n =9)分别为100.60%、100.38%、100.23%,RSD 分别为2.20%、2.21%、1.60%,最低检测限为0.0050 mg·mL -1。结论该方法可用于奥美拉唑镁原料药中残留溶剂醋酸含量的测定,限度为不得过0.05%(500 ppm)。%Objective To establish a method for the determination of residual acetic acid in Omeprazole Magnesium by HPLC Methods The X - Bridge TM C18(4. 6 mm × 250 mm,5 μm)column was adopted,temperature programming and FID detector was used. Results The solvent had good linear relationship and the precision and reproducibility of the meth-od were in accord with the requests. The linear range of acetic acid was 0. 01 ~ 0. 06 mg·mL - 1(r = 0. 999 994);The aver-age recovery rates of low,middle,high concentration(n = 9)were 100. 60% ,100. 38% ,100. 23% ,respectively and the RSDs were 2. 20% ,2. 21% ,1. 60% ,respectively;LOD was 0. 005 0 mg·mL - 1 . Conclusion This method could be used to determine residual acetic acid in Omeprazole Magnesium. The limit was not more than 0. 05%(500 ppm).

  12. 氯化胆碱/草酸型低共熔溶剂氧化脱除模拟油硫化物%Oxidative desulfurization of model oil with choline chloride/oxalic acid as a eutectic solvent

    Institute of Scientific and Technical Information of China (English)

    李佳慧; 胡嘉; 赵荣祥; 乔海燕; 李秀萍

    2014-01-01

    通过氯化胆碱和草酸在100℃下搅拌,合成了氯化胆碱/草酸型低共熔溶剂。以氯化胆碱/草酸为催化剂、过氧化氢为氧化剂、咪唑氟硼酸盐离子液体为萃取剂氧化萃取一体法脱除模拟油中的二苯并噻吩(DBT)。考察了反应温度、反应时间、氧化剂加入量、萃取剂类型、硫化物类型等因素对脱硫效率的影响。结果表明,当以咪唑氟硼酸盐为萃取剂,n(H2 O2)/n(S)=8、反应温度30℃、反应80 min 时,二苯并噻吩的脱除率可以达到95%。催化剂重复使用5次后,脱硫率仍然保持在90%。%Choline chloride / oxalic acid as a eutectic solvent was synthesized by the reaction of choline chloridewith oxalic acid at 100 ℃ via simple stirring. The removal of dibenzothiophene (DBT) in model oil was carried out by using choline chloride / oxalic acid as a catalyst, hydrogen peroxide as oxidant, imidazoliumtetrafluoroborate ionic liquid as extractant; the influence of reaction temperature and time, the amount of hydrogen peroxide, the type of extractant, the type of sulfur-containing compound ( thiophene and itshomologues ) on the desulfurization efficiency were investigated. The results indicated that under the optimal reaction conditions of n ( H2 O2 ) / n ( S ) = 8, reaction temperature of 30 ℃ and time of 80 min, thedesulfurization efficiency for DBT reaches without a significant decrease in the desulfurization activity. 95% . Moreover, the reaction system can be recycled for 5 times.

  13. Solvent Immersion Imprint Lithography

    Energy Technology Data Exchange (ETDEWEB)

    Vasdekis, Andreas E.; Wilkins, Michael J.; Grate, Jay W.; Kelly, Ryan T.; Konopka, Allan; Xantheas, Sotiris S.; Chang, M. T.

    2014-06-21

    The mechanism of polymer disolution was explored for polymer microsystem prototyping, including microfluidics and optofluidics. Polymer films are immersed in a solvent, imprinted and finally brought into contact with a non-modified surface to permanently bond. The underlying polymer-solvent interactions were experimentally and theoretically investigated, and enabled rapid polymer microsystem prototyping. During imprinting, small molecule integration in the molded surfaces was feasible, a principle applied to oxygen sensing. Polystyrene (PS) was employed for microbiological studies at extreme environmental conditions. The thermophile anaerobe Clostridium Thermocellum was grown in PS pore-scale micromodels, revealing a double mean generation lifetime than under ideal culture conditions. Microsystem prototyping through directed polymer dissolution is simple and accessible, while simultaneous patterning, bonding, and surface/volume functionalization are possible in less than one minute.

  14. Study of Recycling Solvent in Preparation of Polyhydroxyl Terephthalic Acid by Kolbe--Schmitt Reaction%Kolbe-Schmitt制备多羟基对苯二甲酸类化合物中甲酸钾的回收利用研究

    Institute of Scientific and Technical Information of China (English)

    王坤; 王建超; 吴狄

    2012-01-01

    阐述了Kolbe--Schmitt反应的原理、常见反应条件,以及甲酸钾废液对环境的危害。结合实验,指出了研究甲酸钾废液的回收利用是实现绿色化工业生产的重要途径。%This paper analyses the principle and reaction conditions of Kolbe--Schmitt Reaction, and the haz- ards of waste solvent of formic acid potassium on the environment. Combined with the experiments, the paper points out that recycling waste solvent of formic acid potassium is important to achieve a green revolution of industrial production.

  15. The role of the resid solvent in coprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W. [Auburn Univ., AL (United States)

    1995-12-31

    The objective of this project is to determine the role of petroleum resid in coprocessing of coal and resid. The question being asked is whether the resid is a reactant in the system or whether the resid is a merely a diluent that is being simultaneously upgraded? To fulfill the objective the hydrogen transfer from model compounds, naphthenes that represent petroleum resids to model acceptors is being determined. The specificity of different catalytic systems for promoting the hydrogen transfer from naphthenes to model acceptors and to coal is also being determined. In addition the efficacy of hydrogen transfer from and solvancy of whole and specific resid fractions under coprocessing conditions is being determined.

  16. Preparation and in vitro characterization of vascular endothelial growth factor (VEGF)-loaded poly(D,L-lactic-co-glycolic acid) microspheres using a double emulsion/solvent evaporation technique.

    Science.gov (United States)

    Karal-Yılmaz, Okşan; Serhatlı, Müge; Baysal, Kemal; Baysal, Bahattin M

    2011-01-01

    Biodegradable Poly(lactic-co-glycolic acid; PLGA), microspheres encapsulating the angiogenic protein recombinant human vascular endothelial growth factor (rhVEGF) were formed to achieve VEGF release in a sustained manner. These microspheres are a promising delivery system which can be used for therapeutic angiogenesis. The PLGA microspheres incorporating two different initial loading amounts of rhVEGF have been prepared by a modified water-in-oil-in-water (w/o/w) double emulsion/solvent evaporation technique. The microspheres have been characterized by particle size distribution, environmental scanning electron microscopy (ESEM), light microscopy, encapsulation efficiency and their degradation was studied in vitro. The rhVEGF released from microspheres was quantified by the competitive enzyme-linked immunosorbent assay (ELISA) and human umbilical vein endothelial cell (HUVEC) proliferation assay was used to assess biological activity of the released VEGF. The microspheres were spherical with diameters of 10-60 µm and the encapsulation efficiency was between 46% and 60%. The release kinetics of rhVEGF was studied for two different amounts: 5 µg VEGF (V5) and 50 µg VEGF (V50) per 500 mg starting polymer. The total protein (VEGF:BSA) release increased up to 4 weeks for two rhVEGF concentrations. The ELISA results showed that the burst release for V5 and V50 microspheres were 4 and 27 ng/mL, respectively. For V5, the microspheres showed an initial burst release, followed by a higher steady-state release until 14 days. VEGF release increased up to 2 weeks for V50 microsphere. HUVEC proliferation assay showed that endothelial cells responded to bioactive VEGF by proliferating and migrating.

  17. Enzymatic synthesis of structured lipid containing conjugated linoleic acid in a solvent-free system%无溶剂体系酶法催化酸解合成共轭亚油酸甘油酯

    Institute of Scientific and Technical Information of China (English)

    惠菊; 单良; 金青哲; 刘元法; 王兴国

    2009-01-01

    A structured lipid (SL) containing conjugated linoleic acid (CLA) was prepared using immobilized lipase(Novozym 435)-catalyzed acidolysis of sunflower seed oil with CLA. The acidolysis reaction was carried out in a solvent-free system. The effects on incorporation of CLA, and the CLA content in Sn-2 position of water content, molar ratio of substrates, enzyme dosage, reaction temperature, and reaction time were evaluated.The results showed that the optimal reaction conditions were as follows:molar ratio of CLA to sunflower seed oil 3 ∶1,enzyme dosage 10%,water content in the system 1%,reaction temperature 55 ℃,reaction time 36 h.Under the optimal condtions,the CLA content and the Sn-2 position CLA content in the finished product were 15.7% and 2.73%,respectively.%采用商业化固定化酶Novozym 435作为生物催化剂,催化共轭亚油酸(CLA)和葵花籽油的酸解反应合成富含CLA的结构脂质(CLA-SL).研究了在无溶剂体系中,底物摩尔比、酶用量、体系含水量、反应温度和反应时间对产物中CLA含量和Sn-2位CLA含量的影响.结果表明,最佳反应条件为:CLA与葵花籽油摩尔比3 :1,酶用量10%,体系含水量1%,反应温度55 ℃,反应时间36 h.在最佳反应条件下,产物中的CLA含量和Sn-2位CLA含量分别为15.7%和2.73%.

  18. CO2捕集溶剂氨基酸的反应活性与机制探讨%Reactivity and Mechanism Study of CO2 With Amino Acids as Carbon Capture Solvents

    Institute of Scientific and Technical Information of China (English)

    郭东方; 王金意; Gabriel da Silva; 郜时旺

    2013-01-01

    Amino acids are potentially attractive solvents for carbon dioxide capture from coal-based power stations, and present certain benefits over amines in CO2 separation systems, such as low toxicity, low volatility and high resistance to oxidative degradation. This paper carried out a study of CO2 reacting with glycine in aqueous media using stopped-flow pH indicator technique. The results show that the reactivity of neutral form is much less than that of base form. Density functional theory calculations at the M062X/6-31G(2df,p) level of theory demonstrate that reactivity of the neutral form is diminished by the thermodynamic instability of the zwitterion reaction product, as opposed to any raising of the intrinsic reaction barrier.%氨基酸盐是一种很具潜力的 CO2捕集分离溶剂,相对于乙醇胺等有机胺类吸收剂,具有低挥发性、抗氧化降解等优点。文中采用停流光谱-pH指示剂技术研究氨基乙酸与CO2的反应行为,表明其中性形式的反应活性远低于碱性形式。M062X/6-31G(2df,p)级别的密度泛函理论的计算表明氨基乙酸中性形式与 CO2的反应能垒较高,其两性离子产物的热力学不稳定性也导致反应活性降低。

  19. Occupational solvent exposure and cognition

    Science.gov (United States)

    Sabbath, E.L.; Glymour, M.M.; Berr, C.; Singh-Manoux, A.; Zins, M.; Goldberg, M.

    2012-01-01

    Objective: Chronic occupational solvent exposure is associated with long-term cognitive deficits. Cognitive reserve may protect solvent-exposed workers from cognitive impairment. We tested whether the association between chronic solvent exposure and cognition varied by educational attainment, a proxy for cognitive reserve. Methods: Data were drawn from a prospective cohort of French national gas and electricity (GAZEL) employees (n = 4,134). Lifetime exposure to 4 solvent types (chlorinated solvents, petroleum solvents, benzene, and nonbenzene aromatic solvents) was assessed using a validated job-exposure matrix. Education was dichotomized at less than secondary school or below. Cognitive impairment was defined as scoring below the 25th percentile on the Digit Symbol Substitution Test at mean age 59 (SD 2.8; 88% of participants were retired at testing). Log-binomial regression was used to model risk ratios (RRs) for poor cognition as predicted by solvent exposure, stratified by education and adjusted for sociodemographic and behavioral factors. Results: Solvent exposure rates were higher among less-educated patients. Within this group, there was a dose-response relationship between lifetime exposure to each solvent type and RR for poor cognition (e.g., for high exposure to benzene, RR = 1.24, 95% confidence interval 1.09–1.41), with significant linear trends (p < 0.05) in 3 out of 4 solvent types. Recency of solvent exposure also predicted worse cognition among less-educated patients. Among those with secondary education or higher, there was no significant or near-significant relationship between any quantification of solvent exposure and cognition. Conclusions: Solvent exposure is associated with poor cognition only among less-educated individuals. Higher cognitive reserve in the more-educated group may explain this finding. PMID:22641403

  20. Solvent effects in chemistry

    CERN Document Server

    Buncel, Erwin

    2015-01-01

    This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds.  It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as ""green"" chemistry, where ut

  1. Solvent Retention Capacities of Oat Flour

    Directory of Open Access Journals (Sweden)

    Qianwen Niu

    2017-03-01

    Full Text Available This study measured the solvent retention capacities (SRCs of flours from eight oat varieties and one wheat variety against different solvents to explore the swelling volume of oat flour with different solvents, and thus provide a theoretical basis for quick β-glucan analysis. The SRC profile consists of water SRC (WSRC, 50% sucrose SRC (SSRC, 5% lactic acid SRC (LASRC, 5% Na2CO3 SRC (SCASRC, NaCl SRC (SCSRC, CaCl2 SRC (CCSRC, FeCl3 SRC (FCSRC, sodium cholate SRC (SCHSRC, NaOH (pH 10 SRC (SHSRC, Na2CO3 (pH 10 SRC (SCABSRC and SDS (pH 10 SRC (SDSSRC values, and a Chopin SRC kit was used to measure the SRC value. SRCs of the oat flours increased when the solvents turned from neutral (water and NaCl to acidic (5% lactic acid or alkaline (5% Na2CO3, CaCl2, FeCl3, NaOH and pH 10 Na2CO3, and rose as the metal ion valencies of the metal salts (NaCl, CaCl2 and FeCl3 increased. The β-glucan contents were significantly positively correlated with the SCSRC (0.83**, CCSRC (0.82**, SCHSRC (0.80** and FCSRC (0.78*. SRC measurements of β-glucan in oat flours revealed that the CCSRC values were related with β-glucan (0.64* but not related with protein and starch. CaCl2 could therefore potentially be exploited as a reagent for β-glucan assay.

  2. Solvent Retention Capacities of Oat Flour

    Science.gov (United States)

    Niu, Qianwen; Pu, Yu; Li, Xiaoping; Ma, Zhen; Hu, Xinzhong

    2017-01-01

    This study measured the solvent retention capacities (SRCs) of flours from eight oat varieties and one wheat variety against different solvents to explore the swelling volume of oat flour with different solvents, and thus provide a theoretical basis for quick β-glucan analysis. The SRC profile consists of water SRC (WSRC), 50% sucrose SRC (SSRC), 5% lactic acid SRC (LASRC), 5% Na2CO3 SRC (SCASRC), NaCl SRC (SCSRC), CaCl2 SRC (CCSRC), FeCl3 SRC (FCSRC), sodium cholate SRC (SCHSRC), NaOH (pH 10) SRC (SHSRC), Na2CO3 (pH 10) SRC (SCABSRC) and SDS (pH 10) SRC (SDSSRC) values, and a Chopin SRC kit was used to measure the SRC value. SRCs of the oat flours increased when the solvents turned from neutral (water and NaCl) to acidic (5% lactic acid) or alkaline (5% Na2CO3, CaCl2, FeCl3, NaOH and pH 10 Na2CO3), and rose as the metal ion valencies of the metal salts (NaCl, CaCl2 and FeCl3) increased. The β-glucan contents were significantly positively correlated with the SCSRC (0.83**), CCSRC (0.82**), SCHSRC (0.80**) and FCSRC (0.78*). SRC measurements of β-glucan in oat flours revealed that the CCSRC values were related with β-glucan (0.64*) but not related with protein and starch. CaCl2 could therefore potentially be exploited as a reagent for β-glucan assay. PMID:28335393

  3. Photochromic Properties of 3-Deoxyanthocyanidin Pigments in Nontoxic Solvents.

    Science.gov (United States)

    Yagishita, Yuki; Mihara, Mai; Kohno, Yoshiumi; Shibata, Masashi

    2016-12-01

    The photochromic properties of some naturally occurring 3-deoxyanthocyanidin pigments were investigated in various nontoxic solvents. When luteolinidin, a representative 3-deoxyanthocyanidin, was dissolved in a mixture of weakly acidic water and an organic solvent with a relative permittivity between 20 and 34, it was possible to repeatedly induce coloration via ultraviolet irradiation and decoloration under light-shielded conditions. 1,3-Butanediol and ethanol, which are approved for use in foods, cosmetics, and household goods, were found to be appropriate organic solvents for this process. In addition, we confirmed that other 3-deoxyanthocyanidins, specifically apigeninidin and tricetinidin, which are commonly found in food grains and tea leaves, also exhibit photochromic properties.

  4. Alternatives to Organic Solvents in Industrial Cleaning Processes

    DEFF Research Database (Denmark)

    Jacobsen, Thomas

    1998-01-01

    cleaning agents in offset printing companies instead of volatile, toxic organic solvents. The present study is based on a project with the aim of defining other industrial processes, where organic solvents used for cleaning or degreasing can be replaced by non-volatile, low-toxic products, which are based...... on esters from fatty acids of vegetable origin (vegetable esters - VE).The study indicates that industrial cleaning/degreasing with organic solvents may be substituted with VEs on metal surfaces and on some coated surfaces, in manufacture of paints and inks, use of paints, use of inks (printing), metal...

  5. In-line monitoring of solvent and CO2 properties: preliminary assessment using design of experiment

    NARCIS (Netherlands)

    Ham, L.V. van der; Bakker, D.E.; Geers, L.F.G. van; Eckeveld, A.C. van; Goetheer. E.L.V.

    2013-01-01

    Removing acid gases such as CO2 and H2S from a gas mixture is nowadays often done using an absorption process. Two essential operating variables of such a process are the amount of active absorbent present in the solvent mixture and the amount of absorbed acid gas. Normally, the solvent concentratio

  6. The solvent absorption-extractive distillation (SAED) process for ethanol recovery from gas/vapor streams

    Energy Technology Data Exchange (ETDEWEB)

    Dale, M.C.

    1993-12-31

    A low energy system for ethanol recovery and dehydration has been developed. This system utilizes a solvent for (1) absorption of ethanol vapors, and then the same solvent for (2) extractive distillation. The ideal solvent for this process would have a high affinity for ethanol, and no affinity for water. Heavy alcohols such as dodecanol, and tridecanol, some phosphorals, and some fatty acids have been determined to meet the desired specifications. These solvents have the effect of making water more volatile than ethanol. Thus, a water stream is taken off initially in the dehydration column, and a near anhydrous ethanol stream is recovered from the ethanol/solvent stripper column. Thus the solvent serves dual uses (1) absorption media, and (2) dehydration media. The SAED process as conceptualized would use a solvent similar to solvents used for direct extractive separation of ethanol from aqueous ethanol solutions.

  7. Molecular and ionic hydrogen bond formation in fluorous solvents.

    Science.gov (United States)

    O'Neal, Kristi L; Weber, Stephen G

    2009-01-08

    There are only a few studies of noncovalent association in fluorous solvents and even fewer that are quantitative. A full understanding, particularly of stoichiometry and binding strength of noncovalent interactions in fluorous solvents could be very useful in improved molecular-receptor-based extractions, advancements in sensor technologies, crystal engineering, and supramolecular chemistry. This work investigates hydrogen bonding between heterocyclic bases and a perfluoropolyether with a terminal carboxylic acid group (Krytox 157FSH (1)), chiefly in FC-72 (a mixture of perfluorohexanes). In particular, we were interested in whether or not proton transfer occurs, and if so, under what conditions in H-bonded complexes. Continuous variations experiments show that in FC-72 weaker bases (pyrazine, pyrimidine, and quinazoline) form 1:1 complexes with 1, whereas stronger bases (quinoline, pyridine, and isoquinoline) form 1:3 complexes. Ultraviolet and infrared spectral signatures reveal that the 1:1 complexes are molecular (B.HA) whereas the 1:3 complexes are ionic (BH+.A-HAHA). Infrared spectra of 1:3 ionic complexes are discussed in detail. Literature and experimental data on complexes between N-heterocyclic bases and carboxylic acids in a range of solvents are compiled to compare solvent effects on proton transfer. Polar solvents support ionic hydrogen bonds at a 1:1 mol ratio. In nonpolar organic solvents, ionic hydrogen bonds are only observed in complexes with 1:2 (base/acid) stoichiometries. In fluorous solvents, a larger excess of acid, 1:3, is necessary to facilitate proton transfer in hydrogen bonds between carboxylic acids and the bases studied.

  8. 全水化无醇提取γ-聚谷氨酸工艺的研究%Study on the separation and purification of poly-γ-glutamtic acid without any organic solvents

    Institute of Scientific and Technical Information of China (English)

    乔长晟; 张苗苗; 刘晓晨; 高明昊; 林虹秀; 楼鹏

    2015-01-01

    For separating γ-PGA without any alcohol,a extractive method was developed to separate and purify γ-PGA from culture broth.The culture broth was filtrated with diatomite to remove cells,and the macromolecular polysaccharide was catabolized by enzymolysis.Then,active carbon was added as decoloring agent and the small molecular weight impurity was removed by ultrafiltration.Finally,purified γ-PGA was obtained by lyophilization.The optimum quantity of using mixed diatomite loading(ratio of coarse to small diatomite 2∶1)was 1.5% (w/v)and over 97% of cells were removed from γ-PGA broth.The optimum conditions of decoloration were as follows:the addition of active carbon 1.5% (w/v),temperature 30℃,pH5,processing time 60min.The optimum membrane module of ultrafiltration was 10ku and the concentration rate of ultrafiltration was 9 ∶ 1.The purity of γ-PGA was 90% after lyophilization for 18h.The study of separation and purification of poly-γ-glutamtic acid without any organic solvents was imperative and it provided an important basis for Industrial production of γ-PGA.%为实现γ-聚谷氨酸无醇提取,利用板框除菌,酶解除大分子多糖,活性炭脱色,超滤除小分子杂质,最后冷冻干燥获得γ-聚谷氨酸(γ-PGA)成品.确定了全水化无醇提取条件:下罐调pH6.0,发酵液稀释2倍;硅藻土和红土配比为2∶1(m∶m),总添加量为1.5% (w/v),除菌率97%以上;脱色条件:活性炭添加量1.5% (w/v)、温度30℃、pH5、时间60min.超滤选择10ku的膜包除杂并最终浓缩至原液的1/9.冷冻干燥18h得到的γ-聚谷氨酸纯度达90%.无醇提取工艺的探索为工业生产提取γ-PGA提供了重要参考依据.

  9. TODGA Process Development: an Improved Solvent Formulation

    Energy Technology Data Exchange (ETDEWEB)

    Geist, Andreas [Forschungszentrum Karlsruhe, Institut fuer Nukleare Entsorgung, 76021 Karlsruhe (Germany); Modolo, Giuseppe [Forschungszentrum Juelich, Institute for Energy Research, Safety Research and Reactor Technology, 52425 Juelich (Germany)

    2009-06-15

    Introduction: TODGA (N,N,N',N'-tetra-n-octyl diglycolamide) is studied in the European ACSEPT project as a promising extractant for actinide separations. A mixture of TODGA and TBP in TPH (a kerosene) [1] was successfully used for spiked and hot continuous counter-current tests for the separation of actinides(III) and lanthanides(III) from PUREX raffinate [2, 3]. Furthermore this solvent composition is used for GANEX (group actinide extraction) process development, i.e., co-extraction of Np, Pu, Am, Cm, and Ln from PUREX raffinate with selective stripping of the actinides [4, 5]. We address two of this solvent's drawbacks by replacing TBP (which acts as phase modifier to prevent third phase formation) with 1-octanol: (1) The presence of a non-CHON compound (TBP); (2) The pronounced co-extraction of nitric acid (e.g., 0.2 M TODGA + 0.5 M TBP in TPH extracts approx. 0.6 M HNO{sub 3} from 4 M HNO{sub 3}). Results: When contacting 0.2 M TODGA in TPH with 0.1 M Nd(NO{sub 3}){sub 3} in 5 M HNO{sub 3}, as little as 3 % vol. 1-octanol suppresses the formation of a third phase. Thus, the following solvent composition is used for further studies: 0.2 M TODGA + 5 % vol. 1-octanol in TPH. Due to the absence of TBP, the amount of HNO{sub 3} extraction is reduced to approx. 50 % as compared to the solvent consisting of 0.2 M TODGA + 0.5 M TBP in TPH. Am(III) and Eu(III) distribution ratios are similar to those with the TODGA + TBP solvent [1]. Loading the solvent by extracting from solutions of up to 0.2 M Nd(NO{sub 3}){sub 3} in 3 M or 4 M HNO{sub 3} confirms a 1:3 stoichiometry of the extracted complex. Further investigations are under way. Conclusion: The improved solvent formulation reduces the HNO{sub 3} co-extraction which may be advantageous especially for GANEX process development. Furthermore, the solvent complies with the CHON principle. 1) G. Modolo, H. Asp, C. Schreinemachers, H. Vijgen, Development of a TODGA based process for partitioning of

  10. Molecular and supramolecular speciations of solvent extraction systems based on malonamide and/or dialkyl-phosphoric acids for An(III)/Ln(III); Speciations moleculaire et supramoleculaire de systemes d'extraction liquide-liquide a base de malonamide et/ou d'acides dialkylphosphoriques pour la separation An(III)/Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Gannaz, B

    2006-06-15

    The solvent extraction system used in the DIAMEX-SANEX process, developed for the actinide(III)/lanthanide(III) separation, is based on the use of mixtures of the malonamide DMDOHEMA and a dialkyl-phosphoric acid (HDEHP or HDHP), in hydrogenated tetra-propylene. The complexity of these systems urges on a novel approach to improve the conventional methods (thermodynamics, solvent extraction) which hardly explain the macroscopic behaviors observed (3. phase, over-stoichiometry). This approach combines studies on both supramolecular (VPO, SANS, SAXS) and molecular (liquid-liquid extraction, ESI-MS, IR, EXAFS) speciations of single extractant systems (DMDOHEMA or HDHP in in n-dodecane) and their mixture. In spite of safety constraints due to the handling of radio-material, they were used in the studies as much as possible, like for SAXS measurements on americium-containing samples, a worldwide first-time. In each of the investigated systems, actinides(III) and lanthanides(III) are extracted to the organic phase in polar cores of reversed micelles, the inner and outer-sphere compositions of which are proposed. Thus, the 4f and 5f cations are extracted by reversed micelles such as [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3}]{sub inn} (DMDOHEMA){sub x}(HNO{sub 3}){sub z}(H{sub 2}O){sub w}]{sub out} and M(DHP){sub 3}(HDHP){sub y-3}(H{sub 2}O){sub w} with y = 3 to 6, for the single extractant systems. In the case of the two extractants system, the less concentrated one acts like a co-surfactant regarding the mixed aggregate formation [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3-v}(DHP){sub v}]{sub inn} [(DMDOFIEMA){sub x}(HDHP){sub y}(HNO{sub 3})z(H{sub 2}O){sub w}]{sub out}. (author)

  11. Lewis acidic (choline chloride.3ZnCl2) ionic liquid: A green and recyclable catalyst for the one-pot synthesis of 4-((3-indolyl)(aryl)methyl)-N,N-dimethylanilines under solvent-free conditions

    Indian Academy of Sciences (India)

    Rahim Hekmatshoar; Farnoush Mousavizadeh; Reyhaneh Rahnamafar

    2013-09-01

    A green and convenient procedure for the one-pot multicomponent synthesis of 4-((3-indolyl)(aryl)methyl)-N,N-dimethylanilines using (choline chloride.3ZnCl2) ionic liquid as catalyst, at 100°C and under solvent-free condition is described. Utilizing environmentally benign reagents, elimination of organic solvents, enhanced rates, reusability and moisture stability of the catalyst are the remarkable features observed in the reported reaction system. The catalyst was recycled up to four times with no noticeable drop in activity.

  12. SOLVENT QUALITY AND SOLUTION BEHAVIOR OF NYLON 12

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The refractive index increment,dynamic and static laser light scattering,intrinsic viscosity [η] and Huggins constant (KH) of nylon 12 have been measured in m-cresol and sulphuric acid/water system at 10-60 ℃.The intrinsic Vicosity,RH,Rg,A2,and (2)1/2 (calculated from vicosity data) and "a" values of nylon 12 are found to be higher in m-cresol than in sulphuric acid.All these parameters decrease with the increase in water contents in sulphuric acid.The refractive index increment,KH and activation energy show an opposite trend to that of [η].The intrinsic viscosity,RH,Rg,A2,20℃.It has been concluded that the variation in size,interaction parameter(second virial coefficient).[η] and KH of the polymer solutions with the alteration in solvent composition and temperature are the out come of change in thermodynamic quality of solvents,selective adsorption,hydrogen bonding and conformational transitions.It has also been concluded that the increase in temperature first enhances the quality of the solvent,encourages hydrogen bonding and specific adsorption,and then deteriorates.bringing conformational transitions in the polymer molecules.However,the addition of water to sulphuric acid continuously deteriorates the solvent quality.This characteristic of the solvent system brings conformational changes in the polymer especially at low temperatures.

  13. Supercritical multicomponent solvent coal extraction

    Science.gov (United States)

    Corcoran, W. H.; Fong, W. S.; Pichaichanarong, P.; Chan, P. C. F.; Lawson, D. D. (Inventor)

    1983-01-01

    The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal.

  14. Reactivity trends of hydroxide ion attack on high spin Fe(II complexes including bromosalicylidene amino acid ligands in some mixed aqueous solvents: Gibb’s Free Energy of Transfer and initial-transition state analysis

    Directory of Open Access Journals (Sweden)

    Laila H. Abdel-Rahman

    2017-05-01

    Full Text Available The kinetics of hydroxide ion attack on bis(bromosalicylidene alanateiron (II (bsali, bis(bromosalicylidene phenylalanateiron(II (bsphali, bis(bromosalicylidene aspartateiron(II (bsasi, (bromosalicylidene histidinateiron(II (bshi, bis(bromosalicylidene arginateiron(II (bsari have been reported in different binary aqueous solvent mixtures at 298 K. The observed reactivity trends are discussed in terms of the hydrophilic and hydrophobic forms of the complexes investigated, as well as the transfer chemical potentials of hydroxide ion and the complex. Both the solvent–solute and solvent–solvent interactions have been considered. The hydrophobic character of the complexes studied was manifested by decreasing in reactivity. Solvent effect on reactivity trends of the investigated complexes has been analyzed into initial and transition state components by using the transfer chemical potentials of the reactants and the kinetic data of the studied compounds. The decrease in the observed rate constant values (kobs of the base hydrolysis of the investigated complexes with increasing of solvent % is dominated by the initial state (IS.

  15. Selection and design of solvents

    DEFF Research Database (Denmark)

    Gani, Rafiqul

    . With increasing interest on issues such as waste, sustainability, environmental impact and green chemistry, the selection and design of solvents have become important problems that need to be addressed during chemical product-process design and development. Systematic methods and tools suitable for selection......Solvents are liquid solutions consisting of one or more chemicals. They have a very wide use and their use is not necessarily restricted to the process industries. This lecture will discuss the different roles and uses of solvents in chemical products and processes that manufacture them...... and design of solvents will be presented together with application examples. The selection problem is defined as finding known chemicals that match the desired functions of a solvent for a specified set of applications. The design problem is defined as finding the molecular structure (or mixture of molecules...

  16. Switchable Polarity Solvents: Are They Green?

    Science.gov (United States)

    Plaumann, Heinz

    2017-03-01

    Solvents play an incredibly important role in large scale chemical reactions. Switchable polarity solvents may prove to be a class of solvent that offers energy and material efficiencies greater than existing solvents. This paper examines such solvents and their potential in a variety of chemical reactions.

  17. PULSED MIXER-SETTLER SOLVENT EXTRACTION CONTACTORS

    Science.gov (United States)

    Figg, W.S.

    1958-08-12

    A mixer-settler extractor is described for contacting immiscible liquids having different specific gravities in order to withdraw one or more components from one liquid with the aid of the other liquid. The extractor consists of a hollow column, a rotary drive shafi extending : through the column with a number of impellers spaced thereon, an equal nunnber of separator plate sets each consisting of one fluorothene and one stainless steel plate with peripheral recesses and flow slots mounted on the column, and a pulse generator. This apparatus is particularly useful in solvent extraction processes for recovering plutonium from aqueous acidic solutions of irradiated uranium.

  18. Methods for recovering a polar solvent from a fluid stream contaminated with at least one polar impurity

    Science.gov (United States)

    Ginosar, Daniel M.; Wendt, Daniel S.

    2012-11-13

    A method of removing a polar solvent from a fluid volume contaminated with at least one polar impurity, such as a free fatty acid, is provided. The method comprises providing a fluid volume that includes at least one polar impurity dissolved in at least one solvent. The fluid volume is contacted with an expanding gas to remove the at least one solvent. The expanding gas may be dissolved into the at least one solvent in the fluid volume to form a gas-expanded solvent. The immiscibility of the polar impurities in the gas-expanded solvent enables separation of the polar impurities from the gas-expanded solvent. After separation of the polar impurities, at least one of the temperature and pressure may be reduced to separate the solvent from the expanding gas such that the clean solvent may be reused.

  19. Handbook of organic solvent properties

    CERN Document Server

    Smallwood, Ian

    2012-01-01

    The properties of 72 of the most commonly used solvents are given, tabulated in the most convenient way, making this book a joy for industrial chemists to use as a desk reference. The properties covered are those which answer the basic questions of: Will it do the job? Will it harm the user? Will it pollute the air? Is it easy to handle? Will it pollute the water? Can it be recovered or incinerated? These are all factors that need to be considered at the early stages of choosing a solvent for a new product or process.A collection of the physical properties of most commonly used solvents, their

  20. The Solvent Selection framework: solvents for organic synthesis, separation processes and ionic-organic synthesis

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Sansonetti, Sascha; Abildskov, Jens

    2012-01-01

    problems are presented: 1) solvent selection and design for organic synthesis, 2) solvent screening and design of solvent mixtures for pharmaceutical applications and 3) ionic liquids selection and design as solvents. The application of the framework is highlighted successfully through case studies...... focusing on solvent replacement problem in organic synthesis and solvent mixture design for ibuprofen respectively....