Olefin metathesis and metathesis polymerization

CERN Document Server

Ivin, K J

1997-01-01

This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

Catalytic olefin polymerization with early transition metal compounds

NARCIS (Netherlands)

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

Olefin copolymerization using atom transfer radical polymerization (ATRP)

NARCIS (Netherlands)

Venkatesh, R.; Klumperman, B.

2003-01-01

Olefin copolymers of alpha-olefins with polar monomers with various architectures remain an ultimate goal in polyolefin engineering. The present paper is a more detailed study on the copolymn. of alpha-olefins (1-octene) with acrylates (Me acrylate). Comparison of reaction kinetics between free

Improved olefinic fat suppression in skeletal muscle DTI using a magnitude-based dixon method.

Science.gov (United States)

Burakiewicz, Jedrzej; Hooijmans, Melissa T; Webb, Andrew G; Verschuuren, Jan J G M; Niks, Erik H; Kan, Hermien E

2018-01-01

To develop a method of suppressing the multi-resonance fat signal in diffusion-weighted imaging of skeletal muscle. This is particularly important when imaging patients with muscular dystrophies, a group of diseases which cause gradual replacement of muscle tissue by fat. The signal from the olefinic fat peak at 5.3 ppm can significantly confound diffusion-tensor imaging measurements. Dixon olefinic fat suppression (DOFS), a magnitude-based chemical-shift-based method of suppressing the olefinic peak, is proposed. It is verified in vivo by performing diffusion tensor imaging (DTI)-based quantification in the lower leg of seven healthy volunteers, and compared to two previously described fat-suppression techniques in regions with and without fat contamination. In the region without fat contamination, DOFS produces similar results to existing techniques, whereas in muscle contaminated by subcutaneous fat signal moved due to the chemical shift artefact, it consistently showed significantly higher (P = 0.018) mean diffusivity (MD). Because fat presence lowers MD, this suggests improved fat suppression. DOFS offers superior fat suppression and enhances quantitative measurements in the muscle in the presence of fat. DOFS is an alternative to spectral olefinic fat suppression. Magn Reson Med 79:152-159, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

Gamma radiolysis of 3-methylpentane. Effect of added olefins on the formation of C12-olefins

International Nuclear Information System (INIS)

Laet, M. de; Tilquin, B.

1991-01-01

Contributions of congruent (parent derived) olefins to the formation of unsaturated heavy products (C 12 H 24 ) are investigated. Effects of dose or of olefinic additives on the G yield values are studied by capillary gas chromatography. The dose dependence is explained by transfer of positive charge to congruent olefins (C 6 H 12 ) even though their concentrations build up linearly with dose. γ Irradiation of 3-methylpentane containing pentenes or butenes (0.2-2 mol %) provides good examples of transfer of energy, however the results are unexpected. C-H scission in the radiolysis of solid 3-methylpentane is also reviewed. (author)

Direct Wittig Olefination of Alcohols.

Science.gov (United States)

Li, Qiang-Qiang; Shah, Zaher; Qu, Jian-Ping; Kang, Yan-Biao

2018-01-05

A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination products. By the strategy of simultaneously in situ generation of ylides and aldehydes, for the first time, alcohols are directly transferred to olefins with no need of prepreparation of either aldehydes or ylides. Thus, the di/monocontrollable olefination of diols is accomplished. This synthetically practical method has been applied in the gram-scale synthesis of pharmaceuticals, such as DMU-212 and resveratrol from alcohols.

Hydride Olefin complexes of tantalum and niobium

NARCIS (Netherlands)

Klazinga, Aan Hendrik

1979-01-01

This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

Carbonyl-Olefin Exchange Reaction: Present State and Outlook

Science.gov (United States)

Kalinova, Radostina; Jossifov, Christo

The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

KAUST Repository

Riache, Nassima; Callens, Emmanuel; Espinas, Jeff; Dé ry, Alexandre; Samantaray, Manoja; Dey, Raju; Basset, Jean-Marie

2015-01-01

Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

Olefins-selective asymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations

KAUST Repository

Xu, Liren

2012-12-01

In this paper, the development of asymmetric carbon molecular sieve (CMS) hollow fiber membranes and advanced processes for olefin/paraffin separations based on the CMS membranes are reported. Membrane-based olefin/paraffin separations have been pursued extensively over the past decades. CMS membranes are promising to exceed the performance upper bound of polymer materials and have demonstrated excellent stability for gas separations. Previously, a substructure collapse phenomenon was found in Matrimid ® precursor derived CMS fiber. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM precursors were selected as potential new precursors for carbon membrane formation. Defect-free asymmetric 6FDA-DAM and 6FDA/BPDA-DAM hollow fibers were successfully fabricated from a dry-jet/wet-quench spinning process. Polymer rigidity, glass-rubber transition and asymmetric morphology were correlated. CMS hollow fiber membranes produced from 6FDA-polymer precursors showed significant improvement in permeance for ethylene/ethane and propylene/propane separations. Further studies revealed that the CMS membranes are olefins-selective, which means the membranes are able to effectively separate olefins (ethylene and propylene) from paraffins (ethane and propane). This unique feature of CMS materials enables advanced hybrid membrane-distillation process designs. By using the olefins-selective membranes, these new processes may provide advantages over previously proposed retrofitting concepts. Further applications of the membranes are explored for hydrocarbons processes. Significant energy savings and even reduced footprint may be achieved in olefins production units. © 2012 Elsevier B.V.

Olefin recovery from FCC off-gas can pay off

International Nuclear Information System (INIS)

Brahn, M.G.

1992-01-01

This paper reports on olefins recovery from refinery FCC offgas streams which offers an attractive cash flow from olefins from a tail-gas stream that has typically been consumed as refinery fuel. Such recovery schemes can be employed in refineries or olefins plants, and can be tailored to fit individual requirements. Mobil Chemical Co. has operated such a dephlegmator-based off-gas recovery unit at its Beaumont, Tex., olefin plant since 1987. It reported that the project was paid out within 11 months of initial start-up

Catalytic olefin polymerization with early transition metal compounds

OpenAIRE

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

Ternary catalyst-olefin-hydroperoxide complexes and their contribution to epoxidation

International Nuclear Information System (INIS)

Svitych, R.B.; Rzhevskaya, N.N.; Buchachenko, A.L.; Yablonskij, O.P.; Petukhov, A.A.; Belyaev, V.A.

1976-01-01

Electron and NMR spectroscopy have been used for studying the complex formation of catalysts (Mo 5+ , Mn 2+ , Co 2+ ) in double and triple systems: metal-olefin and metal-olefin-hydroperoxide. It has been established that ions of metals form complexes with olefins in the first sphere. The formation has been proved of ternary complexes metal-olefin-hydroperoxide. The structure of the complexes has been proposed with olefins in the first and hydroperoxide in the second sphere of the metal ion. The structure explains known kinetic regularities of epoxydation and the mechanism of the formation of final products, oxide and alcohol. It has been shown that the best catalysts for epoxydation of olefins with hydroperoxides must be the compounds of the metals with an electron state of ion d 0 [ru

Metylcyclohexane conversion to light olefins

OpenAIRE

SCOFIELD, C.F.; BENAZZI, E.; CAUFFRIEZ, H.; MARCILLY, C.

1998-01-01

This study consists in the evaluation of the catalytic properties of zeolites with different structures in the conversion of methylcyclohexane to light olefins. Results obtained suggest that the steric constrictions of the catalysts used play an important role in hydrogen transfer reactions. Higher selectivities for light olefins (C3= and C4=) were observed for zeolites having more closed structures, like MFI and ferrerite, when compared to those having more open ones, like beta, omega and fa...

P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

Science.gov (United States)

Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

2017-04-07

An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

Production of olefins from bioethanol. Catalysts, mechanism

Directory of Open Access Journals (Sweden)

Kusman Dossumov

2012-12-01

Full Text Available This review describes methods of catalytic obtaining from bioethanol of valuable industrial products – olefins, particularly ethylene. Аmong olefins, ethylene is the most popular key raw material of petrochemical synthesis. The scope of appllication of ethylene is almost unlimited in petrochemical products: polyethylene, ethylbenzene, styrene, ethylene dichloride, vinyl chloride etc. It also examines catalysts for the production of olefins and their properties. The most promising and commercially advantageous process of ethylene production by catalytic dehydration of ethanol on catalysts based on modified alumina. And this review discusses the mechanisms of catalytic conversion of ethanol to ethylene.

Metylcyclohexane conversion to light olefins

Directory of Open Access Journals (Sweden)

SCOFIELD C.F.

1998-01-01

Full Text Available This study consists in the evaluation of the catalytic properties of zeolites with different structures in the conversion of methylcyclohexane to light olefins. Results obtained suggest that the steric constrictions of the catalysts used play an important role in hydrogen transfer reactions. Higher selectivities for light olefins (C3= and C4= were observed for zeolites having more closed structures, like MFI and ferrerite, when compared to those having more open ones, like beta, omega and faujasite.

Hydroxycarbonylation of olefins and alcohols in ionic liquids

Energy Technology Data Exchange (ETDEWEB)

Lapidus, A.L.; Eliseev, O.L.; Bondarenko, T.N.; Stepin, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

2006-07-01

Palladium-catalysed hydroxycarbonylation of olefins and alcohols proceeds in ionic liquid media. Terminal and internal olefins, cyclohexene, styrene, methanol, ethanol, n-butanol, cyclohexanol, benzyl alcohol and 1-phenylethanol were tested as substrates for the reaction. A number of molten salts were applied as a reaction medium and tetrabutylammonium bromide (m.p. 103 C) seemed to be the best. Carbon monoxide pressure of 2 MPa and reaction temperature of 110 C are suitable conditions to furnish the reaction in 2 hours in the presence of palladium acetate as a precursor. Triphenylphosphine added as a ligand reduces reaction rate. The critical role of counter anion in molten salt was also recognised. Yield of acids decreased in the order: Br{sup -} > Cl{sup -} > BF{sub 4} {approx}PF{sub 6}{sup -}. A two-route reaction scheme is proposed to explain the regularities of styrene and 1-phenylethanol hydroxycarbonylation. The catalytic system can be used repeatedly by simple extraction of products with diethyl ether. Nine cycles were carried out without loss of activity. (orig.)

Production and use of light olefins. Preprints of the conference

Energy Technology Data Exchange (ETDEWEB)

Ernst, S.; Buzzoni, R.; Leitner, W.; Lercher, J.A.; Lichtscheidl, J.; Nees, F.; Santacesaria, E. (eds.)

2009-07-01

Within the conference of the German Society for Petroleum and Coal Science and Technology e.V. (Hamburg, Federal Republic of Germany) in Berlin (Federal Republic of Germany) at 28th to 30th September, 2009, the following lectures were held: (1) Steamcracking - State of the Art (H. Zimmermann); (2) Diversify Feedstock Options to Olefin Production (Q. Ling et al.); (3) Syngas to lower olefins (E. Schwab et al.); (4) STAR process registered for the on-purpose production of propylene (K. Bueker); (5) The catalytic activity of zinc oxide supported on aerosil for C-H activation of light alkanes (S. Arndt et al.); (6) Novel catalytic approaches for the oxidative dehydrogenation of ethane (D. Hartmann); (7) A comparison of the active sites structures of homogeneous and heterogeneous olefin polymerisation catalysts (A. Zecchina); (8) Catalytic strategies in metathesis (C. Coperet); (9) Multi-technology integrated production and consumption of olefins (J. Popp et al.); (10) Olefin oligomerization for the production of fuels and petrochemicals (H. Olivier-Bourbigou et al.); (11) Dieselization of the world - How to increase diesel yield in a refinery (A. Dueker); (12) Isomerization of butenes: LyondellBasell's Isomplus technology development (T. Zak et al.); (13) Valuable products from butadiene, carbon dioxide and further base chemicals (A. Behr); (14) The partial oxidation of propene to propylene oxide using N{sub 2}O as an oxidant (T. Thoemmes); (15) Alternative feedstocks for olefin production: What role will ethanol play? (B.R. Maughon); (16) Production of light olefins from renewable resources - The effect of deoxygenation degree on yields of light olefins (D. Kubicka et al.); (17) Recovery of low olefins from refinery offgases (M. Bender).

The olefin metathesis reaction: reorganization and cyclization of organic compounds

International Nuclear Information System (INIS)

Frederico, Daniel; Brocksom, Ursula; Brocksom, Timothy John

2005-01-01

The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances. (author)

SAXS observation of structural evolution of heated olefin

International Nuclear Information System (INIS)

Sun Minhua; Mou Hongchen; Wang Yuxi; Li Demin; Wang Aiping; Ma Congxiao; Cheng Weidong; Wang Dan; Liu Jia

2007-01-01

Structural evolution of olefin during its heating process was observed with SAXS method at Beijing Synchrotron Radiation Facility. The mean square fluctuation of electron density increased from 468.5 nm -2 at 22 degree C to 2416 nm -2 at 100 degree C, while the electronic gyration radius decreased from 11.61 nm at 22 degree C to 11.16 nm at 100 degree C. Therefore, the olefin softens as a result of the increased thermal motion of the molecules, rather than the shrinking size of fundamental structural units of olefin. (authors)

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

Science.gov (United States)

Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

2017-05-01

Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

Surface-enhanced light olefin yields during steam cracking

NARCIS (Netherlands)

Golombok, M.; Kornegoor, M.; Brink, van den P.; Dierickx, J.; Grotenbreg, R.

2000-01-01

Various papers have shown enhanced olefin yields during steam cracking when a catalytic surface is introduced. Our studies reveal that increased light olefin yields during catalytic steam cracking are mainly due to a surface volume effect and not to a traditional catalytic effect. Augmentation of

Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

Science.gov (United States)

dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

2015-03-01

Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Olefination reactions of phosphorus-stabilized carbon nucleophiles.

Science.gov (United States)

Gu, Yonghong; Tian, Shi-Kai

2012-01-01

A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

Kinetically based NMR method of measuring blending octane number of olefins

NARCIS (Netherlands)

Golombok, M.; Bruijn, J.; Morley, C.

1995-01-01

Olefins are highly nonlinear octane blenders so that standard GC analyses are poor predictors of blend quality. Engine rating is the only way of measuring olefin octane number nonlinearity. It is thus not possible to rapidly assess the quality of the product obtained from an olefin-producing

HIGH-POWER TURBODRILL AND DRILL BIT FOR DRILLING WITH COILED TUBING

Energy Technology Data Exchange (ETDEWEB)

Robert Radtke; David Glowka; Man Mohan Rai; David Conroy; Tim Beaton; Rocky Seale; Joseph Hanna; Smith Neyrfor; Homer Robertson

2008-03-31

Commercial introduction of Microhole Technology to the gas and oil drilling industry requires an effective downhole drive mechanism which operates efficiently at relatively high RPM and low bit weight for delivering efficient power to the special high RPM drill bit for ensuring both high penetration rate and long bit life. This project entails developing and testing a more efficient 2-7/8 in. diameter Turbodrill and a novel 4-1/8 in. diameter drill bit for drilling with coiled tubing. The high-power Turbodrill were developed to deliver efficient power, and the more durable drill bit employed high-temperature cutters that can more effectively drill hard and abrasive rock. This project teams Schlumberger Smith Neyrfor and Smith Bits, and NASA AMES Research Center with Technology International, Inc (TII), to deliver a downhole, hydraulically-driven power unit, matched with a custom drill bit designed to drill 4-1/8 in. boreholes with a purpose-built coiled tubing rig. The U.S. Department of Energy National Energy Technology Laboratory has funded Technology International Inc. Houston, Texas to develop a higher power Turbodrill and drill bit for use in drilling with a coiled tubing unit. This project entails developing and testing an effective downhole drive mechanism and a novel drill bit for drilling 'microholes' with coiled tubing. The new higher power Turbodrill is shorter, delivers power more efficiently, operates at relatively high revolutions per minute, and requires low weight on bit. The more durable thermally stable diamond drill bit employs high-temperature TSP (thermally stable) diamond cutters that can more effectively drill hard and abrasive rock. Expectations are that widespread adoption of microhole technology could spawn a wave of 'infill development' drilling of wells spaced between existing wells, which could tap potentially billions of barrels of bypassed oil at shallow depths in mature producing areas. At the same time, microhole

(Z-Selective Takai olefination of salicylaldehydes

Directory of Open Access Journals (Sweden)

Stephen M. Geddis

2017-02-01

Full Text Available The Takai olefination (or Takai reaction is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E-selectivity; however, herein we report the highly (Z-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

(Z)-Selective Takai olefination of salicylaldehydes.

Science.gov (United States)

Geddis, Stephen M; Hagerman, Caroline E; Galloway, Warren R J D; Sore, Hannah F; Goodman, Jonathan M; Spring, David R

2017-01-01

The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high ( E )-selectivity; however, herein we report the highly ( Z )-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

Pd(II)-Catalyzed Olefination of sp3 C–H Bonds

Science.gov (United States)

Wasa, Masayuki; Engle, Keary M.; Yu, Jin-Quan

2010-01-01

The first Pd(II)-catalyzed sp3 C–H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding γ lactams. Notably, this method was effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C–H olefination of cyclopropane substrates. PMID:20187642

Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

Science.gov (United States)

Chary, Bathoju Chandra; Kim, Sunggak

2013-09-25

Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

Isobutane/olefin-alkylation

Energy Technology Data Exchange (ETDEWEB)

Waitkamp, J.; Maixner, S.

1983-11-01

Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

Techno-economic analysis and comparison of coal based olefins processes

International Nuclear Information System (INIS)

Xiang, Dong; Yang, Siyu; Qian, Yu

2016-01-01

Highlights: • The coal based Fischer–Tropsch-to-olefins (CFTO) process is proposed and analyzed. • The CFTO suffers from lower energy efficiency and serious CO 2 emissions. • Approaches for improving techno-economic performance of the CFTO are obtained. - Abstract: Traditional olefins production is heavily dependent on oil. In the background of the scarcity of oil and richness of coal in China, olefins production from coal has been attracting more attention of the chemical process industry. The first coal based methanol-to-olefins (CMTO) plant has been commercialized in China. For shorter process route and lower capital cost, Fischer–Fropsch has been put forward in the last few years. The coal based Fischer–Tropsch-to-olefins (CFTO) process is designed in this paper and then its techno-economic and environmental performance was detailed studied in this paper, in comparison with the CMTO. Results show that at the present olefins selectivity, the CFTO suffers from relative lower energy efficiency and higher CO 2 emissions. In economic aspect, the capital investment and product cost of the CFTO are roughly equivalent to that of the CMTO. Although the conversion route of the CFTO is shorter, its techno-economic performance is still inferior to that of the CMTO. It is also found that increase of olefins selectivity by cracking oil or decrease of CO 2 selectivity by improving catalyst could significantly improve the performance of the CFTO.

Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes.

Science.gov (United States)

Li, Xuting; Gong, Xue; Zhao, Miao; Song, Guoyong; Deng, Jian; Li, Xingwei

2011-11-04

Rhodium(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides has been achieved at the peri position. Three categories of olefins have been successfully applied. Activated olefins reacted to afford five-membered azacycles as a result of oxidative olefination-hydroamination. Unactivated olefins reacted to give the olefination product. 2-fold oxidative C-C and C-N coupling was achieved for allylbenzenes. © 2011 American Chemical Society

Reactivity of olefin and allyl ligands in π-complexes of metals

International Nuclear Information System (INIS)

Kukushkin, Yu.N.

1987-01-01

The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

Drilling in troubled waters. For an international regulation on offshore gas and oil activities

International Nuclear Information System (INIS)

Rochette, Julien

2014-01-01

Due to an increased energy demand, offshore activities are being extended to deep and ultra-deep waters: nearly one third of consumed oil and one quarter of consumed gas come from offshore drilling. This development threatens the environment and natural resources, and may have an impact on human activities which depend on the concerned ecosystems. As some accident had cross-border consequences, the relevance of the international regulatory framework is put into question again. This article first outlines the incomplete character of the legal framework for the safety of offshore activities: uncoordinated national systems, lack of an international convention, fragmented regional initiatives (some agreements exist for some specific regions: Arctic Sea, Baltic Sea, Mediterranean Sea, North-Eastern Atlantic, Persic Gulf and Oman Sea, Africa, western Indian Ocean). The author outlines that there is no international rules regarding responsibility and compensations. While highlighting the risks of a status-quo on these different issues, the author proposes and discusses a set of recommendations aimed at strengthening the regulation of offshore drilling activities

Radiation-induced copolymerization of hexafluoroacetone with α-olefins

International Nuclear Information System (INIS)

Matsuda, O.; Watanabe, S.; Okamoto, J.; Machi, S.; Tabata, Y.

1977-01-01

The copolymerization of hexafluoroacetone with higher α-olefins above butene, such as 1-pentene (I), 1-hexene (II), 1-octene (III), 2-methyl-1-butene (IV), 2-methyl-1-pentene (V), 3-methyl-1-butene (VI), and 4-methyl-1-pentene (VII) was studied at relatively low temperatures by γ-ray irradiation. Copolymerization of II, IV, V, and VII with hexafluoroacetone was found to scarcely take place at -78 0 C in bulk, but the addition of trichlorotrifluoroethane in amounts to yield equimolar mixtures resulted in conversion of 15.7 percent for IV and of 2.1 to 4.0 percent for the other α-olefins. Higher conversion of V at -78 0 C than at 0 0 C suggest that copolymerization may take place via an ionic mechanism. The effects of various additives on the copolymerization are reported. Infrared spectral studies indicated that the double bond of the α-olefins is opened to form a polymer. The C--O double bond of the hexafluoroacetone and the α-olefin double bond are opened to form the copolymer

Olefin metathesis in nano-sized systems

Directory of Open Access Journals (Sweden)

Denise Méry

2011-01-01

Full Text Available The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM, cross metathesis (CM, enyne metathesis reactions (EYM – for reactions in water without a co-solvent and (ii construction and functionalization of dendrimers by CM reactions.

Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

Science.gov (United States)

Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

2014-10-01

Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

Reactions of rhodium(I) carbonyl chloride with olefins

International Nuclear Information System (INIS)

Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.

1987-01-01

The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

Life cycle assessment of energy consumption and GHG emissions of olefins production from alternative resources in China

International Nuclear Information System (INIS)

Xiang, Dong; Yang, Siyu; Li, Xiuxi; Qian, Yu

2015-01-01

Highlights: • Conduct a life cycle energy use and GHG emissions of olefins production processes. • Analyse effects of carbon capture and efficiency on alternative olefins production. • Analyse life cycle performance of Chinese olefins industry in three key periods. • Present the advantages and challenges of alternative olefins routes. - Abstract: Olefins are important platform chemicals widely used in industry. In terms of the short supply of oil resources, natural gas and coal are two significant alternative feedstocks. In this paper, energy consumption and GHG emissions of olefins production are analysed with life cycle assessment methods. Results showed the energy consumption and GHG emissions of natural gas-to-olefins are roughly equivalent to those of oil-to-olefins, while coal-to-olefins suffers from higher energy consumption and serious GHG emissions, including 5793 kg eq. CO 2 /t olefins of direct emissions and 5714 kg eq. CO 2 /t olefins of indirect emissions. To address the problem, the effect of carbon capture on coal-to-olefins is investigated. In comprehensive consideration of energy utilization, environmental impact, and economic benefit, the coal-to-olefins with 80% CO 2 capture of the direct emissions is found to be an appropriate choice. With this carbon capture configuration, the direct emissions of the coal-to-olefins are reduced to 1161 kg eq. CO 2 /t olefins. However, the indirect emissions are still not captured, which should be strictly monitored and significantly reduced. Finally, a scenario analysis is conducted to estimate resource utilization and GHG emissions of olefins production of China in 2020. Several suggestions are also proposed for policy making on the sustainable development of olefins industry

Direct observation of OH production from the ozonolysis of olefins

Science.gov (United States)

Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

Ionic liquids for separation of olefin-paraffin mixtures

Science.gov (United States)

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2013-09-17

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Direct olefination of fluorinated benzothiadiazoles: a new entry to optoelectronic materials.

Science.gov (United States)

Xiao, Yu-Lan; Zhang, Bo; He, Chun-Yang; Zhang, Xingang

2014-04-14

Fluorinated olefin-containing benzothiadiazoles have important applications in optoelectronic materials. Herein, we reported the direct olefination of fluorinated benzothiadiazoles, as catalyzed by palladium. The reaction proceeds under mild reaction conditions and shows high functional-group compatibility. A preliminary study of the properties of the resulting symmetrical and unsymmetrical olefin-containing fluorinated benzothiadiazoles in red-light-emitting dyes has also been conducted. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparing Ru and Fe-catalyzed olefin metathesis

KAUST Repository

Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

2014-01-01

Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

Oxidative cracking of n-hexane: a catalytic pathway to olefins

NARCIS (Netherlands)

Boyadjian, C.A.

2010-01-01

Steam cracking, the major, current existing route for light olefin production, is the most energy consuming process in the chemical industry. The need for an energy efficient processes, urged substantial research work for the development of new catalytic technologies for light olefin production.

The Swedish Deep Drilling Program - an emerging scientific drilling program and new infrastructure.

Science.gov (United States)

Lorenz, Henning; Juhlin, Christopher

2010-05-01

Scientific drilling projects imply numerous aspects that are difficult to handle for individual research groups. Therefore, about three years ago a joint effort was launched in the Swedish geoscientific community to establish a national program for scientific drilling, the Swedish Deep Drilling Program (SDDP). Soon afterwards, several working groups established drilling proposals with Nordic and, also, international participation. With this serious interest in scientific drilling SDDP was able to successfully promote the Swedish membership in ICDP which commenced in 2008. Two SDDP projects achieved workshop grants from the International Continental Scientific Drilling Program (ICDP) in 2009. In the same year the Swedish Research Council decided to support an application for a truck-mounted drill rig - a big success for the SDDP working group. Scientific Drilling infrastructure: SDDP envisages a mobile platform that is capable of core drilling to at least 2500 m depth. The procurement will be made during 2010 and first operations are planned for 2011. This drill rig is primarily intended for use in the SDDP drilling projects, but will be rented out to other scientific drilling projects or even commercial enterprises in the remaining time to cover maintenance and future upgrade costs. SDDP's drill rig will be unique in Europe and complementary to the deep drilling InnovaRig of the GFZ German Research Centre for Geosciences. Until now, drilling to 2000 - 3000 m implied the use of a full-sized drill rig like the InnovaRig or the mobilization of a core drill rig from another continent. This gap will now be filled by Sweden's upcoming scientific drilling infrastructure. Drilling projects and proposals: Presently, SDDP serves six projects: "Collisional Orogeny in the Scandinavian Caledonides" (COSC; ICDP workshop spring 2010), the "Postglacial Fault Drilling Project" (PFDP; ICDP workshop autumn 2010), a "Deep Rock Laboratory" (DRL), "Palaeoproterozoic Mineralized Volcanic

Allene or alkyne treatment of olefin conversion catalysts

International Nuclear Information System (INIS)

Banks, R.L.

1986-01-01

This patent describes a disproportionation process which comprises contacting at least one olefin from the group consisting of: acyclic mono- and polyenes having at least 3 up to 10 carbon atoms per molecule, and cycloalkyl and aryl derivatives thereof; cyclic mono- and polyenes having at least 4 to 10 carbon atoms per molecule, and alkyl and aryl derivatives thereof; mixtures of two or more of the above olefins; and mixtures of ethylene with one or more of the above olefins capable of undergoing disproportionation with a tungsten oxide on silica disproportionation catalyst system under disproportionation conditions, the improvement comprising contacting the catalyst with an activating amount of at least one alkyne conforming to the formula: R-C=C-R wherein each R is independently H or a C/sub 1/-C/sub 6/ carbon radical per mole of tungsten oxide

Zeolitic imidazolate frameworks with optimized pore structure for olefin/paraffin-separation

Energy Technology Data Exchange (ETDEWEB)

Paula, C.; Boehme, U.; Hartmann, M. [Erlangen-Nuernberg Univ. (Germany). Erlangen Catalysis Resource Center

2013-11-01

In the chemical industry, the largest part of energy is spent on separation processes such as the separation of olefin/paraffin mixtures from steam cracker effluents by low-temperature rectification. A suitable alternative to this energy and cost intensive process is separation by selective adsorption with suitable microporous adsorbent. In this work, different ZIFs (Zeolitic Imidazolate Frameworks) have been explored with respect to their separation of olefins and paraffins. The studied materials (e.g. ZIF-8 (SOD-Topology), ZIF-71 (RHO-Topology)) were selected because of their low diameter of the largest pore entrance (0.29 to 4.2 nm) which is close to the kinetic diameter of the C{sub 2} to C{sub 4} olefins and paraffins under study. In contrast to other MOF- or zeolite-based adsorbents, in ZIF-8 and ZIF-71, the paraffin is preferentially adsorbed, which is evident from the single-component adsorption isotherms at different temperature. In the corresponding mixture breakthrough curves, the olefin breaks through first and the alkane even displaces the olefin from the pores. Thus, ZIF-8 and ZIF-71 are interesting candidates for the envisaged paraffin/olefin separation. Whether the observed separation behavior is due to the structural properties of the studied ZIFs or a consequence of peculiar chemical properties is subject to further studies. (orig.) (Published in summary form only)

Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

Science.gov (United States)

Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

2009-01-01

Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

Alkylation of isobutane with light olefins catalyzed by zeolite beta

NARCIS (Netherlands)

Nivarthy, G.S.; Feller, A.P.; Seshan, Kulathuiyer; Lercher, J.A.

2000-01-01

Alkylation of isobutane with ethene and propene was studied over an H-BEA catalyst in a well-stirred reactor. Under similar conditions of space velocity and paraffin-to-olefin feed ratio, lower initial olefin conversions were observed with ethene or propene than those reported earlier for butene.

Report of the 8th International Symposium on the Observation of the Continental Crust Through Drilling; Dai 8 kai tairiku kagaku kussaku kokusai symposium ni sankashite

Energy Technology Data Exchange (ETDEWEB)

Yoshida, K. [Super Deep Core Drilling Study Group, Japan, Tokyo (Japan)

1996-11-29

This report relates to the 8th International Symposium on the Observation of the Continental Crust Through Drilling, convened at Agency of Industrial Science and Technology, Tsukuba City, on February 26, 1996. The symposium was represented by approximately 200 people from the U.S., Canada, Britain, Germany, France, Russia, China, and some others, who discussed active faults, drilling and logging, transfer of fluids and heat in the crust, history of the earth and climate, ICDP (International Continental Scientific Drilling Program) and international cooperation under this program in the future, etc. In reference to ultradeep drilling in the world, drillings by Germany`s KTB (Kontinentales Tiefbohrprogramm)(9,101m deep) and Russia at Kola Peninsula (l2,261m) were reviewed. Concerning the efforts of U.S. Continental Scientific Drilling Program during the previous 11-year period, it was reported that it had cost a total of $84,000,000; that investigations had been made into volcanos and geotherm, fault tectonics, sedimentary basins, holes due to meteorites, and metal ore deposits; and that 61 holes (total length: 31,310m and maximum depth: 3,510m) had been drilled and investigated. 6 figs., 3 tabs.

Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols.

Science.gov (United States)

Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata

2016-02-04

Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.

Science.gov (United States)

Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong

2014-01-03

A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

Radiation-induced copolymerization of methyl trifluoroacrylate with α-olefins

International Nuclear Information System (INIS)

Matsuda, O.; Watanabe, T.; Tabata, Y.; Machi, S.

1978-01-01

Paper describes the radiation-induced bulk copolymerization of methyl trifluoroacrylate with various α olefins; propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and isobutylene. MTFA (purity above 98%) was synthesized by method described in literature. Reagent grade α-olefins were used. An equimolar mixture of MTFA and α-olefin was charged into the reactor. Trace amounts of oxygen were purged by the freeze-thaw technique. Irradiation was carried out with gamma rays from a 60 Co source under vapor pressure of the monomers at 25 0 C. The product was precipitated and washed with methanol to remove unreacted monomers, and dried under vacuum at 60 0 C. Infrared spectra of the copolymers were measured; compositions were determined from elemental analysis. Reactivity of the α-olefins appears to be related to the electron density at the double bond. All copolymers were found to have almost equimolar compositions and were soluble in polar solvents such as tetrahydrofuran and acetone. Copolymerization was inhibited completely by the addition of 1,1-diphenyl-2-picrihydrazil, but not by water, indicating that the copolymerization proceeds via a radical mechanism. 1 table; 2 figures

A new adjustable parallel drill guide for internal fixation of femoral neck fracture: a developmental and experimental study

OpenAIRE

Yuenyongviwat, Varah; Tuntarattanapong, Pakjai; Tangtrakulwanich, Boonsin

2016-01-01

Background Internal fixation is one treatment for femoral neck fracture. Some devices and techniques reported improved accuracy and decreased fluoroscopic time. However, these are not widely used nowadays due to the lack of available special instruments and techniques. To improve the surgical procedure, the authors designed a new adjustable drill guide and tested the efficacy of the device. Methods The authors developed a new adjustable drill guide for cannulated screw guide wire insertion fo...

Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

International Nuclear Information System (INIS)

Lee, Hyung Soo; Lee, Gab Yong

2005-01-01

The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

Science.gov (United States)

Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

2010-03-20

We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

The progress of SINOPEC methanol-to-olefins (S-MTO) technology

Energy Technology Data Exchange (ETDEWEB)

Liu, Hongxing; Xie, Zaiku; Zhao, Guoliang [SINOPEC Shanghai Research Institute of Petrochemical Technology (China)

2013-11-01

It is widely recognized that naphtha steam crackers and FCC units are the main current sources of ethylene and propylene. On the condition of high oil price, olefin producers are striving to develop new economical routes to produce ethylene and propylene with low-cost feedstocks. Methanol to olefins (MTO) has aroused great attention in recent years, and SINOPEC has developed a new kind of MTO process named S-MTO which features high olefins selectivity, high methanol conversion and low catalyst consumption. Puyang Zhongyuan 200 KTA S-MTO has been in steady operation for more than 17 months. The catalyst used in the process is based on a silicoaluminophosphate, SAPO-34, which has very high carbon selectivity to low carbon olefins. Results from the commercial plant show that S-MTO process converts methanol to ethylene and propylene at about 81% carbon selectivity. The carbon selectivity approaches 92% if butenes are also accounted for as part of the product. Typically, the ratio of propylene to ethylene can range from 0.6 to 1.3. When combined with OCC (Olefin Catalytic Cracking) process to convert the heavier olefins, the overall yield of ethylene and propylene can increase to 85% {proportional_to} 87% and propylene-ethylene ratios of more than 1.5 are achievable. Other co-products include very small amounts of C1-C4 paraffins, hydrogen, CO and CO{sub 2}, as well as heavier oxygenates only with ppm level. Because of the quick deactivation of MTO catalyst, a kind of high efficiency fast fluidized bed reactor is adopted. The activity of deactivated catalyst is recovered by burning the coke in the regenerator. This paper gives an updated introduction of S-MTO technology developed by SINOPEC SRIPT. (orig.)

Thermal 18F atom addition to olefins

International Nuclear Information System (INIS)

Rogers, P.J.M.

1986-01-01

The addition of thermal 18 F atoms to olefins was investigated using various substrate molecules. The 18 F atoms were produced by the 19 F(n,2n) 18 F nuclear reaction with >10 5 eV of energy which is removed by multiple collisions with SF 6 molecules before reaction occurs with an olefin. By varying the SF 6 /substrate mole ratio it was demonstrated that the fraction of non-thermal reactions is dependent upon the frequency of non-reactive energy reducing collisions with SF 6 . The rate constants for addition and abstraction reactions with propene, cis-1-chloropropene and trans-1-chloropropene were determined. The substitution of a C1 atom for the olefinic H atom in the C 1 position does not affect the rate of 18 F bond formation but it changes the orientation of attack. The 18 F atom prefers the terminal carbon-in propene and propene-d 6 by a factor of 1.35 while the preference is less than 0.5 for the terminal carbon in cis-1-chloropropene and trans-1-chloropropene. The addition of 18 F atoms to olefins creates vibrationally excited fluoroalkyl radicals which can either decompose or stabilize by collision with another molecule. The rate constants for decomposition of excited CH 3 CHCHC1F radicals formed by 18 F addition to cis-1-chloropropene and trans-1-chloropropene are competitive with C 1 -C 2 bond rotation. The 18 F atoms add to the parent molecule with retention of geometry and a memory of the geometry persists as demonstrated by the cis-1-fluoropropene/trans-1-fluoropropene decomposition product ratio

Alternative routes to olefins. Chances and challenges

Energy Technology Data Exchange (ETDEWEB)

Meiswinkel, A.; Delhomme, C.; Ponceau, M. [Linde AG, Pullach (Germany)

2013-11-01

In the future, conventional raw materials which are used for the production of olefins will get shorter and more expensive and alternative raw materials and production routes will gain importance. Natural gas, coal, shale oil or bio-mass are potential sources for the production of olefins, especially ethylene and propylene, as major base chemicals. Several potential production routes were already developed in the past, but cost, energy and environmental considerations might make these unattractive or unfeasible in comparison to traditional processes (e.g. steam cracking). Other processes such as methanol to olefins processes were successfully developed and first commercial units are running. In addition, combination of traditional processes (e.g. coal/biomass gasification, Fischer-Tropsch and steam cracking) might enable new pathways. Besides, dehydration of ethanol is opening direct routes from biomass to 'green' ethylene. However, for these 'bio-routes', feedstock availability and potential land use conflict with food production (sugar cane, wheat,..) still need to be evaluated. finally, new oxidative routes, including processes such as oxidative coupling of methane or oxidative dehydrogenation, are still at an early development stage but present potential for future industrial applications. (orig.) (Published in summary form only)

Retrofit with membrane the Paraffin/Olefin separation

Energy Technology Data Exchange (ETDEWEB)

Motelica, A.; Bruinsma, O.S.L.; Kreiter, R.; Den Exter, M.J.; Vente, J.F. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

2012-10-15

Olefins, such as ethylene, propylene, and butadiene, are among the most produced intermediates in petrochemical industry. They are produced from a wide range of hydrocarbon feedstocks (ethane, propane, butane, naphtha, gas oil) via a cracking process. The last step in this process is the separation of olefins from other hydrocarbons, which is traditionally performed with distillation. As the physicochemical properties, such as volatility and boiling point, of the compounds are very similar, the purification becomes capital and energy intensive. For example, the top of an ethylene/ethane distillation column needs to be chilled to -30C and this requires large amount of electric energy consumption. The separation of butadiene from the C4-fraction is performed with the aid of an additional solvent. This solvent has to be regenerated at the cost of additional high temperature steam. To overcome these separation disadvantages of olefin/paraffin separation, different separation methods have been investigated and proposed in recent years. Suggested options are based on better heat integration of the overall process, or on novel separation systems such as Heat Integrated Distillation Columns, membrane separation, adsorption-desorption systems or on hybrid separation methods, for example, distillation combined with membrane separation.

Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

Energy Technology Data Exchange (ETDEWEB)

Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)

1995-12-31

A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

Gum forming olefinic precursors in motor gasoline: a model compound study

Energy Technology Data Exchange (ETDEWEB)

Nagpal, J.M.; Joshi, G.C.; Singh, J.; Rastogi, S.N. (Indian Institute of Petroleum, Dehradun (India))

1994-01-01

The source of the cracked components in motor gasoline are generally (Fluid Catalytic Cracking) FCC and thermal cracking naphthas incorporated in the gasoline pool. The FCC olefins are predominant in isostructures, while thermal cracking naphthas obtained from visbreaking and coking operations contain substantial amounts of cyclic structures. The contribution of various olefinic structures present in these naphthas are likely to vary. The gum forming tendencies of different types of olefinic structures have been studied by taking model compounds in a known sample matrix through potential gum measurements under accelerated test conditions. Peroxide number values have also been determined on aged sample. Cyclic and dicyclic structures have been found to contribute maximum, towards gum formation tendencies. Branching generally increases the gum formation. However, position of branching plays an important role besides the double bond. Synergistic effects of dienes with straight chain and branched olefins have also been studied. 11 refs., 10 figs., 2 tabs.

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

International Nuclear Information System (INIS)

Matsuda, O.; Kostov, G.K.; Tabata, Y.; Machi, S.

1979-01-01

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with α-olefins were carried out in bulk by γ-ray irradiation at 25 0 C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r 1 (FAN) and r 2 (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system

Production of jet fuel range paraffins by low temperature polymerization of gaseous light olefins using ionic liquid

International Nuclear Information System (INIS)

Jiang, Peiwen; Wu, Xiaoping; Zhu, Lijuan; Jin, Feng; Liu, Junxu; Xia, Tongyan; Wang, Tiejun; Li, Quanxin

2016-01-01

Graphical abstract: A novel catalytic transformation of light olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. - Highlights: • A novel transformation of light olefins to jet fuel range paraffins was demonstrated. • The synthetic fuels can be produced by atmospheric olefin polymerizations. • C 8 –C 15 iso-paraffins from light olefins was achieved with a selectivity of 80.6%. - Abstract: This work demonstrated a novel catalytic transformation of gaseous olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. The production of the desired C 8 –C 15 iso-paraffins with the selectivity of 80.6 C mol% was achieved by the room-temperature polymerizations of gaseous light olefins using the [BMIM] Al 2 Cl 7 ionic liquid. The influences of the reaction conditions on the olefinic polymerizations were investigated in detail. The properties of hydrocarbons in the synthetic fuels were determined by the GC–MS analyses combined with 1 H NMR, and 13 C NMR analyses. The formation of C 8 –C 15 hydrocarbons from gaseous light olefins was illustrated by the identified products and the functional groups. This transformation potentially provides a useful avenue for the production of the most important components of iso-paraffins required in jet fuels.

Adsorption heats of olefins on supported MoO3/Al2O3 catalists

International Nuclear Information System (INIS)

Grinev, V.E.; Madden, M.; Khalit, V.A.; Aptekar', E.L.; Aldag, A.; Krylov, O.V.

1983-01-01

Adsorption heats of C 2 H 4 , C 3 H 6 and C 4 H 8 on supported MoO 3 /Al 2 O 3 catalysts containing 6, 10 and 15 wt. % of MoO 3 at 25, 77 and 195 deg are determimed. Adsorption heat of an olefin increases with a growing length of its carbonic chain. The number of adsorbed olefin molecules grows with an increase in the MoO 3 concentration, while initial adsorption heats decrease. The number of adsorbed olefins is proportional to mean rate of molybdenum reduction in catalysts. Adsorption heats of oxygen on the surface of the catalysts with preliminarily adsorbed olefins are determined. It is shown that adsorption of oxygen and olefins proceeeds both on the same and on different centres of the surface. Mechanisms of surface interactions are discussed

In vivo and in vitro olefin cyclopropanation catalyzed by heme enzymes

Science.gov (United States)

Coelho, Pedro S; Brustad, Eric M; Arnold, Frances H; Wang, Zhan; Lewis, Jared C

2015-03-31

The present invention provides methods for catalyzing the conversion of an olefin to any compound containing one or more cyclopropane functional groups using heme enzymes. In certain aspects, the present invention provides a method for producing a cyclopropanation product comprising providing an olefinic substrate, a diazo reagent, and a heme enzyme; and admixing the components in a reaction for a time sufficient to produce a cyclopropanation product. In other aspects, the present invention provides heme enzymes including variants and fragments thereof that are capable of carrying out in vivo and in vitro olefin cyclopropanation reactions. Expression vectors and host cells expressing the heme enzymes are also provided by the present invention.

Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

Science.gov (United States)

2006-08-01

organic, and biochemistry, lectured in chemistry of weapons, and researched on ionic liquids and nucleic acid derivatives. She discovered her joy of...Products from oligomerization of the dimer scaffold or olefin isomerization are excluded from these projected numbers.97,98 The number of...Figure 3-8). This is excluding any olefin isomerization products or oligomerization of the cyclic scaffold. If stereoisomers are considered, then

A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

KAUST Repository

Leitgeb, Anita; Abbas, Mudassar E.; Fischer, Roland C.; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

2012-01-01

An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

Science.gov (United States)

Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

2015-08-21

A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

Experimental investigation of temperature rise in bone drilling with cooling: A comparison between modes of without cooling, internal gas cooling, and external liquid cooling.

Science.gov (United States)

Shakouri, Ehsan; Haghighi Hassanalideh, Hossein; Gholampour, Seifollah

2018-01-01

Bone fracture occurs due to accident, aging, and disease. For the treatment of bone fractures, it is essential that the bones are kept fixed in the right place. In complex fractures, internal fixation or external methods are used to fix the fracture position. In order to immobilize the fracture position and connect the holder equipment to it, bone drilling is required. During the drilling of the bone, the required forces to chip formation could cause an increase in the temperature. If the resulting temperature increases to 47 °C, it causes thermal necrosis of the bone. Thermal necrosis decreases bone strength in the hole and, subsequently, due to incomplete immobilization of bone, fracture repair is not performed correctly. In this study, attempts have been made to compare local temperature increases in different processes of bone drilling. This comparison has been done between drilling without cooling, drilling with gas cooling, and liquid cooling on bovine femur. Drilling tests with gas coolant using direct injection of CO 2 and N 2 gases were carried out by internal coolant drill bit. The results showed that with the use of gas coolant, the elevation of temperature has limited to 6 °C and the thermal necrosis is prevented. Maximum temperature rise reached in drilling without cooling was 56 °C, using gas and liquid coolant, a maximum temperature elevation of 43 °C and 42 °C have been obtained, respectively. This resulted in decreased possibility of thermal necrosis of bone in drilling with gas and liquid cooling. However, the results showed that the values obtained with the drilling method with direct gas cooling are independent of the rotational speed of drill.

Methylenation of perfluoroalkyl ketones using a Peterson olefination approach.

Science.gov (United States)

Hamlin, Trevor A; Kelly, Christopher B; Cywar, Robin M; Leadbeater, Nicholas E

2014-02-07

An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3-trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl substituents and is easily scaled up. The alkenes prepared can be readily transformed into a variety of other perfluoroalkyl-containing compounds.

First examples of intramolecular addition of primary amidyl radicals to olefins

Energy Technology Data Exchange (ETDEWEB)

Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

2005-07-01

This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

Use of water in aiding olefin/paraffin (liquid + liquid) extraction via complexation with a silver bis(trifluoromethylsulfonyl)imide salt

International Nuclear Information System (INIS)

Wang, Yu; Thompson, Jillian; Zhou, Jingjing; Goodrich, Peter; Atilhan, Mert; Pensado, Alfonso S.; Kirchner, Barbara; Rooney, David; Jacquemin, Johan; Khraisheh, Majeda

2014-01-01

Highlights: • Silver-based ILs used as olefin extracting agents for olefin/paraffin mixtures. • Each extraction process is based on the olefin complexation and solvation. • The presence of water influences positively each extraction process. • Each extraction process was evaluated by DFT calculations, NMR, IR and Raman. • LLE data were then correlated by using the UNIQUAC model. - Abstract: This paper describes the extraction of C 5 –C 8 linear α-olefins from olefin/paraffin mixtures of the same carbon number via a reversible complexation with a silver salt (silver bis(trifluoromethylsulfonyl)imide, Ag[Tf 2 N]) to form room temperature ionic liquids [Ag(olefin) x ][Tf 2 N]. From the experimental (liquid + liquid) equilibrium data for the olefin/paraffin mixtures and Ag[Tf 2 N], 1-pentene showed the best separation performance while C 7 and C 8 olefins could only be separated from the corresponding mixtures on addition of water which also improves the selectivity at lower carbon numbers like the C 5 and C 6 , for example. Using infrared and Raman spectroscopy of the complex and Ag[Tf 2 N] saturated by olefin, the mechanism of the extraction was found to be based on both chemical complexation and the physical solubility of the olefin in the ionic liquid ([Ag(olefin) x ][Tf 2 N]). These experiments further support the use of such extraction techniques for the separation of olefins from paraffins

Palladium catalyzed selective distal C-H olefination of biaryl systems.

Science.gov (United States)

Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

2016-11-29

Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

Science.gov (United States)

Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

2013-07-19

A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

KAUST Repository

Dong, G.; Teo, P.; Wickens, Z. K.; Grubbs, R. H.

2011-01-01

Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive

Use of piezosurgery for internal auditory canal drilling in acoustic neuroma surgery.

Science.gov (United States)

Grauvogel, Juergen; Scheiwe, Christian; Kaminsky, Jan

2011-10-01

Piezosurgery is based on microvibrations generated by the piezoelectrical effect and has a selective bone-cutting ability with preservation of soft tissue. This study examined the applicability of Piezosurgery compared to rotating drills (RD) for internal auditory canal (IAC) opening in acoustic neuroma (AN) surgery. Piezosurgery was used in eight patients for IAC drilling in AN surgery. After exposition of the IAC and tumor, the posterior wall of the IAC was drilled using Piezosurgery instead of RD. Piezosurgery was evaluated with respect to practicability, safety, preciseness of bone cutting, preservation of cranial nerves, influences on neurophysiological monitoring, and facial nerve and hearing outcome. Piezosurgery was successfully used for selective bone cutting, while cranial nerves were structurally and functionally preserved, which could be measured by means of neuromonitoring. Piezosurgery guaranteed a safe and precise cut by removing bone layer by layer in a shaping way. Compared to RD, limited influence on neurophysiological monitoring attributable to Piezosurgery was noted, allowing for continuous neuromonitoring. No disadvantage due to microvibrations was noticed concerning hearing function. The angled tip showed better handling in right-sided than in left-sided tumors in the hands of a right-handed surgeon. The short, thick handpiece may be improved for more convenient handling. Piezosurgery is a safe tool for selective bone cutting for opening of the IAC with preservation of facial nerve and hearing function in AN surgery. Piezosurgery has the potential to replace RD for this indication because of its safe and precise bone-cutting properties.

Synthesis of pterostilbene by Julie Olefination

Science.gov (United States)

A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides.

Science.gov (United States)

Mitra, Prithiba; Shome, Brateen; De, Saroj Ranjan; Sarkar, Anindya; Mal, Dipakranjan

2012-04-14

The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone. This journal is © The Royal Society of Chemistry 2012

Conversion of olefins to liquid motor fuels

Science.gov (United States)

Rabo, Jule A.; Coughlin, Peter K.

1988-01-01

Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

hf alkylation in the 1980's: the role of isobutane/olefin ratio

Energy Technology Data Exchange (ETDEWEB)

Hutson, T. Jr.

1978-08-01

Research devoted to maximizing no-lead octane numbers in motor fuel is reported. Results of the studies are the basis for the following conclusions: 1. Isobutane alkylate made from either propylene, butene-2, or C/sub 3/--C/sub 4/ mixed olefins is a low sensitivity, high motor octane product. Typically, C/sub 3/--C/sub 4/ mixed olefin alkylate has a clear motor octane number of about 92.2 and a clear Research octane number of about 93.5. 2. In separate studies with propylene, butene-2 and C/sub 3/--C/sub 4/ mixed olefins, increasing the isobutane-to-olefin ratio suppressed the formation of high molecular weight residue, indicating a substantial reduction in the role of olefin polymerization to large ions. The overall result of increasing ratio was an improvement in selectivity to high-octane components in the alkylate. 3. When alkylating isobutane with propylene, increasing the ratio resulted in a decrease in the concentration of C/sub 7/-fraction (primary product) and an increase in the C/sub 8/-fraction (from chain initiation and subsequent hydrogen transfer). At the same time, the production of chain-termination-product propane also increased. 4. When alkylating isobutane with C/sub 3/--C/sub 4/ mixed olefins, increasing the ratio showed the same trend obtained in separate alkylation tests with propylene and butene-2. As the ratio increased, the concentration of C/sub 7/-fraction (primary propylene--isobutane product) decreased and the concentration of C/sub 8/-fraction increased markedly. Thus, increasing isobutane-to-olefin ratio exerted a strong effect on alkylate quality in the area of about 5 to 1 to 20 to 1; this effect diminished at ratios 20:1.

Cyclic olefin copolymer-silica nanocomposites foams

Czech Academy of Sciences Publication Activity Database

Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

2016-01-01

Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

Comparative toxicity of various ozonized olefins to bacteria suspended in air

Energy Technology Data Exchange (ETDEWEB)

Dark, P A; Nash, T

1970-01-01

Air containing olefin vapor was treated with known amounts of ozone simulating natural concentrations. The bactericidal effect of the mixture was tested using microthreads sprayed with washed cultures of Escherichia coli var. communis or Micrococcus albus, aerosol strain. With 20 different olefins a wide range of activity was found, those in which the double bond formed part of a ring being the most bactericidal; gasoline vapor was about as active as the average open-chain olefin. The two organisms behaved similarly at the experimental relative humidity of 80%. The estimated amount of bactericidal substance present was only about one hundreth of that required to give the same kill with a 'conventional' air disinfectant; a simple physical explanation is proposed for this enhanced effect.

Methyltrioxorhenium as catalyst of a novel aldehyde olefination

Energy Technology Data Exchange (ETDEWEB)

Herrmann, W.A. (Technische Univ. Muenchen, Garching (Germany). Anorganisch-Chemisches Inst.); Wang Mei (Academia Sinica, Dalian Inst. of Chemical Physics (China))

1991-12-01

From aldehydes or cyclic ketones, diazoalkanes, and teritiary phosphanes, olefins may be prepared with MTO as catalyst. In particular, diazoacetates and -malonates (R{sup 2}, R{sup 3} = H, CO{sub 2}Et, or 2 x CO{sub 2}Me) can be transformed into olefins with aliphatic and aromatic aldehydes (R{sup 1} = iPr, trans-PhCH=CH, Ph, 4-NO{sub 2}C{sub 6}H{sub 4}, etc.). Readily accessible starting materials, easy handling, mild reaction conditions, and good yields characterize the new synthesis method. (R' = Ph, 3-C{sub 6}H{sub 4}SO{sub 3}Na, nBu.) (orig.).

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

Science.gov (United States)

Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

2017-10-17

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ligand-enabled ortho-C-H olefination of phenylacetic amides with unactivated alkenes.

Science.gov (United States)

Lu, Ming-Zhu; Chen, Xing-Rong; Xu, Hui; Dai, Hui-Xiong; Yu, Jin-Quan

2018-02-07

Although chelation-assisted C-H olefination has been intensely investigated, Pd(ii)-catalyzed C-H olefination reactions are largely restricted to acrylates and styrenes. Here we report a quinoline-derived ligand that enables the Pd(ii)-catalyzed olefination of the C(sp 2 )-H bond with simple aliphatic alkenes using a weakly coordinating monodentate amide auxiliary. Oxygen is used as the terminal oxidant with catalytic copper as the co-oxidant. A variety of functional groups in the aliphatic alkenes are tolerated. Upon hydrogenation, the ortho -alkylated product can be accessed. The utility of this reaction is also demonstrated by the late-stage diversification of drug molecules.

Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

International Nuclear Information System (INIS)

Desrosiers, M.F.; Trifunac, A.D.

1986-01-01

The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

Propagation/depropagation equilibrium and structural factors in the radiation degradation of poly(olefin sulfone)s

International Nuclear Information System (INIS)

Bowmer, T.N.; O'Donnell, J.H.

1981-01-01

The principal volatile products observed after γ irradiation of nine different poly(olefin sulfone)s in the solid state were the two comonomers, i.e., the respective olefin and sulfur dioxide. An exponential increase in yield, G (volatile products), with increasing irradiation temperature, T/sub irr/, was observed for each copolymer through the ceiling temperature, T/sub c/, for the corresponding propagation/depropagation equilibrium. Thus the G value increased by ca. 3 orders of magnitude from T/sub irr/ = 0.7 T/sub c/ to T/sub irr/ = 1.3 T/sub c/ for all of the poly(olefin sulfone)s. Depropagation sensitivity was considered to be best measured by G(SO 2 ) since radiation induced, cationic homopolymerization of the product olefin occurred to a variable extent. Five of the poly(olefin sulfone)s had similar rates of depropagation at their respective T/sub c's/ but the polysulfones of 1-hexene, cyclohexene and 2-butene showed anomalously high depropagation rates. This may be related to greater steric hinderance to segmental chain mobility in the polysulfones of the 1,2 disubstituted olefins. Poly(1-hexene sulfone) appears to be anomalous, as in other respects

Quo Vadis ICDP? The Science Plan of the International Continental Scientific Drilling Program.

Science.gov (United States)

Horsfield, Brian

2014-05-01

The rocks and fluids of our ever-changing planet contain heat, energy, and life as well as archived records of what has gone before. These precious relicts and living systems need to be probed, collected, monitored and analyzed. The science results obtained cover the spectrum of the earth sciences from climate change, natural hazards and earth resources to the origins of life on Earth. The need to drill has never been greater, and this requires improved coordination between the marine, terrestrial and ice-coring communities and the research and private sector communities, effectively addressing the needs of our growing population for energy, sustenance, and quality of life. The ICDP is an infrastructure for scientific drilling that facilitates outstanding science. It is the only international platform for scientific research drilling in terrestrial environments. ICDP brings together scientists and stakeholders from 24 nations to work together at the highest scientific and technical niveaux. More than 30 drilling projects and 55 planning workshops have been supported to date. It is an efficient organisation, run according to the philosophy "lean and mean", with an average annual budget of about 5 million, and further third-party drilling expenditures that more than doubles this yearly investment. Here we report on ICDP's 2013 Science Conference "Imaging the Past to Imagine our Future", held November 11-14, 2013 in Potsdam whose goal was to set the new ICDP Science Plan in motion. New insights into geoprocesses and the identification of hot topics were high on the agenda, and debated in closed sessions, via posters and through oral presentations, and where appropriate dovetailed with socio-economic challenges. The conference was used to strengthen and expand our ties with member countries, and to debate incorporating industry into selected ICDP strategic activities where it makes sense to do so (ICDP remains science-driven). In addition, the conference paved the way

Radiation degradation of poly(olefin sulphone)s - Fundamental research to practical applications

International Nuclear Information System (INIS)

Bowden, M.J.; O'Donnell, J.H.

1985-01-01

The degradation of poly(olefin sulphone)s by high energy radiation, particularly by γ-rays and electron beams, provides an example of the application of fundamental science to high technology industry. Scientific interest in the radiation degradation of these polymers was first aroused by the discovery that they underwent highly specific bond scission in the backbone chain as the primary result of absorption of high energy radiation and in fact they were the first polymers in which such an effect had been demonstrated. This conclusion was initially based mainly on evidence from electron spin resonance spectroscopy and was subsequently verified by studies of molecular weight changes. These studies showed that the poly(olefin sulphone)s not only degraded by main chain scission but were also among the most radiation-sensitive polymers known. The extremely high sensitivity of poly(olefin sulphone)s to radiation-induced main-chain scission has found application in the field of microelectronics. Electron beam writing on poly(olefin sulphone) films is used to produce lithographic masks for the manufacture of integrated circuits on silicon wafers. Poly(1-butene sulphone) (PBS) is currently used in the production of a substantial proportion of the masks for the industry. The fundamental aspects of the radiation degradation of poly(olefin sulphone)s and the practical applications to high technology are reviewed. (author)

Alternative Test Method for Olefins in Gasoline

Science.gov (United States)

This action proposes to allow for an additional alternative test method for olefins in gasoline, ASTM D6550-05. The allowance of this additional alternative test method will provide more flexibility to the regulated industry.

Decarbonisation of olefin processes using biomass pyrolysis oil

International Nuclear Information System (INIS)

Sharifzadeh, M.; Wang, L.; Shah, N.

2015-01-01

Highlights: • Decarbonization of olefin processes using biomass pyrolysis oil was proposed. • The decarbonization is based on integrated catalytic processing of bio-oil. • The retrofitted process features significant economic and environmental advantages. - Abstract: An imperative step toward decarbonisation of current industrial processes is to substitute their petroleum-derived feedstocks with biomass and biomass-derived feedstocks. For decarbonisation of the petrochemical industry, integrated catalytic processing of biomass pyrolysis oil (also known as bio-oil) is an enabling technology. This is because, under certain conditions, the reaction products form a mixture consisting of olefins and aromatics, which are very similar to the products of naphtha hydro-cracking in the conventional olefin processes. These synergies suggest that the catalytic bio-oil upgrading reactors can be seamlessly integrated to the subsequent separation network with minimal retrofitting costs. In addition, the integrated catalytic processing provides a high degree of flexibility for optimization of different products in response to market fluctuations. With the aim of assessing the techno-economic viability of this pathway, five scenarios in which different fractions of bio-oil (water soluble/water insoluble) were processed with different degrees of hydrogenation were studied in the present research. The results showed that such a retrofit is not only economically viable, but also provides a high degree of flexibility to the process, and contributes to decarbonisation of olefin infrastructures. Up to 44% reductions in greenhouse gas emissions were observed in several scenarios. In addition, it was shown that hydrogen prices lower than 6 $/kg will result in bio-based chemicals which are cheaper than equivalent petrochemicals. Alternatively, for higher hydrogen prices, it is possible to reform the water insoluble phase of bio-oil and produce bio-based chemicals, cheaper than

Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

KAUST Repository

Dong, G.

2011-09-15

Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

A three-membered ring approach to carbonyl olefination.

Science.gov (United States)

Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno

2017-10-23

The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

Science.gov (United States)

Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su

2016-11-18

The rhodium(III)-catalyzed olefination of various carboxamides with α-CF 3 -substituted allylic carbonate is described. This reaction provides direct access to linear CF 3 -allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF 3 -allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

A new adjustable parallel drill guide for internal fixation of femoral neck fracture: a developmental and experimental study.

Science.gov (United States)

Yuenyongviwat, Varah; Tuntarattanapong, Pakjai; Tangtrakulwanich, Boonsin

2016-01-11

Internal fixation is one treatment for femoral neck fracture. Some devices and techniques reported improved accuracy and decreased fluoroscopic time. However, these are not widely used nowadays due to the lack of available special instruments and techniques. To improve the surgical procedure, the authors designed a new adjustable drill guide and tested the efficacy of the device. The authors developed a new adjustable drill guide for cannulated screw guide wire insertion for multiple screw fixation. Eight orthopaedic surgeons performed the experimental study to evaluate the efficacy of this device. Each surgeon performed guide wire insertion for multiple screw fixation in six synthetic femurs: three times with the new device and three times with the conventional technique. The fluoroscopic time, operative time and surgeon satisfaction were evaluated. In the operations with the new adjustable drill guide, the fluoroscopic and operative times were significantly lower than the operations with the conventional technique (p level of satisfaction of this device was also statistically significantly better (p = 0.02) than the conventional technique. The fluoroscopic and operative times with the new adjustable drill guide were reduced for multiple screw fixation of femoral neck fracture and the satisfaction of the surgeons was good.

Olefin Autoxidation in Flow

OpenAIRE

Neuenschwander Ulrich; Jensen Klavs F.

2014-01-01

Handling hazardous multiphase reactions in flow brings not only safety advantages but also significantly improved performance due to better mass transfer characteristics. In this paper we present a continuous microreactor setup capable of performing olefin autoxidations with O2 under solvent free and catalyst free conditions. Owing to the transparent reactor design consumption of O2 can be visually followed and exhaustion of the gas bubbles marks a clear end point along the channel length coo...

ATUCHA I NPP - Emergency drill practice

International Nuclear Information System (INIS)

Sanda, Alejandro; Rosales, Gabriel

2008-01-01

Full text: Atucha I NPP performs an Emergency Drill Practice once a year. Its main goals are: -) Fulfill the requirements of the Argentine Nuclear Regulatory Authority (ARN) regarding Atucha I NPP's Operating License; -) Fulfill the commitment with the community regarding the safe and reliable operation Atucha I NPP; -) Verify the response of the Civil Organizations, Security Forces, and Armed Forces, as well as the correct application of the Emergency Plan; -) Perform the 'General Alarm Drill' periodic control; -) Perform a re-training of the members of the Security Advisor Internal Committee (CIAS) on the Internal and External Aspects of the Emergency Plan and on the related procedures; -) Test the Emergency Communications System. New goals are added every year, considering the Drill's scope. This drill comprises two different kinds of practices: Internal practices (practices in the station, with our personnel) and external practices (practices outside the station with governmental organizations). Internal practices comprise: -) Internal and external communications practices; -) Acoustic alarms; -) Personnel gathering in the Meeting Points; -) Safety of selected Meeting Points; -) Personnel count, selective evacuation; -) Iodide Potassium pills distribution; -) CICE (Internal Group for Emergency Control) Coordination. External practices comprise: -) Nuclear Regulatory Authority; -) Argentine Navy, Comando Area Naval Fluvial, Base Naval Zarate; -) Lima firemen; -) Zarate firemen; -) Municipal Civil Defense (Zarate and Lima); -) National Guard, Escuadron Atucha; -) Zarate Regional Hospital; -) Lima Police Department; -) Zarate Police Department; -) Argentine Coast Guard, Zarate; -) Local radios: Radio FM Libre, FM El Sitio; -) First Aid clinic. The following activities are performed together with the aforementioned organizations: -) Formation of an 'Operative committee'; -) Evacuation of citizens in a 3 km radio; -) Control of every access to Lima; -) Control of

Kinetics of H-D exchange in olefins with complicating reactions

International Nuclear Information System (INIS)

Trokhimets, A.I.

1979-01-01

The kinetics of H-D-exchange is considered for olefins under conditions when simple and complicated exchange occur together with hydrogenation. If hydrogenation takes place in the system, it is theoretically impossible to derive the integrated rate equation for the accumulation of deuterium in the olefin. The variation of the concentration of different deuteroolefins during the process can be calculated numerically. A method is proposed for evaluating the contribution of individual steps to the overall process and determining the rate constants of the most important reactions. (author)

Advanced Drilling through Diagnostics-White-Drilling

International Nuclear Information System (INIS)

FINGER, JOHN T.; GLOWKA, DAVID ANTHONY; LIVESAY, BILLY JOE; MANSURE, ARTHUR J.; PRAIRIE, MICHAEL R.

1999-01-01

A high-speed data link that would provide dramatically faster communication from downhole instruments to the surface and back again has the potential to revolutionize deep drilling for geothermal resources through Diagnostics-While-Drilling (DWD). Many aspects of the drilling process would significantly improve if downhole and surface data were acquired and processed in real-time at the surface, and used to guide the drilling operation. Such a closed-loop, driller-in-the-loop DWD system, would complete the loop between information and control, and greatly improve the performance of drilling systems. The main focus of this program is to demonstrate the value of real-time data for improving drilling. While high-rate transfer of down-hole data to the surface has been accomplished before, insufficient emphasis has been placed on utilization of the data to tune the drilling process to demonstrate the true merit of the concept. Consequently, there has been a lack of incentive on the part of industry to develop a simple, low-cost, effective high-speed data link. Demonstration of the benefits of DWD based on a high-speed data link will convince the drilling industry and stimulate the flow of private resources into the development of an economical high-speed data link for geothermal drilling applications. Such a downhole communication system would then make possible the development of surface data acquisition and expert systems that would greatly enhance drilling operations. Further, it would foster the development of downhole equipment that could be controlled from the surface to improve hole trajectory and drilling performance. Real-time data that would benefit drilling performance include: bit accelerations for use in controlling bit bounce and improving rock penetration rates and bit life; downhole fluid pressures for use in the management of drilling hydraulics and improved diagnosis of lost circulation and gas kicks; hole trajectory for use in reducing directional

Stability of cracked naphthas from thermal and catalytic processes and their additive response. Part II. Composition and effect of olefinic structures

Energy Technology Data Exchange (ETDEWEB)

Nagpal, J.M.; Joshi, G.C.; Rastogi, S.N. [Indian Institute of Petroleum, Dehradun (India)

1995-05-01

Olefinic concentrates were separated from two naphthas, one from fluid catalytic cracking (FCC) and one thermal crackate, using column chromatography. The composition and structure of the olefins were determined by a combination of analytical techniques. FCC naphthas contain relatively higher levels of conjugated dienes. The monoolefins are highly branched. The thermal crackates have higher levels of {alpha}-olefins and abound in mono-, di-, tri- and conjugated cyclic olefins. Stability tests on these olefinic concentrates blended in low-S,N straight-run naphtha showed that cyclic olefins are very active gum formers. Representative commercial antioxidants (hindered phenols and phenylenediamines) both gave good responses to different olefin concentrate test blends. Hindered phenols had a marginally better effect. 14 refs., 5 figs., 3 tabs.

The conversion of biomass to light olefins on Fe-modified ZSM-5 catalyst: Effect of pyrolysis parameters.

Science.gov (United States)

Zhang, Shihong; Yang, Mingfa; Shao, Jingai; Yang, Haiping; Zeng, Kuo; Chen, Yingquan; Luo, Jun; Agblevor, Foster A; Chen, Hanping

2018-07-01

Light olefins are the key building blocks for the petrochemical industry. In this study, the effects of in-situ and ex-situ process, temperature, Fe loading, catalyst to feed ratio and gas flow rate on the olefins carbon yield and selectivity were explored. The results showed that Fe-modified ZSM-5 catalyst increased the olefins yield significantly, and the ex-situ process was much better than in-situ. With the increasing of temperature, Fe-loading amount, catalyst to feed ratio, and gas flow rate, the carbon yields of light olefins were firstly increased and further decreased. The maximum carbon yield of light olefins (6.98% C-mol) was obtained at the pyrolysis temperature of 600°C, catalyst to feed ratio of 2, gas flow rate of 100ml/min, and 3wt% Fe/ZSM-5 for cellulose. The selectivity of C 2 H 4 was more than 60% for all feedstock, and the total light olefins followed the decreasing order of cellulose, corn stalk, hemicelluloses and lignin. Copyright © 2018 Elsevier B.V. All rights reserved.

Optimizing drilling performance using a selected drilling fluid

Science.gov (United States)

Judzis, Arnis [Salt Lake City, UT; Black, Alan D [Coral Springs, FL; Green, Sidney J [Salt Lake City, UT; Robertson, Homer A [West Jordan, UT; Bland, Ronald G [Houston, TX; Curry, David Alexander [The Woodlands, TX; Ledgerwood, III, Leroy W.

2011-04-19

To improve drilling performance, a drilling fluid is selected based on one or more criteria and to have at least one target characteristic. Drilling equipment is used to drill a wellbore, and the selected drilling fluid is provided into the wellbore during drilling with the drilling equipment. The at least one target characteristic of the drilling fluid includes an ability of the drilling fluid to penetrate into formation cuttings during drilling to weaken the formation cuttings.

Proceedings of the DGMK-Conference 'Creating value from light olefins - production and conversion'. Authors' manuscripts

Energy Technology Data Exchange (ETDEWEB)

Emig, G; Kraemer, H J; Weitkamp, J [eds.

2001-07-01

Main topics of the conference were: production of light olefin by steamcracking and catalytic cracking processes, catalysts, methanol to olefin processes, oxidative dehydrogenation, partial oxidation, selective oxidation of alkanes with various catalysts. (uke)

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

2014-01-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert

2014-08-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

Methanol conversion to lower olefins over RHO type zeolite

KAUST Repository

Masih, Dilshad

2013-07-01

Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET specific surface area (812 m2 g-1), micropore volume (0.429 cm3 g-1), and acid amount (2.53 mmol g-1). Scanning electron microscopy observations showed small crystallites of about 1 μm. The zeolite was active for MTO reaction with 100% methanol conversions at 623-723 K, whereas selectivity to lower olefins changed with time. © 2013 Elsevier B.V.

A novel drill design for photoacoustic guided surgeries

Science.gov (United States)

Shubert, Joshua; Lediju Bell, Muyinatu A.

2018-02-01

Fluoroscopy is currently the standard approach for image guidance of surgical drilling procedures. In addition to the harmful radiation dose to the patient and surgeon, fluoroscopy fails to visualize critical structures such as blood vessels and nerves within the drill path. Photoacoustic imaging is a well-suited imaging method to visualize these structures and it does not require harmful ionizing radiation. However, there is currently no clinical system available to deliver light to occluded drill bit tips. To address this challenge, a prototype drill was designed, built, and tested using an internal light delivery system that allows laser energy to be transferred from a stationary laser source to the tip of a spinning drill bit. Photoacoustic images were successfully obtained with the drill bit submerged in water and with the drill tip inserted into a thoracic vertebra from a human cadaver.

Slimhole drilling and directional drilling for on-site inspections under a Comprehensive Test Ban - An initial assessment

International Nuclear Information System (INIS)

Heuze, F.E.

1995-07-01

It appears that a short list of four suppliers should be further evaluated to formulate OSI-applicable packages. They are Baker-Hughes ESTTEQ, SLIMDRIL International, Halliburton Energy/ENSCO Technology, and Schlumberger-Dowell/Anadrill. It is noteworthy that all of them are headquartered in Houston, TX, making it a logical place to present the OSI requirements to a community of expert drillers. We have requested from these companies that they let us know of operations with coiled tubing to be conducted in California, so as to use such opportunities to view the systems in action. On such job was just completed by Schlumberger-Dowell near Bakersfield, and they have another one coming up in late July in Long Beach. An example of the 'footprint' of such a C-T drilling operation is shown. The Verification community also can take advantage of drilling conferences to keep up with the state-of-the-art. The next such meeting, co-sponsored by the International Association of Drilling Contractors (IADC) and the Society of Petroleum Engineers (SPE), is scheduled for March 12-15, 1996, in New Orleans. The next step in this study should be to determine an optimal combination of the new drilling methods with the health and safety procedures and the diagnostics which are required when drilling in a radioactive environment. This will involve bringing together the expertise of the NTS/National Laboratories with those of the exploration/production drillers. The final outcome will be the formulation of drilling systems which have significant cost and weight advantages over those of the equipment previously used at NTS

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert; Cavallo, Luigi

2015-01-01

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert

2015-09-29

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

Cobalt carbide nanoprisms for direct production of lower olefins from syngas

Science.gov (United States)

Zhong, Liangshu; Yu, Fei; An, Yunlei; Zhao, Yonghui; Sun, Yuhan; Li, Zhengjia; Lin, Tiejun; Lin, Yanjun; Qi, Xingzhen; Dai, Yuanyuan; Gu, Lin; Hu, Jinsong; Jin, Shifeng; Shen, Qun; Wang, Hui

2016-10-01

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer-Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

Environment-friendly drilling operation technology

Science.gov (United States)

Luo, Huaidong; Jing, Ning; Zhang, Yanna; Huang, Hongjun; Wei, Jun

2017-01-01

Under the circumstance that international safety and environmental standards being more and more stringent, drilling engineering is facing unprecedented challenges, the extensive traditional process flow is no longer accepted, the new safe and environment-friendly process is more suitable to the healthy development of the industry. In 2015, CNPCIC adopted environment-friendly drilling technology for the first time in the Chad region, ensured the safety of well control, at the same time increased the environmental protection measure, reduced the risk of environmental pollution what obtain the ratification from local government. This technology carries out recovery and disposal of crude oil, cuttings and mud without falling on the ground. The final products are used in road and well site construction, which realizes the reutilization of drilling waste, reduces the operating cost, and provides a strong technical support for cost-cutting and performance-increase of drilling engineering under low oil price.

Ligand-Enabled γ-C(sp(3))-H Olefination of Amines: En Route to Pyrrolidines.

Science.gov (United States)

Jiang, Heng; He, Jian; Liu, Tao; Yu, Jin-Quan

2016-02-17

Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp(3))-H olefination reactions. The use of Ns protecting group to direct C(sp(3))-H activation of alkyl amines is also a significant step toward practical C-H functionalizations of alkyl amines.

Well drilling by rotary percussive drill above ground

International Nuclear Information System (INIS)

Sabatier, G.

1987-01-01

Originally, the Well Drilling Section of Cogema used only the diamond core drilling technique. The appearance of independent rotation for compressed air rock drills has led to the use and to the development of this drilling system, as a drill core is not indispensable, when the material of the search is radioactive. During the last few years, hydraulic drills have replaced the compressed air drills and have resulted in a very marked improvement: - of the penetration rates; - of the depth achieved. The Well Drilling Section of Cogema has to drill about 400 km per year with rock drills above ground and holds also the record for depth achieved with this technique, i.e. 400 m in granite. In France, the costs of these types of drilling are for the same depth of the order of one-quarter of the core drilling and half of the drilling with a down-the-hole drill. Cogema has greatly developed the types of well logging which now permits the extension of this type of drilling to the search for other materials than uranium [fr

Olefin metathesis in air

Directory of Open Access Journals (Sweden)

Lorenzo Piola

2015-10-01

Full Text Available Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

Environmental aspect of oil and water-based drilling muds and ...

African Journals Online (AJOL)

Administrator

2010-03-19

Mar 19, 2010 ... both oil based and water-based drilling wastes collected from the same depth were analyzed for metals. (iron, copper ... include well cuttings, drilling muds, formation water, cement slurry ..... in the drill wastes (2.38 mg/kg) (Figure 3d). The water .... Organization, International Programme on Chemical Safety.

Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

Science.gov (United States)

Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

2017-01-09

Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Avoiding pollution in scientific ocean drilling

International Nuclear Information System (INIS)

Francis, T.J.G.

1999-01-01

Scientific ocean drilling has been carried out in the world's oceans since the nineteen sixties. From 1968-83 the Deep Sea Drilling Project (DSDP), managed by the Scripps Institution of Oceanography in California under a contract with the US National Science Foundation, employed the drilling vessel Glomar Challenger for this purpose. In January 1985 the Ocean Drilling Program (GDP), operated by Texas A and M University, began operations with the drillship JOIDES Resolution which continue to this day. The principal funding agency remains the US National Science Foundation, but since its inception GDP has been an international program and currently receives financial support from 21 countries. The ODP operates globally and, as with DSDP before it, drills without a riser or blowout preventer in a wide range of geological environments. Water depths at GDP drill sites have ranged from 38 m to 5969 m, but are typically within the range 1000-5000 m. Depths of penetration at GDP drill sites, while generally less than 1000 m, have ranged up to 2111 m below the sea floor. The drilling fluid is seawater, although occasional slugs of mud are circulated to clean or condition the hole. Thus drilling is carried out without well control, i.e. without the ability to control pressures within the well. Because of the absence of well control, it is vital to ensure that the drillship does not drill into an accumulation of oil or gas. Drilling into a charged reservoir and causing oil or gas to escape into the marine environment is recognised as the main pollution hazard in scientific ocean drilling

Extreme ultraviolet (EUV) degradation of poly(olefin sulfone)s: Towards applications as EUV photoresists

International Nuclear Information System (INIS)

Lawrie, Kirsten; Blakey, Idriss; Blinco, James; Gronheid, Roel; Jack, Kevin; Pollentier, Ivan; Leeson, Michael J.; Younkin, Todd R.; Whittaker, Andrew K.

2011-01-01

Poly(olefin sulfone)s, formed by the reaction of sulfur dioxide (SO 2 ) and an olefin, are known to be highly susceptible to degradation by radiation and thus have been identified as candidate materials for chain scission-based extreme ultraviolet lithography (EUVL) resist materials. In order to investigate this further, the synthesis and characterisation of two poly(olefin sulfone)s namely poly(1-pentene sulfone) (PPS) and poly(2-methyl-1-pentene sulfone) (PMPS), was achieved and the two materials were evaluated for possible chain scission EUVL resist applications. It was found that both materials possess high sensitivities to EUV photons; however; the rates of outgassing were extremely high. The only observed degradation products were found to be SO 2 and the respective olefin suggesting that depolymerisation takes place under irradiation in a vacuum environment. In addition to depolymerisation, a concurrent conversion of SO 2 moieties to a sulfide phase was observed using XPS.

Radiation-induced terpolymerization of methyl α,β,β-trifluoroacrylate with tetrafluoroethylene and α-olefin

International Nuclear Information System (INIS)

Matsuda, O.; Watanabe, T.; Tabata, Y.; Machi, S.

1980-01-01

Radiation-induced terpolymerizations of methyl α,β,β-trifluoroacrylate (MTFA) with tetrafluoroethylene (TFE) and α-olefins, such as ethylene, propylene, and isobutylene, were carried out in bulk at 25 0 C for the purpose of controlling the content of ester group in the MTFA-α-olefin alternating copolymers. These monomers polymerized to form alternating terpolymers which contained 50 mole % α-olefin in a wide range of monomer composition. The content of MTFA, namely, the ester group in polymer, can be varied without destruction of the alternating structures between fluoroolefins (MTFA, TFE) and α-olefin by changing the MTFA/TFE ratio in the monomer mixture. The relative reactivities of MTFA and TFE in the terpolymerization were discussed according to kinetic treatments by free propagating and complex mechanisms. The relation between the MTFA/TFE ratio in the monomer mixture and that in terpolymer was explained favorably by the complex mechanism. It was also concluded that the relative reactivity of MTFA is larger than that of TFE in the terpolymerizations

Stereoselective Wittig Olefination as a Macrocyclization Tool. Synthesis of Large Carbazolophanes.

Science.gov (United States)

Myśliwiec, Damian; Lis, Tadeusz; Gregoliński, Janusz; Stępień, Marcin

2015-06-19

Z-Selective Wittig olefination was applied to the synthesis of large carbazolophanes containing up to eight heteroaromatic subunits. A number of strategies were devised and tested, showing that cyclooligomerization yields can be significantly improved by using one-component schemes involving heterobifunctional reactants. [4]- and [6]Carbazolophanes were characterized in the solid state, revealing compact, highly folded structures. Electronic and steric effects of substitution and chain length on the Wittig olefination rates and Z-selectivities were explored theoretically using DFT calculations.

Olefin copolymerization via reversible addition-fragmentation chain transfer

NARCIS (Netherlands)

Venkatesh, R.; Staal, B.B.P.; Klumperman, B.

2004-01-01

Successful statistical copolymn. of an a-olefin (1-octene) with an acrylate (Bu acrylate, BA) and with a methacrylate (Me methacrylate, MMA), employing reversible addn.-fragmentation chain transfer (RAFT) mediated polymn. has been accomplished

Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

OpenAIRE

Kenji Michiue; Makoto Mitani; Terunori Fujita

2015-01-01

In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’)2]ZrCl2 (Indenyl’ = generic substituted indenyl), after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenyl)zirconium dichloride (1), rac-dimethyls...

Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

Science.gov (United States)

Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

2017-01-18

Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

New Trends in Olefin Production

Directory of Open Access Journals (Sweden)

Ismaël Amghizar

2017-04-01

Full Text Available Most olefins (e.g., ethylene and propylene will continue to be produced through steam cracking (SC of hydrocarbons in the coming decade. In an uncertain commodity market, the chemical industry is investing very little in alternative technologies and feedstocks because of their current lack of economic viability, despite decreasing crude oil reserves and the recognition of global warming. In this perspective, some of the most promising alternatives are compared with the conventional SC process, and the major bottlenecks of each of the competing processes are highlighted. These technologies emerge especially from the abundance of cheap propane, ethane, and methane from shale gas and stranded gas. From an economic point of view, methane is an interesting starting material, if chemicals can be produced from it. The huge availability of crude oil and the expected substantial decline in the demand for fuels imply that the future for proven technologies such as Fischer-Tropsch synthesis (FTS or methanol to gasoline is not bright. The abundance of cheap ethane and the large availability of crude oil, on the other hand, have caused the SC industry to shift to these two extremes, making room for the on-purpose production of light olefins, such as by the catalytic dehydrogenation of propane.

Olefin Recovery from Chemical Industry Waste Streams

Energy Technology Data Exchange (ETDEWEB)

A.R. Da Costa; R. Daniels; A. Jariwala; Z. He; A. Morisato; I. Pinnau; J.G. Wijmans

2003-11-21

The objective of this project was to develop a membrane process to separate olefins from paraffins in waste gas streams as an alternative to flaring or distillation. Flaring these streams wastes their chemical feedstock value; distillation is energy and capital cost intensive, particularly for small waste streams.

Study for increasing micro-drill reliability by vibrating drilling

International Nuclear Information System (INIS)

Yang Zhaojun; Li Wei; Chen Yanhong; Wang Lijiang

1998-01-01

A study for increasing micro-drill reliability by vibrating drilling is described. Under the experimental conditions of this study it is observed, from reliability testing and the fitting of a life-distribution function, that the lives of micro-drills under ordinary drilling follow the log-normal distribution and the lives of micro-drills under vibrating drilling follow the Weibull distribution. Calculations for reliability analysis show that vibrating drilling can increase the lives of micro-drills and correspondingly reduce the scatter of drill lives. Therefore, vibrating drilling increases the reliability of micro-drills

At the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.

Science.gov (United States)

Rangheard, Claudine; de Julián Fernández, César; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; de Vries, Johannes G

2010-09-28

The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and alkynes. Olefin hydrogenation is relatively fast at 5 bar using 5 mol% of catalyst. The catalyst is also active for terminal olefins and 1,1' and 1,2-cis disubstituted olefins while trans-olefins react much slower. 1-Octyne is hydrogenated to mixtures of 1-octene and octane. Kinetic studies led us to propose a mechanism for this latter transformation where octane is obtained by two different pathways. Characterization of the nanoparticles via TEM, magnetic measurements and poisoning experiments were undertaken to understand the true nature of our catalyst.

Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

Science.gov (United States)

Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

2018-03-26

Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of surfactant application for synthetic drilling fluid; Otimizacao da aplicacao de emulsificante em fluidos de perfuracao sinteticos

Energy Technology Data Exchange (ETDEWEB)

Arruda, Jefferson Teixeira [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Santos, Telma Pitanga; Medeiros, Ana Catarina da Rocha; Garcia, Rosangela Balaban [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Lab. de Pesquisa em Petroleo

2008-07-01

The most common synthetic drilling fluids are made of polymerized olefins, paraffin and esters, which have absence of aromatics hydrocarbons and biodegradability as advantages. These fluids have good performance during the drilling operations (high thermal stability) and have low toxicity. Nevertheless, their big disadvantage is the high cost, which limits their use. One of the biggest challenges in working with synthetic fluids is the control of water/oil emulsion stability, being the surfactant the main agent responsible for keeping this stability between both phases of the fluid. The water/oil and oil/water emulsion is defined by the chemical nature of the surfactant. The emulsions can be changed from oil/water to water/oil and vice versa by many mechanisms, such as temperature variation, addition of another surfactant and alteration of the disperse phase volumetric percentage. The aim of this work was the optimization of synthetic drilling fluids formulations by using commercial surfactants. The optimized formulations showed similar rheological properties. After aging at high temperature (300 deg F), some tendency to migration of oil phase in both fluids was observed. This result was associated to the fluid's viscosity. However, the formulations showed high electrical stability, indicating formation of stable emulsions. The HTHP filtration volumes were small. (author)

On the impact of olefins and aromatics in the methanol-to-hydrocarbon conversion over H-ZSM-5 catalysts

Energy Technology Data Exchange (ETDEWEB)

Sun, X.; Mueller, S.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

2012-07-01

Methanol-to-hydrocarbons processes using HZSM-5 archetype acidic zeolites or zeotype SAPO-34 catalysts are regarded as a vital suite of conversion technologies to bypass petroleum-based routes for the production of specific fuels and petrochemical commodities. Special significance of the methanol chemistry originates from its versatility enabling selective transformations towards various products. Industry demonstrated successfully implementations of Methanol-To-Gasoline, Methanol-To-Olefin, and Methanol-To-Propylene processes, although the typical single-pass selectivity remained limited and recycling is necessary. Considerable fundamental research efforts both from experimental and computational sides contributed to unravel the underlying complex reaction mechanism. The indirect hydrocarbon pool mechanism, in which Broensted acid sites combined with adsorbed light olefins or lower methylbenzenes act as active centers, is generally accepted to explain the formation of light olefins. As olefin and aromatics populated catalytic sites show different reactivity in terms of activity and selectivity to ethylene or propylene, one could envision optimizing the product distribution by suitable co-feeding of specific hydrocarbons. The present work addresses three questions with an experimental study conducted under realistic MTP operation conditions: (1) How are ethylene and propylene formed at molecular level? (2) Which reaction pathway leads to the formation of undesired hydrogen transfer products? (3) Does olefin or aromatics co-feeding change the selectivity to ethylene or propylene? Xylenes and various olefins were co-fed with methanol to achieve a detailed understanding of the reaction mechanism over acidic HZSM-5 zeolites. Results suggest, that an olefin homologation/cracking route (olefin cycle) accounts for the autocatalytic (-like) nature and the majority of methanol consumption rather than the route involving aromatic intermediates (aromatics cycle). Co

Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

Directory of Open Access Journals (Sweden)

Yasutaka Ishii

2010-03-01

Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

Science.gov (United States)

Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

2012-12-01

Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Olefins from conventional and heavy feedstocks: Energy use in steam cracking and alternative processes

International Nuclear Information System (INIS)

Ren Tao; Patel, Martin; Blok, Kornelis

2006-01-01

Steam cracking for the production of light olefins, such as ethylene and propylene, is the single most energy-consuming process in the chemical industry. This paper reviews conventional steam cracking and innovative olefin technologies in terms of energy efficiency. It is found that the pyrolysis section of a naphtha steam cracker alone consumes approximately 65% of the total process energy and approximately 75% of the total exergy loss. A family portrait of olefin technologies by feedstocks is drawn to search for alternatives. An overview of state-of-the-art naphtha cracking technologies shows that approximately 20% savings on the current average process energy use are possible. Advanced naphtha cracking technologies in the pyrolysis section, such as advanced coil and furnace materials, could together lead to up to approximately 20% savings on the process energy use by state-of-the-art technologies. Improvements in the compression and separation sections could together lead to up to approximately 15% savings. Alternative processes, i.e. catalytic olefin technologies, can save up to approximately 20%

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

International Nuclear Information System (INIS)

Kawaguchi, M.; Watanabe, T.; Matsuda, O.; Tabata, Y.; Machi, S.

1981-01-01

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25 0 C, a dose rate of 1 x 10 6 rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene were nearly 1/2 over a wide range of the monomer compositions. The Mayo-Lewis method gave negative r 1 (FVA) and r 1 (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model

Ozonolysis of Model Olefins-Efficiency of Antiozonants

NARCIS (Netherlands)

Huntink, N.M.; Datta, Rabin; Talma, Auke; Noordermeer, Jacobus W.M.

2006-01-01

In this study, the efficiency of several potential long lasting antiozonants was studied by ozonolysis of model olefins. 2-Methyl-2-pentene was selected as a model for natural rubber (NR) and 5-phenyl-2-hexene as a model for styrene butadiene rubber (SBR). A comparison was made between the

77 FR 71607 - Mobile Offshore Drilling Unit (MODU) Electrical Equipment Certification Guidance

Science.gov (United States)

2012-12-03

... DEPARTMENT OF HOMELAND SECURITY Coast Guard [Docket No. USCG-2012-0839] Mobile Offshore Drilling... hazardous areas on foreign-flagged Mobile Offshore Drilling Units (MODUs) that have never operated, but... International Maritime Organization (IMO) Code for the Construction and Equipment of Mobile Offshore Drilling...

A method for producing lower olefins

Energy Technology Data Exchange (ETDEWEB)

Lemayev, N.V.; Grigorovich, V.A.; Isayev, V.A.; Liakumovich, A.G.; Mitrofanov, A.I.; Orekhov, A.I.; Trifonov, S.V.; Vernov, P.A.

1983-01-01

In the known method for producing lower olefins by pyrolysis of a hydrocarbon raw material in the presence of an initiator which contains ammonia, in order to increase the output of the target products, morpholine or piperidine are additionally introduced into the initiator in a volume of 0.00001 to 0.1 percent each, converted for the raw material. The compounds to be added may be introduced into the pyrolysis zone by dissolving them in the hydrocarbon raw material or in water, which forms vapors with dilution of the raw material being subjected to pyrolysis. The increase in the outputs of the lower olefins in the process through the use of additives may be explained by the synergistic effect of the mixture of ammonia, morpholine and piperidine used. With benzine pyrolysis without the additives the output of ethylene is 24.1 percent; in comparable conditions with additives of ammonia or morpholine alone, or of piperidine alone, the outputs are 24.0, 26.2 and 25.8 percent, respectively. With the joint presence of ammonia and piperidine, the output of ethylene reaches 27.2 percent and with the addition of ammonia and morpholine, it reaches 27.4 percent.

Co-Aromatization of Methane with Olefins: The Role of Inner Pore and External Surface Catalytic Sites

Energy Technology Data Exchange (ETDEWEB)

Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); He, Peng [University of Calgary; Jarvis, Jack [University of Calgary; Meng, Shijun [University of Calgary; Wang, Aiguo [University of Calgary; Kou, Shiyu [University of Calgary; Gatip, Richard [University of Calgary; Liu, Lijia [Soochow University; Song, Hua [University of Calgary

2018-04-22

The co-aromatization of methane with olefins is investigated using Ag-Ga/HZSM-5 as the catalyst at 400 degrees C. The presence of methane has a pronounced effect on the product distribution in terms of increased average carbon number and substitution index and decreased aromatic carbon fraction compared with its N2 environment counterpart. The participation of methane during the co-aromatization over the Ag-Ga/HZSM-5 catalyst diminishes as the co-fed olefin feedstock molecule becomes larger, from 1-hexene to 1-octene and 1-decene, in diameter. The effect of suppressed methane participation with larger olefinic molecules is not as significant when Ag-Ga/HY is employed as the catalyst, which might be attributed to the larger pore size of HY that gives more room to hold olefin and methane molecules within the inner pores and reduces the diffusion limitation of olefin molecules. The effect of olefin feedstock on the methane participation during the co-aromatization over Ag-Ga/HZSM-5 is experimentally evidenced by 13C and 2D NMR. The incorporation of the methane carbon atoms into the phenyl ring of product molecules is reduced significantly with larger co-fed olefins, whereas its incorporation into the substitution groups of the formed aromatic molecules is not notably affected, suggesting that the methane participation in the phenyl ring formation might preferably occur within inner pores, while its incorporation into substitution groups may mainly take place on external catalytic sites. This hypothesis is well supported by the product selectivity obtained over Ag-Ga/HZSM-5 catalysts prepared using conventional ZSM-5, ZSM-5 with the external catalytic sites deactivated, nanosize ZSM-5, ZSM-5 with a micro/meso pore structure and ZSM-5 with the inner pores blocked, and further confirmed by the isotopic labeling studies.

NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

CERN Document Server

1998-01-01

The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

International Nuclear Information System (INIS)

Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

1982-01-01

By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

Science.gov (United States)

Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

2017-02-01

A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

75 FR 8113 - Drill Pipe From China

Science.gov (United States)

2010-02-23

... INTERNATIONAL TRADE COMMISSION [Investigation Nos. 701-TA-474 and 731-TA-1176 (Preliminary)] Drill Pipe From China AGENCY: United States International Trade Commission. ACTION: Revised schedule for the subject antidumping and countervailing duty investigations. DATES: Effective Date: February 16, 2010. FOR...

Optimization of catalytic glycerol steam reforming to light olefins using Cu/ZSM-5 catalyst

International Nuclear Information System (INIS)

Zakaria, Z.Y.; Amin, N.A.S.; Linnekoski, J.

2014-01-01

Highlights: • Glycerol steam reforming to light olefin using Cu/ZSM-5 process was optimized. • Response surface methodology and multi-objective genetic algorithm were employed. • Second order polynomial model produced adequately fitted experimental data. • Thermodynamic study inferred high temperature requirement for ethylene formation. • Turn-over-frequency at optimized responses is higher than the non-optimized process. - Abstract: Response surface methodology (RSM) and multi-objective genetic algorithm was employed to optimize the process parameters for catalytic conversion of glycerol, a byproduct from biodiesel production, to light olefins using Cu/ZSM-5 catalyst. The effects of operating temperature, weight hourly space velocity (WHSV) and glycerol concentration on light olefins selectivity and yield were observed. Experimental results revealed the data adequately fitted into a second-order polynomial model. The linear temperature and quadratic WHSV terms gave significant effect on both responses. Optimization of both the responses indicated that temperature favouring high light olefin formation lied beyond the experimental design range. The trend in the temperature profile concurred commensurately with the thermodynamic analysis. Multi-objective genetic algorithm was performed to attain a single set of processing parameters that could produce both the highest light olefin selectivity and yield. The turn-over-frequency (TOF) of the optimized responses demonstrated a slightly higher value than the one which was not optimized. Combination of RSM, multi-objective response and thermodynamic is useful to determine the process optimal operating conditions for industrial applications

Pressured drilling riser design for drilling in ultra deep water with surface bop

Energy Technology Data Exchange (ETDEWEB)

Zhang, J.; Morrison, D.; Efthymiou, M.; Lo, K.H. [Shell Global Solutions, 78 - Velizy Villacoublay (France); Magne, E.; Leach, C. [Shell Internationale Exploration and Production (Netherlands)

2002-12-01

In conventional drilling with a semi-submersible rig valuable rig time is used to run and retrieve the BOP and its accessories on the seabed, and this time increases with water depth. Furthermore, use of the conventional sub-sea BOP requires a large-diameter riser, which requires substantial rig storage and deck load capacity prior to installation. It also requires high riser-tensioning capacity or additional buoyancy. Thus as the water depth increases, it leads to a need for heavy duty 4. and 5. generation rigs with escalation in costs. The high cost of deep-water drill rigs is leading to the development of Surface BOP technology. In this development, the BOP is placed above sea level and the riser is simply a continuation of the casing (typical diameter 13-3/8''). This eliminates the need for a heavy 21'' riser and for running the BOP to the sea bed and retrieving it. Moreover, the reduced tension requirement for the smaller riser extends the water depth capability of 3. generation drilling semi-submersibles, enabling them to drill in deeper waters. A critical success factor for this development is the ability to design the riser/casing to withstand high internal pressures due to well kicks, in addition to environmental loads, and to restrict vessel offsets within certain limits so as not to overload the riser under the prevailing weather conditions. This paper addresses the design considerations of a pressured drilling riser that can be used with a surface BOP in deep-water. Key design issues that are sensitive to ultra-deep-water applications are discussed. The technical aspects of using (disposable) standard casing with threaded connector for the drilling riser are discussed, with a particular emphasis on the connector fatigue-testing program to quantify the stress concentration factor for fatigue design. Emerging composite material offers some alternatives to the steel riser when drilling in ultra-deep water Design issues related to the

Ligand-Enabled γ-C(sp3)–H Olefination of Amines: En Route to Pyrrolidines

Science.gov (United States)

Jiang, Heng; He, Jian; Liu, Tao

2016-01-01

Pd(II)-catalyzed olefination of γ-C(sp3)–H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp3)–H olefination reaction. The use of Ns protecting group to direct C(sp3)–H activation of alkyl amine is also a significant step towards practical C–H functionalizations of alkyl amines. PMID:26796676

Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

Science.gov (United States)

Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

2010-01-01

A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

Synthesis of thermoplastic poly(ester-olefin elastomers

Directory of Open Access Journals (Sweden)

Tanasijević Branka

2004-01-01

Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

U.S. drilling contractors could face stiff challenges

International Nuclear Information System (INIS)

Simmons, M.R.

1993-01-01

Although the outlook for most segments of the contract drilling business is now more optimistic than in the past decade, the increased activity has brought several problems: the availability of fully trained crews, the need for new capital, and the limited number of quality drillstrings. These problems will grow in importance if natural gas deliverability begins to decline visibly and once the scramble to correct this decline begins. As the drilling recovery unfolds, the most important lesson to remember, based on worldwide activity in the past year, is how rapidly conditions can change and how quickly excess capacity can turn into chronic shortages. The various segments of the world wide contract drilling industry's prospects have changed dramatically during the past 12 months, and oddly, some market sectors have improved while others have become worse. These quick changes highlight the unpredictable and volatile nature of the markets for contract drilling and other services needed to drill and complete oil and gas wells. The paper describes the business of well drilling onshore and offshore in the US, drilling activities in Canada, international markets, capacity, the supplies of natural gas, Gulf of Mexico activities, drill pipe shortages, manpower shortages, and challenges offshore

Ligand-Promoted C(sp(3) )-H Olefination en Route to Multi-functionalized Pyrazoles.

Science.gov (United States)

Yang, Weibo; Ye, Shengqing; Schmidt, Yvonne; Stamos, Dean; Yu, Jin-Quan

2016-05-17

A Pd-catalyzed/N-heterocycle-directed C(sp(3) )-H olefination has been developed. The monoprotected amino acid ligand (MPAA) is found to significantly promote Pd-catalyzed C(sp(3) )-H olefination for the first time. Cu(OAc)2 instead of Ag(+) salts are used as the terminal oxidant. This reaction provides a useful method for the synthesis of alkylated pyrazoles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

KAUST Repository

Urbina-Blanco, Cé sar A.; Poater, Albert; Lé bl, Tomá š; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

2013-01-01

Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

KAUST Repository

Urbina-Blanco, César A.

2013-05-08

Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

IODP New Ventures in Exploring Scientific Targets (INVEST: Defining the New Goals of an International Drilling Program

Directory of Open Access Journals (Sweden)

Fumio Inagaki

2010-04-01

Full Text Available The INVEST conference, an international meeting to define the scientific goals and required technology for a new ocean drilling program, was held at the University of Bremen on 22–25 September 2009. Based on the large attendance and vigorous engagement of scientists in the discussion of new science/technology ideas, INVEST was extremely successful. Initially 400 participants were expected, but the INVEST steering and organization committees were thrilled to see a much larger number of scientists flock to Bremen to demonstrate their support and enthusiasm for the continuation of an international scientific ocean drilling program. In all, 584 participants, including sixty-four students, from twenty-one nations and >200 institutions and agencies attended the INVEST conference. Contributions to INVEST included 103 submitted white papers that were posted on the INVEST webpage (http://www.marum.de/iodp-invest. html, and breakout discussions in fifty working groups that focused on a range of topics during the course of the conference. In addition, students and early career scientists, as well as national funding agency managers and platform providers, presented a total of eighty-six posters. Interspersed with the working group and plenary sessions were twelve keynote lectures, chosen to highlight overarching themes and new directions in research and technology.

76 FR 5319 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

Science.gov (United States)

2011-01-31

... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... gasoline. This proposed rule will provide flexibility to the regulated community by allowing an additional... A. Alternative Test Method for Olefins in Gasoline III. Statutory and Executive Order Reviews A...

76 FR 65382 - Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline

Science.gov (United States)

2011-10-21

... Regulation of Fuel and Fuel Additives: Alternative Test Method for Olefins in Gasoline AGENCY: Environmental... gasoline. This final rule will provide flexibility to the regulated community by allowing an additional... Method for Olefins in Gasoline III. Statutory and Executive Order Reviews A. Executive Order 12866...

Catalytic polymerization of olefins in supercritical carbon dioxide

NARCIS (Netherlands)

Kemmere, M.F.; Vries, de T.J.; Keurentjes, J.T.F.

2004-01-01

A novel process is being developed for the catalytic polymerization of olefins in supercritical carbon dioxide (sc CO2), for which potential applications will mainly be in the production of EPDM and other elastomers. For this purpose, the Brookhart catalyst has been tested for the homopolymerization

Synthesis of o-Alkenylated 2-Arylbenzoxazoles via Rh-Catalyzed Oxidative Olefination of 2-Arylbenzoxazoles: Scope Investigation, Structural Features, and Mechanism Studies.

Science.gov (United States)

Zhou, Quan; Zhang, Jing-Fan; Cao, Hui; Zhong, Rui; Hou, Xiu-Feng

2016-12-16

2-Arylbenzazoles are promising molecules for potential applications in medicine and material areas. Efficient protocols for direct regioselective functionalization of 2-arylbenzoxazoles are in high demand. Herein, we disclose a general method for selective ortho-olefination of 2-arylbenzo[d]oxazoles with alkenes enabled by versatile Cp*Rh(III) in high yields. This protocol features broad functional group tolerance and high regioselectivity. Intermolecular competition studies and kinetic isotope effect experiments imply that the oxidative olefination process occurs via an electrophilic C-H activation pathway. The molecular structure of the m-fluoro-substituted olefination product confirms regioselective C-H activation/olefination at the more hindered site in cases where the meta F atom or heteroatom substituent existed. Apparent torsion angles were observed in the structures of mono- and bis-olefination products, which resulted in distinct different chemical shifts of olefinic protons. Additionally, two gram-scale reactions and further transformation experiments demonstrate that this method is practical for synthesis of ortho-alkenylated 2-arylbenzoxazole derivatives.

Finite element modeling and experimentation of bone drilling forces

International Nuclear Information System (INIS)

Lughmani, W A; Bouazza-Marouf, K; Ashcroft, I

2013-01-01

Bone drilling is an essential part of many orthopaedic surgery procedures, including those for internal fixation and for attaching prosthetics. Estimation and control of bone drilling forces are critical to prevent drill breakthrough, excessive heat generation, and mechanical damage to the bone. This paper presents a 3D finite element (FE) model for prediction of thrust forces experienced during bone drilling. The model incorporates the dynamic characteristics involved in the process along with the accurate geometrical considerations. The average critical thrust forces and torques obtained using FE analysis, for set of machining parameters are found to be in good agreement with the experimental results

Automatic real time drilling support on Ekofisk utilizing eDrilling

Energy Technology Data Exchange (ETDEWEB)

Rommetveit, Rolv; Bjorkevoll, Knut S.; Halsey, George W.; Kluge, Roald; Molde, Dag Ove; Odegard, Sven Inge [SINTEF Petroleum Research, Trondheim (Norway); Herbert, Mike [HITEC Products Drilling, Stavanger (Norway); ConocoPhillips Norge, Stavanger (Norway)

2008-07-01

eDrilling is a new and innovative system for real time drilling simulation, 3D visualization and control from a remote drilling expert centre. The concept uses all available real time drilling data (surface and downhole) in combination with real time modelling to monitor and optimize the drilling process. This information is used to visualize the wellbore in 3D in real time. eDrilling has been implemented in an Onshore Drilling Center in Norway. The system is composed of the following elements, some of which are unique and ground-breaking: an advanced and fast Integrated Drilling Simulator which is capable to model the different drilling sub-processes dynamically, and also the interaction between these sub-processes in real time; automatic quality check and corrections of drilling data; making them suitable for processing by computer models; real time supervision methodology for the drilling process using time based drilling data as well as drilling models / the integrated drilling simulator; methodology for diagnosis of the drilling state and conditions. This is obtained from comparing model predictions with measured data. Advisory technology for more optimal drilling. A Virtual Wellbore, with advanced visualization of the downhole process. Dat low and computer infrastructure. e-Drilling has been implemented in an Onshore Drilling Center on Ekofisk in Norway. The system is being used on drilling operations, and experiences from its use are presented. The supervision and diagnosis functionalities have been useful in particular, as the system has given early warnings on ECD and friction related problems. This paper will present the eDrilling system as well as experiences from its use. (author)

Rhodium(I) catalysis in olefin photoreactions

International Nuclear Information System (INIS)

Salomon, R.G.; El Sanadi, N.

1975-01-01

The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

An Improved Protocol for the Aldehyde Olefination Reaction Using (bmim ( as Reaction Medium

Directory of Open Access Journals (Sweden)

Vivek Srivastava

2013-01-01

Full Text Available [Ru(CODCl2]/CuCl2·2H2O/LiCl catalytic system works efficiently in ionic liquid media for aldehyde olefination reaction. It offers good yield and selectivity with the added advantage of 5 times recyclability for [Ru(CODCl2] /CuCl2·2H2O/LiCl catalytic system. We also successfully reduced the reaction time from 12 hours to 9 hours for the aldehyde olefination reaction.

General regularities of olefin epoxidation by hydroperoxide catalyzed by V, W and Ti compounds

International Nuclear Information System (INIS)

Sapunov, V.N.; Sharykin, V.G.; Logvinov, A.S.; Litvintsev, I.Yu.; Lebedev, N.N.

1983-01-01

The kinetic analysis of cyclohexane epoxidation by ethylbenzene hydroperoxide when catalyzed by titanium- and tungsten cyclohexandiolates has shown that the reaction follows the main regularities of hydroperoxide epoxidation previously established for catalysis by molybdenum- and vanadiUm compounds. The catalyst activity varies depending on the metal nature and forms the following series: Mo>V>W>Ti, which agrees with their π-acceptor capacity. During the cyclohexane epoxidation on all catalysts the hydroperoxide activities vary according to the following series: ethylbenzene hydroperoxide>cumene>tertiarybutyl>tertiaryamyl. Correlation relationships between the olefine structure, characterized by th constants, and the reactivity of olefines are foUnd. The reaction sensitivity during catalysis by WV, and Ti cyclohexandiolates is -1.2, -1.0- and -1.3, respectively. The mechanism of hydroperoxide epoxidation of olefine is discussed

Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

Energy Technology Data Exchange (ETDEWEB)

Cheng, Yu-Ting; Huber, George W.

2011-06-03

The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysis–mass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/Al ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO₂, aromatics, and olefins at temperatures from 400 to 600 °C. Aromatics (e.g., benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C₁₂{sub +} oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 min of time on-stream. We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO₂, allene, C₂–C₆ olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 °C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450–600 °C). At low temperatures (450 °C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include Diels–Alder condensation (e.g., two furans form benzofuran and water

The effect of ultralow temperature on olefin cation formation by ionic fragmentation in the radiolysis of 2,3-dimethylbutane

International Nuclear Information System (INIS)

Miyazaki, Tetsuo

1991-01-01

The formation of olefin cations in the radiolysis of 2,3-dimethylbutane (DMB) was studied by ESR at 4.2 and 77 K. When a DMB-SF 6 mixture is γ-irradiated at 77 K, tetramethylethylene (TME) cations are formed remarkably. The formation of the TME cations, however, is suppressed at 4.2 K. When the DMB-SF 6 mixture is γ-irradiated at 4.2 K and then warmed to 77 K, TME cations are formed by thermal annealing. The TME cations are not formed by a charge transfer to olefinic impurities or olefinic products in radiolysis, but by H 2 elimination from parent DMB cations in the ground state. The remarkable formation of olefin cations at 77 K corresponds to the large yields of unsaturated dimers in the radiolysis of DMB at 77 K. The suppression of olefin cation formation at 4.2 K corresponds to the low yields of unsaturated dimers in the radiolysis of DMB at 4.2 K. (author)

Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

National Research Council Canada - National Science Library

Low, Tammy K

2006-01-01

.... Our research goals consisted of employing olefin metathesis in the synthesis of peptidomimetics, and studying the feasibility of this method in dynamic combinatorial chemistry and molecular imprinting of nerve agents...

New drilling optimization technologies make drilling more efficient

Energy Technology Data Exchange (ETDEWEB)

Chen, D.C.-K. [Halliburton Energy Services, Calgary, AB (Canada). Sperry Division

2004-07-01

Several new technologies have been adopted by the upstream petroleum industry in the past two decades in order to optimize drilling operations and improve drilling efficiency. Since financial returns from an oil and gas investment strongly depend on drilling costs, it is important to reduce non-productive time due to stuck pipes, lost circulation, hole cleaning and well bore stability problems. The most notable new technologies are the use of computer-based instrumentation and data acquisition systems, integrated rig site systems and networks, and Measurement-While-Drilling and Logging-While-Drilling (MWD/LWD) systems. Drilling optimization should include solutions for drillstring integrity, hydraulics management and wellbore integrity. New drilling optimization methods emphasize information management and real-time decision making. A recent study for drilling in shallow water in the Gulf of Mexico demonstrates that trouble time accounts for 25 per cent of rig time. This translates to about $1.5 MM U.S. per well. A reduction in trouble time could result in significant cost savings for the industry. This paper presents a case study on vibration prevention to demonstrate how the drilling industry has benefited from new technologies. 13 refs., 10 figs.

Proceedings of the DGMK-Conference 'Creating value from light olefins - production and conversion'. Authors' manuscripts

Energy Technology Data Exchange (ETDEWEB)

Emig, G.; Kraemer, H.J.; Weitkamp, J. (eds.)

2001-07-01

Main topics of the conference were: production of light olefin by steamcracking and catalytic cracking processes, catalysts, methanol to olefin processes, oxidative dehydrogenation, partial oxidation, selective oxidation of alkanes with various catalysts. (uke)

On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

Energy Technology Data Exchange (ETDEWEB)

Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

1992-03-25

Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

Casing drilling

Energy Technology Data Exchange (ETDEWEB)

Heenan, D. [Tesco Corp., Calgary, AB (Canada)

2003-07-01

This paper reviewed the experience that Tesco has gained by drilling several wells using only casings as the drill stem. Tesco has manufactured a mobile and compact hydraulic drilling rig called the Casing Drilling {sup TM} system. The system could be very effective and efficient for exploration and development of coalbed methane (CBM) reserves which typically require extensive coring. Continuous coring while drilling ahead, along wire line retrieval, can offer time savings and quick core recovery of large diameter core which is typically required for exploration core desorption tests. The proposed system may also have the potential to core or drill typically tight gas sands or underbalanced wells with air or foam. This would reduce drilling fluid damage while simultaneously finding gas. Compared to conventional drill pipes, Casing Drilling {sup TM} could also be effective with water production from shallow sands because of the smaller annual clearance which requires less air volumes to lift any produced water. 9 figs.

Nitrogen-Doped Carbon Encapsulated Nickel/Cobalt Nanoparticle Catalysts for Olefin Migration of Allylarenes

DEFF Research Database (Denmark)

Kramer, Søren; Mielby, Jerrik Jørgen; Buss, Kasper Spanggård

2017-01-01

Olefin migration of allylarenes is typically performed with precious metal-based homogeneous catalysts. In contrast, very limited progress has been made using cheap, earth-abundant base metals as heterogeneous catalysts for these transformations - in spite of the obvious economic and environmental...... advantages. Herein, we report on the use of an easily prepared heterogeneous catalyst material for the migration of olefins, in particular allylarenes. The catalyst material consists of nickel/cobalt alloy nanoparticles encapsulated in nitrogen-doped carbon shells. The encapsulated nanoparticles are stable...

Drilling Information System (DIS and Core Scanner

Directory of Open Access Journals (Sweden)

Ronald Conze

2016-04-01

Full Text Available The Drilling Information System is a modular structure of databases, tailored user applications as well as web services and instruments including appropriate interfaces to DIS. This tool set has been developed for geoscientific drilling projects but is applicable to other distributed scientific operations. The main focuses are the data acquisition on drill sites (ExpeditionDIS, and the curation of sample material e.g., in core repositories (CurationDIS. Due to the heterogeneity of scientific drilling projects, a project-specific DIS is arranged and adjusted from a collection of existing templates and modules according to the user requirements during a one week training course. The collected data are provided to the Science Team of the drilling project by secured Web services, and stored in long-term archives hosted at GFZ. At the end the data sets and sample material are documented in an Operational Report (e.g., Lorenz et al., 2015 and published with assigned DOI (Digital Object Identifier and IGSN (International Geo Sample Number; for physical samples by GFZ Data Services.

Highly Convergent Total Synthesis of (+)-Lithospermic Acid via a Late-Stage Intermolecular C–H Olefination

Science.gov (United States)

Wang, Dong-Hui; Yu, Jin-Quan

2011-01-01

The total synthesis of (+)-lithospermic acid is reported, which exploits two successive C–H activation reactions as the key steps. Rh-catalyzed carbene C–H insertion reaction using Davies’ catalyst built the dihydrobenzofuran core, and a late-stage intermolecular C–H olefination coupled the olefin unit with the dihydrobenzofuran core to construct the molecule in a highly convergent manner. PMID:21443224

Ligand-Enabled Reactivity and Selectivity in a Synthetically Versatile Aryl C–H Olefination*

Science.gov (United States)

Wang, Dong-Hui; Engle, Keary M.; Shi, Bing-Feng; Yu, Jin-Quan

2010-01-01

The Mizoroki–Heck reaction, which couples aryl halides with olefins, has been widely used to stitch together the carbogenic cores of numerous complex organic molecules. Given that the position-selective introduction of a halide onto an arene is not always straightforward, direct olefination of aryl C–H bonds would obviate the inefficiencies associated with generating halide precursors or their equivalents; however, methods for carrying out such a reaction have suffered from narrow substrate scope and low positional selectivity. Here we report an operationally simple, atom-economical, carboxylate-directed Pd(II)-catalyzed C–H olefination reaction with phenylacetic acid and 3-phenylpropionic acid substrates, using oxygen at atmospheric pressure as the oxidant. The positional selectivity can be tuned by introducing amino acid derivatives as ligands. We demonstrate the versatility of the method through direct elaboration of commercial drug scaffolds and efficient synthesis of 2-tetralone and naphthoic acid natural product cores. PMID:19965380

Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates.

Science.gov (United States)

Feng, Chao; Feng, Daming; Loh, Teck-Peng

2013-07-19

Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

International Nuclear Information System (INIS)

Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

1981-01-01

By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

Synthetic lubricants based on copolymers of n-butyl methacrylate and α-olefins

Directory of Open Access Journals (Sweden)

Đakov Tatjana A.

2002-01-01

Full Text Available Synthetic fluids obtained by the copolymerization of α -olefins with alkyl esters of unsaturated carboxylic acids have a unique combination of properties of non-polar poly-a-olefins (PAOs and polar esters in a single molecule. These compounds are characterized by superior thermal, oxidative and hydrolytic stability, miscibility with mineral and synthetic base oils solubility of additives and neutral elastomer behavior. Depending on the molar masses and comonomer ratios in the copolymer molecule, synthetic fluids with a wide range of properties are obtained. These compounds are valuable components in lubricating oil formulations for different applications.

Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

KAUST Repository

Poater, Albert; Correa, Andrea; Pump, Eva; Cavallo, Luigi

2014-01-01

In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

KAUST Repository

Poater, Albert

2014-05-25

In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

Methanol conversion to lower olefins over RHO type zeolite

KAUST Repository

Masih, Dilshad; Imai, Hiroyuki; Yokoi, Toshiyuki; Kondo, Junkonomura; Tatsumi, Takashi

2013-01-01

Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET

Olefination of carbonyl compounds: modern and classical methods

Energy Technology Data Exchange (ETDEWEB)

Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

2004-10-31

The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

Olefination of carbonyl compounds: modern and classical methods

Science.gov (United States)

Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.

2004-10-01

The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

Importance of drill string assembly swivel in horizontal drilling

Directory of Open Access Journals (Sweden)

Edmund Tasak

2006-10-01

Full Text Available A part of the drill string – the swivel (rotational connector – accomplishes an important task in the horizontal drilling. Its malfunctioning makes it impossible to draw in ( install large diameter and length pipelines. The causes of the connector break-down during the horizontal drilling are investigated in the paper. The drilling has been made for twenty inches gas pipeline installation during reaming operations. A trouble was encountered making good work conditions of a system consisting of the drilling machine drill string reamer swivel tube shield of Cardan joint and the gas pipeline 500 m long. In this case, the swivel brokes down and the planned operation was not finished. The assessment of improper drilling conditions, selection of operation system components, and drilling parameters and the insufficient technological supervising have created an excessive risk of failure. A proper application of technical analysis would considerably decrease the hazard of failure which cause large costs, delays and decrease of confidence to the drilling contractor and pipeline installation.

Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

Science.gov (United States)

Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

2017-04-19

Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

Drilling comparison in "warm ice" and drill design comparison

DEFF Research Database (Denmark)

Augustin, L.; Motoyama, H.; Wilhelms, F.

2007-01-01

For the deep ice-core drilling community, the 2005/06 Antarctic season was an exciting and fruitful one. In three different Antarctic locations, Dome Fuji, EPICA DML and Vostok, deep drillings approached bedrock (the ice-water interface in the case of Vostok), emulating what had previously been...... achieved at NorthGRIP, Greenland, (summer 2003 and 2004) and at EPICA Dome C2, Antarctica (season 2004/05). For the first time in ice-core drilling history, three different types of drill (KEMS, JARE and EPICA) simultaneously reached the depth of 'warm ice' under high pressure. After excellent progress...... at each site, the drilling rate dropped and the drilling teams had to deal with refrozen ice on cutters and drill heads. Drills have different limits and perform differently. In this comparative study, we examine depth, pressure, temperature, pump flow and cutting speed. Finally, we compare a few...

The Newberry Deep Drilling Project (NDDP)

Science.gov (United States)

Bonneville, A.; Cladouhos, T. T.; Petty, S.; Schultz, A.; Sorle, C.; Asanuma, H.; Friðleifsson, G. Ó.; Jaupart, C. P.; Moran, S. C.; de Natale, G.

2017-12-01

We present the arguments to drill a deep well to the ductile/brittle transition zone (T>400°C) at Newberry Volcano, central Oregon state, U.S.A. The main research goals are related to heat and mass transfer in the crust from the point of view of natural hazards and geothermal energy: enhanced geothermal system (EGS supercritical and beyond-brittle), volcanic hazards, mechanisms of magmatic intrusions, geomechanics close to a magmatic system, calibration of geophysical imaging techniques and drilling in a high temperature environment. Drilling at Newberry will bring additional information to a very promising field of research initiated by ICDP in the Deep Drilling project in Iceland with IDDP-1 on Krafla in 2009, followed by IDDP-2 on the Reykjanes ridge in 2016, and the future Japan Beyond-Brittle project and Krafla Magma Testbed. Newberry Volcano contains one of the largest geothermal heat reservoirs in the western United States, extensively studied for the last 40 years. All the knowledge and experience collected make this an excellent choice for drilling a well that will reach high temperatures at relatively shallow depths (< 5000 m). The large conductive thermal anomaly (320°C at 3000 m depth), has already been well-characterized by extensive drilling and geophysical surveys. This will extend current knowledge from the existing 3000 m deep boreholes at the sites into and through the brittle-ductile transition approaching regions of partial melt like lateral dykes. The important scientific questions that will form the basis of a full drilling proposal, have been addressed during an International Continental Drilling Program (ICDP) workshop held in Bend, Oregon in September 2017. They will be presented and discussed as well as the strategic plan to address them.

Development of vertical drilling apparatus (Terra-Drill); Entwicklung eines Vertikal-Bohrgeraets (Terra-Drill) - Schlussbericht

Energy Technology Data Exchange (ETDEWEB)

Jenne, D.

2009-05-15

This well-illustrated final report for the Swiss Federal Office of Energy (SFOE) reports on the development of a vertical drilling apparatus named Terra-Drill. The various stages of the development of the apparatus, which is based on earlier designs, is discussed. New norms issued in Germany for the size of boreholes for buried vertical heat-exchangers and the appropriate linings to be used are discussed. The new Terra Drill 4407 V drilling apparatus and its testing are discussed. The drill is quoted as being particularly suitable for cramped locations. Technical details are presented and a comprehensive collection of photographs is included. Various preliminary reports and development documentation are included.

The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

KAUST Repository

Poater, Albert

2014-10-14

The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

KAUST Repository

Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

2014-01-01

The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

The asymmetric Schrock olefin metathesis catalysts. A computational study

NARCIS (Netherlands)

Goumans, T.P.M.; Ehlers, A.W.; Lammertsma, K.

2005-01-01

The mechanism of the transition metal catalyzed olefin metathesis reaction with the Schrock catalyst is investigated with pure (BP86) and hybrid (B3LYP) density functional theory. On the free-energy surface there is no adduct between ethylene and model catalyst (MeO)

Gas phase reactions of nitrogen oxides with olefins

Energy Technology Data Exchange (ETDEWEB)

Altshuller, A P; Cohen, I

1961-01-01

The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

Esterase-sensitive sulfur dioxide prodrugs inspired by modified Julia olefination.

Science.gov (United States)

Wang, Wenyi; Wang, Binghe

2017-09-12

Sulfur dioxide (SO 2 ) is an endogenously produced gaseous molecule, and is emerging as a potential gasotransmitter. Herein, we describe the first series of esterase-sensitive prodrugs inspired by modified Julia olefination as SO 2 donors.

Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation-carbonyl olefination synergy.

Science.gov (United States)

Negishi, Ei-ichi; Huang, Zhihong; Wang, Guangwei; Mohan, Swathi; Wang, Chao; Hattori, Hatsuhiko

2008-11-18

Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a

Drilling bits for deep drilling and process for their manufacture

Energy Technology Data Exchange (ETDEWEB)

Rhode, H.; Juergens, R.; Feenstra, R.; Busking, B.E.

1978-11-30

The invention concerns a drilling head or a drilling bit for use in deep drilling in underground formations and particularly concerns a drilling bit with a drilling bit body, which has a shank and a hollow space, which is connected with a duct extending through the shank. The drilling bit body has several separate cutting elements for removing material from the floor of a borehole and hydraulic devices for cooling and/or cleaning the cutting elements are provided.

Manganese oxide as a promoter for C2-C4 olefin production in the hydrogenation of carbon dioxide

International Nuclear Information System (INIS)

Kim, C.; Chen, K.; Hanson, F.V.; Oblad, A.G.; Tsai, Y.

1986-01-01

A number of active research and development programs have been initiated to explore the potential of CO hydrogenation process as a source of low molecular weight (C 2 -C 4 ) olefins. Metal catalysts such as Co-Mn, Ni-zeolite, Rd and Mo have been evaluated for low molecular weight olefin selectivity. The coprecipitated Fe-Mn system (Mn/Fe=9/1) was reported to be highly olefin selective. Recently, many investigators reported supporting evidence for the promotional effect of Mn for precipitated Fe catalysts. In this study, Raney Fe promoted with Mn has been evaluated for C 2 -C 4 olefin selectivity in the hydrogenation of CO relative to coprecipitated Fe-Mn catalysts. Catalyst characterization, including BET surface area, X-ray diffraction, selective chemisorption and ESCA, has been carried to provide insight into the role of manganese in both the Coprecipitated and Raney catalyst systems

Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant.

Science.gov (United States)

Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan

2015-03-01

The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

Science.gov (United States)

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Key product development based on cyclo olefin polymer for LCD-TV

Science.gov (United States)

Konishi, Yuichiro; Kobayashi, Masahi; Arakawa, Kouhei

2006-09-01

Cyclo Olefin Polymer (COP), which was developed by Zeon Corporation, is well known and used as an optical plastic in optical markets, having unique properties such as high light transmission, low water absorption, low birefringence etc. Optes Inc, who is ZEON CORPORATION's affiliate optical parts manufacturer, has succeeded in the development of high performance optical base films. These are used for retardation and polarizing films in LCD's (Liquid Crystal Displays), made from Cyclo Olefin Polymer with own film extrusion technologies. The Optical base film developed by Optes Inc has superior properties compared with those of existing products such as polycarbonate (PC), polyethylene terephthalate (PET) and Triacetate Cellulose (TAC) base in terms of low birefringence, high optical isotropy and high dimensional stability under high humidity and temperature conditions.

Oman Drilling Project Phase I Borehole Geophysical Survey

Science.gov (United States)

Matter, J. M.; Pezard, P. A.; Henry, G.; Brun, L.; Célérier, B.; Lods, G.; Robert, P.; Benchikh, A. M.; Al Shukaili, M.; Al Qassabi, A.

2017-12-01

The Oman Drilling Project (OmanDP) drilled six holes at six sites in the Samail ophiolite in the southern Samail and Tayin massifs. 1500-m of igneous and metamorphic rocks were recovered at four sites (GT1, GT2, GT3 and BT1) using wireline diamond core drilling and drill cuttings at two sites (BA1, BA2) using air rotary drilling, respectively. OmanDP is an international collaboration supported by the International Continental Scientific Drilling Program, the Deep Carbon Observatory, NSF, NASA, IODP, JAMSTEC, and the European, Japanese, German and Swiss Science Foundations, and with in-kind support in Oman from Ministry of Regional Municipalities and Water Resources, Public Authority of Mining, Sultan Qaboos University and the German University of Technology. A comprehensive borehole geophysical survey was conducted in all the OmanDP Phase I boreholes shortly after drilling in April 2017. Following geophysical wireline logs, using slim-hole borehole logging equipment provided and run by the Centre National De La Recherche Scientifique (CNRS) and the Université de Montpellier/ Géosciences Montpellier, and logging trucks from the Ministry of Regional Municipalities and Water Resources, were collected in most of the holes: electrical resistivity (dual laterolog resistivity, LLd and LLs), spectral gamma ray (K, U, and Th contents), magnetic susceptibility, total natural gamma ray, full waveform sonic (Vp and Vs), acoustic borehole wall imaging, optical borehole wall imaging, borehole fluid parameters (pressure, temperature, electrical conductivity, dissolved oxygen, pH, redox potential, non-polarized spontaneous electrical potential), and caliper (borehole diameter). In addition, spinner flowmeter (downhole fluid flow rate along borehole axis) and heatpulse flow meter logs (dowhole fluid flow rate along borehole axis) were collected in BA1 to characterize downhole fluid flow rates along borehole axis. Unfortuantely, only incomplete wireline logs are available for

Distributions of imidacloprid, imidacloprid-olefin and imidacloprid-urea in green plant tissues and roots of rapeseed (Brassica napus) from artificially contaminated potting soil.

Science.gov (United States)

Seifrtova, Marcela; Halesova, Tatana; Sulcova, Klara; Riddellova, Katerina; Erban, Tomas

2017-05-01

Imidacloprid-urea is the primary imidacloprid soil metabolite, whereas imidacloprid-olefin is the main plant-relevant metabolite and is more toxic to insects than imidacloprid. We artificially contaminated potting soil and used quantitative UHPLC-QqQ-MS/MS to determine the imidacloprid, imidacloprid-olefin and imidacloprid-urea distributions in rapeseed green plant tissues and roots after 4 weeks of exposure. In soil, the imidacloprid/imidacloprid-urea molar ratios decreased similarly after the 250 and 2500 µg kg -1 imidacloprid treatments. The imidacloprid/imidacloprid-urea molar ratios in the root and soil were similar, whereas in the green plant tissue, imidacloprid-urea increased more than twofold compared with the root. Although imidacloprid-olefin was prevalent in the green plant tissues, with imidacloprid/imidacloprid-olefin molar ratios of 2.24 and 1.47 for the 250 and 2500 µg kg -1 treatments respectively, it was not detected in the root. However, imidacloprid-olefin was detected in the soil after the 2500 µg kg -1 imidacloprid treatment. Significant proportions of imidacloprid-olefin and imidacloprid-urea in green plant tissues were demonstrated. The greater imidacloprid supply increased the imidacloprid-olefin/imidacloprid molar ratio in the green plant tissues. The absence of imidacloprid-olefin in the root excluded its retransport from leaves. The similar imidacloprid/imidacloprid-urea ratios in the soil and root indicated that the root serves primarily for transporting these substances. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

Science.gov (United States)

Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

2017-08-30

Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

Rapid Response Fault Drilling Past, Present, and Future

Directory of Open Access Journals (Sweden)

Demian M. Saffer

2009-09-01

Full Text Available New information about large earthquakes can be acquired by drilling into the fault zone quickly following a large seismic event. Specifically, we can learn about the levels of friction and strength of the fault which determine the dynamic rupture, monitor the healing process of the fault, record the stress changes that trigger aftershocks and capture important physical and chemical properties of the fault that control the rupture process. These scientific and associated technical issues were the focus of a three-day workshop on Rapid Response Fault Drilling: Past, Present, and Future, sponsored by the International Continental Scientific Drilling Program (ICDP and the Southern California Earthquake Center (SCEC. The meeting drewtogether forty-four scientists representing ten countries in Tokyo, Japan during November 2008. The group discussed the scientific problems and how they could be addressed through rapid response drilling. Focused talks presented previous work on drilling after large earthquakes and in fault zones in general, as well as the state of the art of experimental techniques and measurement strategies. Detailed discussion weighed the tradeoffs between rapid drilling andthe ability to satisfy a diverse range of scientific objectives. Plausible drilling sites and scenarios were evaluated. This is a shortened summary of the workshop report that discusses key scientific questions, measurement strategies, and recommendations. This report can provide a starting point for quickly mobilizing a drilling program following future large earthquakes. The full report can be seen at http://www.pmc.ucsc.edu/~rapid/.

Kinetics of olefin arylation by bis(triphenylphosphine) diacetatopalladium(II) (PPAP) and trans-cis isomerization of the latter

Energy Technology Data Exchange (ETDEWEB)

Ryabov, A.D.; Yatsimirskii, A.K.

1979-01-01

In the absence of olefins, at 70/sup 0/C, PPAP dissolved in glacial acetic acid rapidly decomposed into triphenylphosphine (TPP) oxide, biphenyl, and metallic palladium, after an induction period of about ten minutes. At lower temperatures in this solvent, pure trans-PPAP was converted into the more stable cis-isomer. The conversion was 70-80Vertical Bar3<, increased with temperature (25/sup 0/-45/sup 0/C), and was inhibited by free TPP. Interaction of PPAP with styrene in glacial acetic acid at 70/sup 0/C occurred with an induction period and gave stilbene (80Vertical Bar3< yield) and TPP oxide. The induction period was independent of the concentration of PPAP or olefin and coincided with that in PPAP decomposition in the absence of olefin. Similar regularities were observed in PPAP interaction with p-methoxystyrene and p-nitrostyrene. Apparently, the induction period involves Pd(II) reduction to a phenypalladium(0) species stabilized by TPP and is followed by rapid transfer of phenyl from palladium to olefin.

Catalytic Cracking of Triglyceride-Rich Biomass toward Lower Olefins over a Nano-ZSM-5/SBA-15 Analog Composite

Directory of Open Access Journals (Sweden)

Xuan Hoan Vu

2015-10-01

Full Text Available The catalytic cracking of triglyceride-rich biomass toward C2–C4 olefins was evaluated over a hierarchically textured nano-ZSM-5/SBA-15 analog composite (ZSC-24 under fluid catalytic cracking (FCC conditions. The experiments were performed on a fully automated Single-Receiver Short-Contact-Time Microactivity Test unit (SR-SCT-MAT, Grace Davison at 550 °C and different catalyst-to-oil mass ratios (0–1.2 g∙g−1. The ZSC-24 catalyst is very effective for transformation of triglycerides to valuable hydrocarbons, particularly lower olefins. The selectivity to C2–C4 olefins is remarkably high (>90% throughout the investigated catalyst-to-oil ratio range. The superior catalytic performance of the ZSC-24 catalyst can be attributed to the combination of its medium acid site amount and improved molecular transport provided by the bimodal pore system, which effectively suppresses the secondary reactions of primarily formed lower olefins.

Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination.

Science.gov (United States)

Breit, Bernhard

1998-03-02

Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae

NARCIS (Netherlands)

Jongedijk, E.J.; Cankar, K.; Ranzijn, J.; Krol, van der A.R.; Bouwmeester, H.J.; Beekwilder, M.J.

2015-01-01

Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a

Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

Science.gov (United States)

Chang, Chi-Hao; Chou, Chih-Ming

2018-04-06

This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

Chesapeake Bay Impact Structure Deep Drilling Project Completes Coring

Directory of Open Access Journals (Sweden)

the Scientific Staff of the Chesapeake Bay Impact Structure Deep Drilling Project

2006-09-01

Full Text Available The Chesapeake Bay Impact Structure Deep Drilling Project (CBIS Project completed its coring operations during September–December 2005 and April–May 2006. Cores were collected continuously to a total depth of 1766 m. The recovered section consists of 1322 m of impactites beneath 444 m of post-impact continental shelf sediments.The CBIS Project is a joint venture of the International Continental Scientifi c Drilling Program (ICDP and the U.S. Geological Survey (USGS. Project activities began with a planning workshop in September 2003 attended by sixtythree scientists from ten countries. Field operations began with site preparation in July 2005, and coring began in September 2005. Drilling, Observation and Sampling of theEarth’s Continental Crust (DOSECC was the general contractor for the drilling operations throughout 2005.

Synthesis of a gamma irradiation grafted polytetrafluoroethylene (PTFE) based olefinic copolymer

International Nuclear Information System (INIS)

Ferreto, Helio Fernando Rodrigues

2006-01-01

The extrusion of linear low density polyethylene (LLDPE) is limited by a process related defect known as 'melt fracture' or 'sharkskin', which is a surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and in alterations of specific surface properties. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by the addition of an olefinic monomer to graft the latter in the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to permit recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. Three olefinic monomers were used, namely; acetylene, ethylene and 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). 0.2-2.0 wt% of the copolymer that was obtained was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the process used rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'. (author)

Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

Energy Technology Data Exchange (ETDEWEB)

McCann, Ronán [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin 9 (Ireland); Bagga, Komal; Groarke, Robert [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); Stalcup, Apryll [Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); School of Chemical Sciences, Dublin City University, Dublin 9 (Ireland); Vázquez, Mercedes, E-mail: mercedes.vazquez@dcu.ie [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); School of Chemical Sciences, Dublin City University, Dublin 9 (Ireland); Brabazon, Dermot [Advanced Processing Technology Research Centre, Dublin City University, Glasnevin, Dublin 9 (Ireland); School of Mechanical and Manufacturing Engineering, Dublin City University, Dublin 9 (Ireland); Irish Separation Science Cluster, National Centre for Sensor Research, Dublin City University, Dublin 9 (Ireland); National Centre for Plasma Science and Technology, Dublin City University, Dublin 9 (Ireland)

2016-11-30

Highlights: • Rapid single-step microchannel fabrication on optically transparent cyclic olefin polymer using IR Nd:YAG laser. • Ability to tailor channel depth between 12–47 μm demonstrated for single laser pass. • Use of multiple laser passes showed capability for finer depth control. • Potential applications in lab-on-chip and microfluidic devices. - Abstract: This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

Microchannel fabrication on cyclic olefin polymer substrates via 1064 nm Nd:YAG laser ablation

International Nuclear Information System (INIS)

McCann, Ronán; Bagga, Komal; Groarke, Robert; Stalcup, Apryll; Vázquez, Mercedes; Brabazon, Dermot

2016-01-01

Highlights: • Rapid single-step microchannel fabrication on optically transparent cyclic olefin polymer using IR Nd:YAG laser. • Ability to tailor channel depth between 12–47 μm demonstrated for single laser pass. • Use of multiple laser passes showed capability for finer depth control. • Potential applications in lab-on-chip and microfluidic devices. - Abstract: This paper presents a method for fabrication of microchannels on cyclic olefin polymer films that have application in the field of microfluidics and chemical sensing. Continuous microchannels were fabricated on 188-μm-thick cyclic olefin polymer substrates using a picosecond pulsed 1064 nm Nd:YAG laser. The effect of laser fluence on the microchannel morphology and dimensions was analysed via scanning electron microscopy and optical profilometry. Single laser passes were found to produce v-shaped microchannels with depths ranging from 12 μm to 47 μm and widths from 44 μm to 154 μm. The ablation rate during processing was lower than predicted theoretically. Multiple laser passes were applied to examine the ability for finer control over microchannel morphology with channel depths ranging from 22 μm to 77 μm and channel widths from 59 μm to 155 μm. For up to five repeat passes, acceptable reproducibility was found in the produced microchannel morphology. Infrared spectroscopy revealed oxidation and dehydrogenation of the polymer surface following laser ablation. These results were compared to other work conducted on cyclic olefin polymers.

Conceptual design and system analysis of a poly-generation system for power and olefin production from natural gas

International Nuclear Information System (INIS)

Qian Yu; Liu Jingyao; Huang Zhixian; Kraslawski, Andrzej; Cui Jian; Huang Yinlun

2009-01-01

In this paper, a novel poly-generation system for olefin and power production from natural gas is proposed, which integrates hydrocarbon production and the combined cycle power generation. Economic and technological evaluation based on the internal rate of return (IRR) and exergy efficiency is performed. The energy integration results in the proposed poly-generation system for simultaneous production of chemical products (ethylene and propylene) and electricity being more thermodynamically efficient and economically viable than single purpose power generation and chemical products production plants. IRR and exergy efficiency of the proposed poly-generation system are higher than that of natural gas methanol to olefin (NGMTO) system, 18.9% and 49.9%, respectively. The biggest exergy destruction segments, their causes, and possible measures for improvement are investigated simulation and thermodynamic analysis. To analyze the effect of unreacted syngas recycle on the exergy efficiency and economic gains from the proposed poly-generation system, its thermoeconomic optimization model is built by combining economic with thermodynamic analysis. Optimization analysis shows that when 78% of the unreacted syngas is recycled back to the reactor in the methanol synthesization process, the thermoeconomic performance of the poly-generation system is at its optimum.

CASING DRILLING TECHNOLOGY

Directory of Open Access Journals (Sweden)

Nediljka Gaurina-Međimurec

2005-12-01

Full Text Available Casing drilling is an alternative option to conventional drilling and uses standard oilfield casing instead of drillstring. This technology is one of the greatest developments in drilling operations. Casing drilling involves drilling and casing a well simultaneously. In casing driling process, downhole tools can be retrieved, through the casing on wire-line, meaning tool recovery or replacement of tools can take minutes versus hours under conventional methods. This process employs wireline-retrievable tools and a drill-lock assembly, permitting bit and BHA changes, coring, electrical logging and even directional or horizontal drilling. Once the casing point is reached, the casing is cemented in place without tripping pipe.

Growth in the measurement-while-drilling sector continues

International Nuclear Information System (INIS)

Hall, G.T.

1991-01-01

This book reports that the measurement while drilling (MWD) market is showing some of the most impressive growth in the oil field. Tremendous improvements in the reliability and capability of MWD tools have spurred the expansion of this market. During 1990, the worldwide MWD market expanded by 48%, rising from $250 million in 1989 to $370 million in 1990. The MWD market should expand 15-20% to exceed $430 million in 1991. Although an expansion of 15-20% is considered good, further growth will be impeded by the slowdown of drilling in the Gulf of Mexico. Total market growth should return to greater than 20% per year in 1992 and 1993. MWD technology is in the midst of a rapid adaptation phase, led by expansion of formation evaluation and other logs and by international expansion in long-reach directional and horizontal drilling. The formation evaluation-while- drilling market will have minimal impact on the size and growth of the wire line market. Customers will increasingly employ teams which include drilling and petrophysics personnel to make MWD purchase decisions. Integration of performance drilling systems including all bottom hole components will accelerate because of increases in automation and the need for cost reduction

Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

Science.gov (United States)

Meng, Xiangtao; Edgar, Kevin J

2015-11-05

Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

Drilling unit

Energy Technology Data Exchange (ETDEWEB)

Umanchik, N P; Demin, A V; Khrustalev, N N; Linnik, G N; Lovchev, S V; Rozin, M M; Sidorov, R V; Sokolov, S I; Tsaregradskiy, Yu P

1981-01-01

A drilling unit is proposed which includes a hydraulic lifter, hydraulic multiple-cylinder pump with valve distribution and sectional drilling pump with separators of the working and flushing fluid. In order to reduce metal consumption and the overall dimensions of the drilling unit, the working cavity of each cylinder of the hydraulic multiple-cylinder pump is equipped with suction and injection valves and is hydraulically connected to the working cavity by one of the sections of the drilling pump.

Individual Drilling Bit Design and Optimization in Mahu Area

Directory of Open Access Journals (Sweden)

Zhang Wenbo

2017-01-01

Full Text Available There are three sets of gravels in Mahu region. The gravels formation is characterized by high heterogeneity, high abrasiveness and poor drillability. It is so difficult to optimize bit that restrict seriously the overall exploration and development process. The compressive strength, internal friction angle, and drillability of the formation are tested to check the rock mechanical characteristic profile established by logging data. The individual bit design is carried out by the 3D simulation technology. A new PDC bit type is designed to form the drill bit series for Mahu area. Single PDC bit increases 90% of the drilling footage. The trip average footage is improved 3.45 times, the horizontal section average penetration increased 34.8%. The technical achievements have greatly improved economic development benefits of Mahu region by improving drilling speed and saving drilling costs.

Positive ion scavenging by olefins in trans-decalin: TRMC and product analysis studies

International Nuclear Information System (INIS)

Warman, J.M.; Leng, H.C. de; Haas, M.P. de; Anisimov, O.A.

1990-01-01

The rate constants for scavenging of the mobile positive ion in trans-decalin have been measured using the time-resolved microwave conductivity (TRMC) pulse radiolysis technique for a series of olefins and cyclopropane. For the olefins the values vary from ≤2 x 10 8 dm 3 /mol/s for ethylene to 1.6 x 10 11 dm 3 /mol/s for cyclohexene. Steady-state (γ) radiolysis of solutions of isobutene in trans-decalin results in the formation of isobutane and C 8 and C 14 products which display different dependences on solute concentration. The results are explained in terms of the formation of a complex between the solvent radical cation and isobutene which can dissociate, within a timescale of approx. 1 ns, to give isobutane or on neutralisation leads to the formation of C 14 condensation products. The C 8 products which are formed above 5 x 10 -2 mol/dm 3 are attributed to reaction of the complex with isobutene to form the olefin dimer cation. Cyclopropane is unreactive, i.e. k 8 dm 3 /mol/s, towards the mobile positive ion in trans-decalin (author)

Clean subglacial access: prospects for future deep hot-water drilling

Science.gov (United States)

Pearce, David; Hodgson, Dominic A.; Smith, Andrew M.; Rose, Mike; Ross, Neil; Mowlem, Matt; Parnell, John

2016-01-01

Accessing and sampling subglacial environments deep beneath the Antarctic Ice Sheet presents several challenges to existing drilling technologies. With over half of the ice sheet believed to be resting on a wet bed, drilling down to this environment must conform to international agreements on environmental stewardship and protection, making clean hot-water drilling the most viable option. Such a drill, and its water recovery system, must be capable of accessing significantly greater ice depths than previous hot-water drills, and remain fully operational after connecting with the basal hydrological system. The Subglacial Lake Ellsworth (SLE) project developed a comprehensive plan for deep (greater than 3000 m) subglacial lake research, involving the design and development of a clean deep-ice hot-water drill. However, during fieldwork in December 2012 drilling was halted after a succession of equipment issues culminated in a failure to link with a subsurface cavity and abandonment of the access holes. The lessons learned from this experience are presented here. Combining knowledge gained from these lessons with experience from other hot-water drilling programmes, and recent field testing, we describe the most viable technical options and operational procedures for future clean entry into SLE and other deep subglacial access targets. PMID:26667913

How much life is left in your olefin unit

International Nuclear Information System (INIS)

Baas, J.; Warner, R.

1992-01-01

Highly attractive economics in the olefin industry has justified increasing capacity via plant expansion and using aging olefin units beyond expected limitations. If these existing units are to operate well beyond their design life, what type of analysis and information is necessary to make this decision? What technologies or methods should be used for continued safe and controlled operation of these not so new units. This paper reports that the plant's mechanical integrity is the focal point of this analysis and decision-making method. Plant life expectancy study (PLES) looks at an operating plant's mechanical integrity from several vantage points. Four basic principles, such as plant history, process upsets and operating records, assessment of plant fires, and how to conduct records, assessment of plant fires, and how to conduct inspection and testing, provide the basis of how well a plant has been operated and maintained. Furthermore, the analysis includes a critical component inventory. These items address additional potential-failure causes, such as creep, fatigue, toughness, corrosion, erosion and carburization/oxidation

1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

Science.gov (United States)

Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

2006-07-21

A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8.

Science.gov (United States)

Böhme, Ulrike; Barth, Benjamin; Paula, Carolin; Kuhnt, Andreas; Schwieger, Wilhelm; Mundstock, Alexander; Caro, Jürgen; Hartmann, Martin

2013-07-09

Two types of metal-organic frameworks (MOFs) have been synthesized and evaluated in the separation of C2 and C3 olefins and paraffins. Whereas Co2(dhtp) (=Co-CPO-27 = Co-MOF-74) and Mg2(dhtp) show an adsorption selectivity for the olefins ethene and propene over the paraffins ethane and propane, the zeolitic imidazolate framework ZIF-8 behaves in the opposite way and preferentially adsorbs the alkane. Consequently, in breakthrough experiments, the olefins or paraffins, respectively, can be separated.

The Role of Well Control Training in Developing Safe Onshore and Offshore Oil Drilling Operations

Science.gov (United States)

Abulhassn, Aber

2016-01-01

This research investigates the role of the International Well Control Forum (IWCF) Rotary Drilling Well Control Training Program in developing safe oil drilling operations from the perspective of onshore and offshore drilling crews. The research methodology is a qualitative case study. A total of 40 IWCF candidates were interviewed, with 10 from…

A new drilling method-Earthworm-like vibration drilling.

Science.gov (United States)

Wang, Peng; Ni, Hongjian; Wang, Ruihe

2018-01-01

The load transfer difficulty caused by borehole wall friction severely limits the penetration rate and extended-reach limit of complex structural wells. A new friction reduction technology termed "earthworm-like drilling" is proposed in this paper to improve the load transfer of complex structural wells. A mathematical model based on a "soft-string" model is developed and solved. The results show that earthworm-like drilling is more effective than single-point vibration drilling. The amplitude and frequency of the pulse pressure and the installation position of the shakers have a substantial impact on friction reduction and load transfer. An optimization model based on the projection gradient method is developed and used to optimize the position of three shakers in a horizontal well. The results verify the feasibility and advantages of earthworm-like drilling, and establish a solid theoretical foundation for its application in oil field drilling.

Omega-functionalized fatty acids, alcohols, and ethers via olefin metathesis

Science.gov (United States)

Methyl 17-hydroxy stearate was converted to methyl octadec-16-enoate using copper sulfate adsorbed on silica gel. This compound, possessing unsaturation at the opposite end of the chain from the carboxylate, served as a useful substrate for the olefin metathesis reaction. As a result, several fatt...

Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

DEFF Research Database (Denmark)

Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio

2011-01-01

A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

Engineering work plan for container venting system drill press assembly troubleshooting. Revision 1

International Nuclear Information System (INIS)

Prather, M.C.

1994-11-01

This work plan is for troubleshooting the current CVS drill press to ensure that the drill bit assembly doesn't bind in the press plate. A drill press assembly has been fabricated for the Container Venting System (CVS). The drill bit assembly has bound in the press plate in previous revisions of this design. Initial troubleshooting of the drill press per Rev. 0 of this work plan was performed at the 200W Kaiser Machine Shop under Work Package 2H9401670F, Internal Work Order E20027. The drill press operated without jamming. Then, during the pre-operational test on 11/14/17 and the operational test on 11/17/94, two drum lids were drilled. Immediately after the test on 11/17/94, the drill was again operated, and it jammed. An inspection found shavings at the bottom of the drill bit assembly, between the drill bit sleeve and the press plate bore. This revised work plan provides direction for the machine shop to diagnose and correct this recent problem

Copper(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones.

Science.gov (United States)

Xu, Shuai; Gao, Yunpeng; Chen, Ri; Wang, Kang; Zhang, Yan; Wang, Jianbo

2016-03-25

The Cu(I)-catalyzed olefination of N-sulfonylhydrazones with sulfones via metal carbene intermediates is reported. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of carbon-carbon double bonds. Mechanistically, Cu(I) carbene formation and subsequent carbene migratory insertion are proposed as the key steps.

Drilling reorganizes

Science.gov (United States)

Richman, Barbara T.

As the first in a proposed series of steps that would move scientific ocean drilling from its own niche within the National Science Foundation's (NSF) Directorate for Astronomical, Atmospheric, Earth, and Ocean Sciences (AAEO) into the agency's Division of Ocean Sciences, Grant Gross, division director, has been appointed acting director of the Office of Scientific Ocean Drilling (OSOD). Gross will retain the directorship of the division, which also is part of AAEO. Allen M. Shinn, Jr., OSOD director for nearly 2 years, has been reassigned effective July 10 to a position in NSF's Office of Planning and Resource Management.The move aims to tie drilling operations more closely to the science with which it is associated, Gross said. This first step is an organizational response to the current leaning toward using a commercial drilling vessel as the drilling platform, he said. Before the market for such commercial drill ships opened (Eos, February 22, 1983, p . 73), other ship options for scientific ocean drilling included refurbishing the aging Glomar Challenger or renovating, at great expense, the Glomar Explorer. A possible next step in the reorganization is to make OSOD the third section within the Ocean Sciences Division. Currently, the division is divided into the Oceanographic Facilities and Support Section and the Ocean Sciences Research Section.

Argentation gas chromatography revisited: Separation of light olefin/paraffin mixtures using silver-based ionic liquid stationary phases.

Science.gov (United States)

Nan, He; Zhang, Cheng; Venkatesh, Amrit; Rossini, Aaron J; Anderson, Jared L

2017-11-10

Silver ion or argentation chromatography utilizes stationary phases containing silver ions for the separation of unsaturated compounds. In this study, a mixed-ligand silver-based ionic liquid (IL) was evaluated for the first time as a gas chromatographic (GC) stationary phase for the separation of light olefin/paraffin mixtures. The selectivity of the stationary phase toward olefins can be tuned by adjusting the ratio of silver ion and the mixed ligands. The maximum allowable operating temperature of these stationary phases was determined to be between 125°C and 150°C. Nuclear magnetic resonance (NMR) spectroscopy was used to characterize the coordination behavior of the silver-based IL as well as provide an understanding into the retention mechanism of light olefins. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of a Short Drilling Implant Protocol on Osteotomy Site Temperature and Drill Torque.

Science.gov (United States)

Mihali, Sorin G; Canjau, Silvana; Cernescu, Anghel; Bortun, Cristina M; Wang, Hom-Lay; Bratu, Emanuel

2018-02-01

To establish a protocol for reducing the drilling sequence during implant site preparation based on temperature and insertion torque. The traditional conventional drilling sequence (used several drills with 0.6-mm increment each time) was compared with the proposed short drilling protocol (only used 2 drills: initial and final drill). One hundred drilling osteotomies were performed in bovine and porcine bones. Sets of 2 osteotomy sites were created in 5 bone densities using 2 types of drilling protocols. Thermographic pictures were captured throughout all drilling procedures and analyzed using ThermaCAM Researcher Professional 2.10. Torque values were determined during drilling by measuring electrical input and drill speed. There were statistically significant differences in bone temperature between the conventional and short drilling protocols during implant site preparation (analysis of variance P = 0.0008). However, there were no significant differences between the 2 types of drilling protocols for both implant diameters. Implant site preparation time was significantly reduced when using the short drilling protocol compared with the conventional drilling protocol (P drilling protocol proposed herein may represent a safe approach for implant site preparation.

Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

Directory of Open Access Journals (Sweden)

Tanveer Mahamadali Shaikh

2013-08-01

Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

Surgical drill system and surgical drill bit to be used therein

NARCIS (Netherlands)

Margallo Balbas, E.; Wieringa, P.A.; French, P.J.; Lee, R.A.; Breedveld, P.

2007-01-01

Surgical drill system comprising a mechanical drill bit and means for imaging the vicinity of the drill bit tip, said means comprising: at least one optical fiber having a distal end and a proximal end, said distal end being located adjacent said drill bit tip, an optical processing unit, said

75 FR 877 - Drill Pipe From China

Science.gov (United States)

2010-01-06

... Pipe From China AGENCY: International Trade Commission. ACTION: Institution of antidumping and... States is materially retarded, by reason of imports from China of drill pipe, provided for in subheadings... Government of China. Unless the Department of Commerce extends the time for initiation pursuant to sections...

Dismantlable Thermosetting Adhesives Composed of a Cross-Linkable Poly(olefin sulfone) with a Photobase Generator.

Science.gov (United States)

Sasaki, Takeo; Hashimoto, Shouta; Nogami, Nana; Sugiyama, Yuichi; Mori, Madoka; Naka, Yumiko; Le, Khoa V

2016-03-02

A novel photodetachable adhesive was prepared using a photodepolymerizable cross-linked poly(olefin sulfone). A mixture of a cross-linkable poly(olefin sulfone), a cross-linking reagent, and a photobase generator functioned as a thermosetting adhesive and exhibited high adhesive strength on quartz plates comparable to that obtained for commercially available epoxy adhesives. The cured resin was stable in the absence of UV light irradiation but completely lost its adhesive strength upon exposure of glued quartz plates to UV light in conjunction with heating to 100 °C.

Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

Science.gov (United States)

Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

2018-05-02

Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Slow drilling speeds for single-drill implant bed preparation. Experimental in vitro study.

Science.gov (United States)

Delgado-Ruiz, R A; Velasco Ortega, E; Romanos, G E; Gerhke, S; Newen, I; Calvo-Guirado, J L

2018-01-01

To evaluate the real-time bone temperature changes during the preparation of the implant bed with a single-drill protocol with different drill designs and different slow drilling speeds in artificial type IV bone. For this experimental in vitro study, 600 implant bed preparations were performed in 10 bovine bone disks using three test slow drilling speeds (50/150/300 rpm) and a control drilling speed (1200 rpm). The temperature at crestal and apical areas and time variations produced during drilling with three different drill designs with similar diameter and length but different geometry were recorded with real-life thermographic analysis. Statistical analysis was performed by two-way analysis of variance. Multiple comparisons of temperatures and time with the different drill designs and speeds were performed with the Tukey's test. T Max values for the control drilling speed with all the drill designs (D1 + 1200; D2 + 1200; D3 + 1200) were higher compared to those for the controls for 11 ± 1.32 °C (p drilling at 50 rpm resulted in the lowest temperature increment (22.11 ± 0.8 °C) compared to the other slow drilling speeds of 150 (24.752 ± 1.1 °C) and 300 rpm (25.977 ± 1.2 °C) (p drilling speeds compared to that for the control drilling speed. Slow drilling speeds required significantly more time to finish the preparation of the implant bed shown as follows: 50 rpm > 150 rpm > 300 rpm > control (p drill protocol with slow drilling speeds (50, 150, and 300 rpm) without irrigation in type IV bone increases the temperature at the coronal and apical levels but is below the critical threshold of 47 °C. The drill design in single-drill protocols using slow speeds (50, 150, and 300 rpm) does not have an influence on the thermal variations. The time to accomplish the implant bed preparation with a single-drill protocol in type IV bone is influenced by the drilling speed and not by the drill design. As the speed decreases, then

Reduced abrasion drilling fluid

NARCIS (Netherlands)

2010-01-01

A reduced abrasion drilling fluid system and method of drilling a borehole by circulating the reduced abrasion drilling fluid through the borehole is disclosed. The reduced abrasion drilling fluid comprises a drilling fluid, a first additive and a weighting agent, wherein the weighting agent has a

Reduced abrasion drilling fluid

NARCIS (Netherlands)

2012-01-01

A reduced abrasion drilling fluid system and method of drilling a borehole by circulating the reduced abrasion drilling fluid through the borehole is disclosed. The reduced abrasion drilling fluid comprises a drilling fluid, a first additive and a weighting agent, wherein the weighting agent has a

Immobilisation of homogeneous olefin polymerisation catalysts. Factors influencing activity and stability

NARCIS (Netherlands)

Severn, J.R.; Chadwick, J.C.

2013-01-01

The activity and stability of homogeneous olefin polymerisation catalysts, when immobilised on a support, are dependent on both chemical and physical effects. Chemical factors affecting catalyst activity include the ease of formation of the active species, which is strongly dependent on the

Lower crustal section of the Oman Ophiolite drilled in Hole GT1A, ICDP Oman Drilling Project

Science.gov (United States)

Umino, S.; Kelemen, P. B.; Matter, J. M.; Coggon, J. A.; Takazawa, E.; Michibayashi, K.; Teagle, D. A. H.

2017-12-01

Hole GT1A (22° 53.535'N, 58° 30.904'E) was drilled by the Oman Drilling Project (OmDP) into GT1A of the Samail ophiolite, Oman. OmDP is an international collaboration supported by the International Continental Scientific Drilling Program, the Deep Carbon Observatory, NSF, IODP, JAMSTEC, and the European, Japanese, German and Swiss Science Foundations, with in-kind support in Oman from the Ministry of Regional Municipalities and Water Resources, Public Authority of Mining, Sultan Qaboos University, and the German University of Technology. Hole GT1A was diamond cored in 22 Jan to 08 Feb 2017 to a total depth of 403.05 m. The outer surfaces of the cores were imaged and described on site before being curated, boxed and shipped to the IODP drill ship Chikyu, where they underwent comprehensive visual and instrumental analysis. Hole GT1A drilled the lower crustal section in the southern Oman Ophiolite and recovered 401.52 m of total cores (99.6% recovery). The main lithology is dominated by olivine gabbro (65.9%), followed in abundance by olivine-bearing gabbro (21.5%) and olivine melagabbro (3.9%). Minor rock types are orthopyroxene-bearing olivine gabbro (2.4%), oxide-bearing olivine gabbro (1.5%), gabbro (1.1%), anorthositic gabbro (1%), troctolitic gabbro (0.8%); orthopyroxene-bearing gabbro (0.5%), gabbronorite (0.3%); and dunite (0.3%). These rocks are divided into Lithologic Unit I to VII at 26.62 m, 88.16 m, 104.72 m, 154.04 m, 215.22 m, 306.94 m in Chikyu Curated Depth in descending order; Unit I and II consist of medium-grained olivine gabbro with lower olivine abundance in Unit II. Unit III is medium-grained olivine melagabbros, marked by an increase in olivine. Unit IV is relatively homogenous medium-grained olivine gabbros with granular textures. Unit V is identified by the appearance of fine-grained gabbros, but the major rocktypes are medium grained olivine gabbros. Unit VI is medium-grained olivine gabbro, marked by appearance of orthopyroxene. Unit VII

A model for self-defocusing in laser drilling of polymeric materials

International Nuclear Information System (INIS)

Zhang Chong; Quick, Nathaniel R.; Kar, Aravinda

2008-01-01

A numerical thermal model is presented for laser microvias drilling in multilayer electronic substrates with Nd:YAG (YAG denotes yttrium aluminum garnet) and CO 2 lasers. Such substrates have different optical properties such as the refractive index and absorption coefficient at these two laser wavelengths, resulting in different drilling mechanisms. Since the skin depth of the polymer is large for both the lasers, volumetric heating is considered in the model. As soon as a small cavity is formed during the drilling process, the concave curvature of the drilling front acts as a concave lens that diverges the incident laser beam. This self-defocusing effect can greatly reduce the drilling speed as predicted by the model. This effect makes the refractive index of the substrate at different wavelengths an important parameter for laser drilling. The model was used to calculate the laser ablation thresholds which were found to be 8 and 56 J/cm 2 for the CO 2 and Nd:YAG lasers respectively. Due to the expulsion of materials because of high internal pressures in the case of Nd:YAG laser microvia drilling, the ablation threshold may be far below the calculated value. A particular laser beam shape, such as pitch fork, was found to drill better holes than the Gaussian beam

Development and Manufacture of Cost-Effective Composite Drill Pipe

Energy Technology Data Exchange (ETDEWEB)

James C. Leslie

2008-12-31

fields up to 74 kilohertz (KHz), a removable section of copper wire can be placed inside the composite pipe to short the tool joints electrically allowing electromagnetic signals inside the collar to induce and measure the same within the rock formation. By embedding a pair of wires in the composite section and using standard drill pipe box and pin ends equipped with a specially developed direct contact joint electrical interface, power can be supplied to measurement-while-drilling (MWD) and logging-while-drilling (LWD) bottom hole assemblies. Instantaneous high-speed data communications between near drill bit and the surface are obtainable utilizing this 'smart' drilling technology. The composite drill pipe developed by ACPT has been field tested successfully in several wells nationally and internationally. These tests were primarily for short radius and ultra short radius directional drilling. The CDP in most cases performed flawlessly with little or no appreciable wear. ACPT is currently marketing a complete line of composite drill collars, subs, isolators, casing, and drill pipe to meet the drilling industry's needs and tailored to replace metal for specific application requirements.

Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Čejka, Jiří

2013-01-01

Roč. 257, 21-22 (2013), s. 3107-3124 ISSN 0010-8545 R&D Projects: GA AV ČR IAA400400805; GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Olefin metathesis * mesoporous molecular sieves * Heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.098, year: 2013

Activity plan: Directional drilling and environmental measurements while drilling

International Nuclear Information System (INIS)

Myers, D.A.

1998-01-01

This activity plan describes the testing of directional drilling combined with environmental measurements while drilling at two Hanford Site locations. A cold test is to be conducted at the 105A Mock Tank Leak Facility in the 200 East Area. A hot test is proposed to be run at the 216-B-8 tile field north of the 241-B Tank Farm in 200 East Area. Criteria to judge the success, partial success or failure of various aspects of the test are included. The TWRS program is assessing the potential for use of directional drilling because of an identified need to interrogate the vadose zone beneath the single-shell tanks. Because every precaution must be taken to assure that investigation activities do not violate the integrity of the tanks, control of the drill bit and ability to follow a predetermined drill path are of utmost importance and are being tested

Case drilling - an innovative approach to reducing drilling costs

Energy Technology Data Exchange (ETDEWEB)

Madell, G.; Tessari, R. M. [Tesco Corp., Calgary, AB (Canada); Warren, T. [Tesco Drilling Technology, Calgary, AB (Canada)

1999-11-01

Casing drilling is introduced as a new drilling technique that uses standard oil field casing to simultaneously drill and case the well. The technology includes both rig and downhole equipment, customized to function effectively as an integrated drilling system. This paper describes the testing program designed to identify and overcome technical challenges. Although not fully optimized, it appears that the system is functional. Test results indicate the need for improvements in the pump down cement float equipment and the tools and procedures for drilling up the cement plugs. The pump down latch and retrieval system also needs to be further developed and tested for high angle directional applications. Cost savings in the range of 10 to 15 per cent are expected for trouble-free wells. By eliminating the cost of unscheduled events encountered in troublesome wells, cost savings may reach as high as 30 per cent. 3 refs., 7 figs.

Activity plan: Directional drilling and environmental measurements while drilling

Energy Technology Data Exchange (ETDEWEB)

Myers, D.A.

1998-07-16

This activity plan describes the testing of directional drilling combined with environmental measurements while drilling at two Hanford Site locations. A cold test is to be conducted at the 105A Mock Tank Leak Facility in the 200 East Area. A hot test is proposed to be run at the 216-B-8 tile field north of the 241-B Tank Farm in 200 East Area. Criteria to judge the success, partial success or failure of various aspects of the test are included. The TWRS program is assessing the potential for use of directional drilling because of an identified need to interrogate the vadose zone beneath the single-shell tanks. Because every precaution must be taken to assure that investigation activities do not violate the integrity of the tanks, control of the drill bit and ability to follow a predetermined drill path are of utmost importance and are being tested.

Environmental Measurement-While-Drilling System and Horizontal Directional Drilling Technology Demonstration, Hanford Site

International Nuclear Information System (INIS)

Williams, C.V.; Lockwood, G.J.; Normann, R.A.; Myers, D.A.; Gardner, M.G.; Williamson, T.; Huffman, J.

1999-01-01

The Environmental Measurement-While-Drilling (EMWD) system and Horizontal Directional Drilling (HDD) were successfully demonstrated at the Mock Tank Leak Simulation Site and the Drilling Technology Test Site, Hanford, Washington. The use of directional drilling offers an alternative to vertical drilling site characterization. Directional drilling can develop a borehole under a structure, such as a waste tank, from an angled entry and leveling off to horizontal at the desired depth. The EMWD system represents an innovative blend of new and existing technology that provides the capability of producing real-time environmental and drill bit data during drilling operations. The technology demonstration consisted of the development of one borehole under a mock waste tank at a depth of approximately minus8 m (minus27 ft.), following a predetermined drill path, tracking the drill path to within a radius of approximately1.5 m (5 ft.), and monitoring for zones of radiological activity using the EMWD system. The purpose of the second borehole was to demonstrate the capability of drilling to a depth of ∼ -21 m (-70 ft.), the depth needed to obtain access under the Hanford waste tanks, and continue drilling horizontally. This report presents information on the HDD and EMWD technologies, demonstration design, results of the demonstrations, and lessons learned

Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

Directory of Open Access Journals (Sweden)

Shaheen M. Sarkar

2014-01-01

Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

Science.gov (United States)

Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

2009-01-01

N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

Drilling cost analysis

International Nuclear Information System (INIS)

Anand, A.B.

1992-01-01

Drilling assumes greater importance in present day uranium exploration which emphasizes to explore more areas on the basis of conceptual model than merely on surface anomalies. But drilling is as costly as it is important and consumes a major share (50% to 60%) of the exploration budget. As such the cost of drilling has great bearing on the exploration strategy as well as on the overall cost of the project. Therefore, understanding the cost analysis is very much important when planning or intensifying an exploration programme. This not only helps in controlling the current operations but also in planning the budgetary provisions for future operations. Also, if the work is entrusted to a private party, knowledge of in-house cost analysis helps in fixing the rates of drilling in different formations and areas to be drilled. Under this topic, various factors that contribute to the cost of drilling per meter as well as ways to minimize the drilling cost for better economic evaluation of mineral deposits are discussed. (author)

Energy and materials flows in the production of olefins and their derivatives

Energy Technology Data Exchange (ETDEWEB)

Gaines, L.L.; Shen, S.Y.

1980-08-01

Production of olefins and their derivatives uses almost 3.5% of the oil and gas consumed annually in the United States. It is estimated that their production requires an input energy of 2 Q, which is 50% of the energy used in the production of all petrochemicals. Substantial amounts of this energy could be recovered through recycling. For example, recycling of a single plastic product, polyester soft drink bottles, could have recovered about 0.014 Q in 1979. (About 1.4 Q is used to produce plastic derivatives of olefins). Petrochemical processes use fuels as feedstocks, as well as for process energy, and a portion of this energy is not foregone and can be recovered through combustion of the products. The energy foregone in the production of ethylene is estimated to be 7800 Btu/lb. The energy foregone in plastics production ranges from 12,100 Btu/lb for the new linear low-density polyethylene to 77,200 Btu/lb for nylon 66, which is about 60% of the total energy input for that product. Further investigation of the following areas could yield both material and energy savings in the olefins industry: (1) recycling of petrochemical products to recover energy in addition to that recoverable through combustion, (2) impact of feedstock substitution on utilization of available national resources, and (3) effective use of the heat embodied in process steam. This steam accounts for a major fraction of the industry's energy input.

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

International Nuclear Information System (INIS)

Pan Yang; Zhao Junshu; Ji Yuanyuan; Yan Lei; Yu Shuqin

2006-01-01

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields 3 TMB* after rapid intersystem crossing from 1 TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), α-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property (π-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k q T values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k q S have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k q values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation

Effects of calcination and activation conditions on ordered mesoporous carbon supported iron catalysts for production of lower olefins from synthesis gas

NARCIS (Netherlands)

Oschatz, M; van Deelen, T W; Weber, J L; Lamme, W S; Wang, G; Goderis, B; Verkinderen, O; Dugulan, A I; de Jong, K P

2016-01-01

Lower C2–C4 olefins are important commodity chemicals usually produced by steam cracking of naphtha or fluid catalytic cracking of vacuum gas oil. The Fischer–Tropsch synthesis of lower olefins (FTO) with iron-based catalysts uses synthesis gas as an alternative feedstock. Nanostructured carbon

Tacticities study of high poly-α-olefins, from poly-1-hexene to poly-1-octadecene, obtained with metallocenes catalysts

International Nuclear Information System (INIS)

Silva, Luciano F. da; Galland, Griselda B.

2003-01-01

High poly-α-olefins such as poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, poly-1-tetradecene, poly-1-hexadecene and poly-1-octadecene were obtained with the homogeneous iso specific catalyst rac-Et[Ind]ZrCl 2 /MAO and with the homogeneous syndiospecific catalyst Me 2 C[Cp(9-Flu)]ZrCl 2 /MAO at the polymerization temperatures of 0 deg C, 30 deg C and 60 deg C. The polymers were analyzed by 13 C NMR to study the influence of the α - olefins sizes, the catalysts type and the polymerization temperatures in their tacticities. The stereospecific control of both catalytic systems decreased with the increase of the reaction temperature and with the α-olefin size. (author)

Improving energy efficiency of an Olefin plant – A new approach

International Nuclear Information System (INIS)

Tahouni, Nassim; Bagheri, Narges; Towfighi, Jafar; Hassan Panjeshahi, M.

2013-01-01

Highlights: • The retrofit of an Olefin plant is studied to improve the overall energy efficiency. • Three levels of retrofit and optimization of this process are suggested. • A simultaneous method is presented to optimize low-temperature separation processes. - Abstract: Low-temperature gas separation processes are the most important gas separation routes. There is a complex interaction between core process (separation columns), associated heat exchanger network and refrigeration cycles in sub ambient processes. The aim of this paper is performing a comprehensive retrofit study of an Olefin plant (as an industrial example) to improve the overall energy efficiency. In this regard, the effect of improving column operating parameters and refrigeration cycles are first evaluated separately. Then, column operating parameters and refrigeration cycles as well as heat exchanger network are optimized simultaneously using genetic algorithm or simulated annealing. Having compared all results, one can conclude that simultaneous optimization leads to higher efficiency of the overall system

Robotic Planetary Drill Tests

Science.gov (United States)

Glass, Brian J.; Thompson, S.; Paulsen, G.

2010-01-01

Several proposed or planned planetary science missions to Mars and other Solar System bodies over the next decade require subsurface access by drilling. This paper discusses the problems of remote robotic drilling, an automation and control architecture based loosely on observed human behaviors in drilling on Earth, and an overview of robotic drilling field test results using this architecture since 2005. Both rotary-drag and rotary-percussive drills are targeted. A hybrid diagnostic approach incorporates heuristics, model-based reasoning and vibration monitoring with neural nets. Ongoing work leads to flight-ready drilling software.

OPTIMIZATION OF MUD HAMMER DRILLING PERFORMANCE - A PROGRAM TO BENCHMARK THE VIABILITY OF ADVANCED MUD HAMMER DRILLING

Energy Technology Data Exchange (ETDEWEB)

Arnis Judzis

2003-01-01

This document details the progress to date on the ''OPTIMIZATION OF MUD HAMMER DRILLING PERFORMANCE -- A PROGRAM TO BENCHMARK THE VIABILITY OF ADVANCED MUD HAMMER DRILLING'' contract for the quarter starting October 2002 through December 2002. Even though we are awaiting the optimization portion of the testing program, accomplishments included the following: (1) Smith International participated in the DOE Mud Hammer program through full scale benchmarking testing during the week of 4 November 2003. (2) TerraTek acknowledges Smith International, BP America, PDVSA, and ConocoPhillips for cost-sharing the Smith benchmarking tests allowing extension of the contract to add to the benchmarking testing program. (3) Following the benchmark testing of the Smith International hammer, representatives from DOE/NETL, TerraTek, Smith International and PDVSA met at TerraTek in Salt Lake City to review observations, performance and views on the optimization step for 2003. (4) The December 2002 issue of Journal of Petroleum Technology (Society of Petroleum Engineers) highlighted the DOE fluid hammer testing program and reviewed last years paper on the benchmark performance of the SDS Digger and Novatek hammers. (5) TerraTek's Sid Green presented a technical review for DOE/NETL personnel in Morgantown on ''Impact Rock Breakage'' and its importance on improving fluid hammer performance. Much discussion has taken place on the issues surrounding mud hammer performance at depth conditions.

Drilling trends in the nineties

International Nuclear Information System (INIS)

1993-01-01

At a conference on various aspects of well drilling in the 1990s, papers were presented on drilling waste management, well completion and workovers, drilling fluids, drilling rig equipment and design, drilling mechanics, drill stem testing and materials, cementing, business management, health and safety, environmental issues, and directional drilling technology. Separate abstracts have been prepared for 46 papers from this conference

Scientific Drilling with the Sea Floor Drill Rig MeBo

Directory of Open Access Journals (Sweden)

Gerold Wefer

2007-09-01

Full Text Available In March 2007 the sea floor drill rig MeBo (short for “Meeresboden-Bohrgerät”, ‘sea floor drill rig’ in German returned from a 17-day scientific cruise with the new German research vessel Maria S. Merian. Four sites between 350 m and 1700 m water depth were sampled at the continental slope off Morocco by push coring and rotary drilling. Up to 41.5-m-long sediment cores were recovered from Miocene, Pliocene, and Pleistocene marls. MeBo bridges the gapbetween conventional sampling methods from standard multipurpose research vessels (gravity corer, piston corer, dredges and drill ships. Most bigger research vessels will be able to support deployment of the MeBo. Since the drill system can be easily transported within 20-ft containers, worldwide operation from vessels of opportunity is possible. With the MeBo a new system is available for marine geosciences that allows the recovery of high quality samples from soft sediments and hard rock from the deep sea withoutrelying on the services of expensive drilling vessels.

Drilling contract issues

International Nuclear Information System (INIS)

Davison, G.B.; Worden, D.R.; Borbridge, G.K.D.

1997-01-01

Some selected issues which are facing both operators and contractors in drilling for oil and gas, such as the allocation of risk by contract and by statute and the implementation of new technologies, were discussed. There are three varieties of written drilling contracts used in Canada: (1) day work and meterage contracts, (2) master drilling agreements, and (3) contracts that are used in construction projects that do not specifically relate to drilling. Issues relevant to the contractual allocation of risk, to implementing new drilling technologies, to reconciling contract and statute liability, and the formation of strategic alliances for mutual benefit, and the factors contributing to the success of such alliances were explored. 12 refs

Addressing submarine geohazards through scientific drilling

Science.gov (United States)

Camerlenghi, A.

2009-04-01

Natural submarine geohazards (earthquakes, volcanic eruptions, landslides, volcanic island flank collapses) are geological phenomena originating at or below the seafloor leading to a situation of risk for off-shore and on-shore structures and the coastal population. Addressing submarine geohazards means understanding their spatial and temporal variability, the pre-conditioning factors, their triggers, and the physical processes that control their evolution. Such scientific endeavour is nowadays considered by a large sector of the international scientific community as an obligation in order to contribute to the mitigation of the potentially destructive societal effects of submarine geohazards. The study of submarine geohazards requires a multi-disciplinary scientific approach: geohazards must be studied through their geological record; active processes must be monitored; geohazard evolution must be modelled. Ultimately, the information must be used for the assessment of vulnerability, risk analysis, and development of mitigation strategies. In contrast with the terrestrial environment, the oceanic environment is rather hostile to widespread and fast application of high-resolution remote sensing techniques, accessibility for visual inspection, sampling and installation of monitoring stations. Scientific Drilling through the IODP (including the related pre site-survey investigations, sampling, logging and in situ measurements capability, and as a platform for deployment of long term observatories at the surface and down-hole) can be viewed as the centre of gravity of an international, coordinated, multi-disciplinary scientific approach to address submarine geohazards. The IODP Initial Science Plan expiring in 2013 does not address openly geohazards among the program scientific objectives. Hazards are referred to mainly in relation to earthquakes and initiatives towards the understanding of seismogenesis. Notably, the only drilling initiative presently under way is the

Scientific Drilling in the Arctic Ocean: A challenge for the next decades

Science.gov (United States)

Stein, R.; Coakley, B.

2009-04-01

Although major progress in Arctic Ocean research has been made during the last decades, the knowledge of its short- and long-term paleoceanographic and paleoclimatic history as well as its plate-tectonic evolution is much behind that from the other world's oceans. That means - despite the importance of the Arctic in the climate system - the data base we have from this area is still very weak, and large parts of the climate history have not been recovered at all in sedimentary sections. This lack of knowledge is mainly caused by the major technological/ logistic problems in reaching this permanently ice-covered region with normal research vessels and in retrieving long and undisturbed sediment cores. With the successful completion of IODP Expedition 302 ("Arctic Coring Expedition" - ACEX), the first Mission Specific Platform (MSP) expedition within the Integrated Ocean Drilling Program - IODP, a new era in Arctic research has begun. For the first time, a scientific drilling in the permanently ice-covered Arctic Ocean was carried out, penetrating about 430 meters of Quaternary, Neogene, Paleogene and Campanian sediment on the crest of Lomonosov Ridge close to the North Pole. The success of ACEX has certainly opened the door for further scientific drilling in the Arctic Ocean, and will frame the next round of questions to be answered from new drill holes to be taken during the next decades. In order to discuss and plan the future of scientific drilling in the Arctic Ocean, an international workshop was held at the Alfred Wegener Institute (AWI) in Bremerhaven/Germany, (Nov 03-05, 2008; convenors: Bernard Coakley/University of Alaska Fairbanks and Ruediger Stein/AWI Bremerhaven). About 95 scientists from Europe, US, Canada, Russia, Japan, and Korea, and observers from oil companies participated in the workshop. Funding of the workshop was provided by the Consortium for Ocean Leadership (US), the European Science Foundation, the Arctic Ocean Sciences Board, and the

Casing and liners for drilling and completion

CERN Document Server

Byrom, Ted G

2007-01-01

The Gulf Drilling Series is a joint project between Gulf Publishing Company and the International Association of Drilling Contractors. The first text in this Series presents casing design and mechanics in a concise, two-part format. The first part focuses on basic casing design and instructs engineers and engineering students how to design a safe casing string. The second part covers more advanced material and special problems in casing design in a user-friendly format. Learn how to select sizes and setting depths to achieve well objectives, determine casing loads for design purposes, design casing properties to meet burst, collapse and tensile strength requirements and conduct casing running operations safely and successfully.

South African drilling

International Nuclear Information System (INIS)

Anon.

1984-01-01

According to the president of the South African Drilling Association, the drilling industry is meeting head-on the challenges created by the worldwide recession. The paper is a synopsis of several of the papers presented at the SADA symposium and a look at several mining-related drilling projects in South Africa. These papers include grouting techniques, the use of impregnated bits in hard rock drilling, tunnel boring for mines, surveying improvement methods and the use of explosives to increase groundwater yield

Tuned dynamics stabilizes an idealized regenerative axial-torsional model of rotary drilling

Science.gov (United States)

Gupta, Sunit K.; Wahi, Pankaj

2018-01-01

We present an exact stability analysis of a dynamical system idealizing rotary drilling. This system comprises lumped parameter axial-torsional modes of the drill-string coupled via the cutting forces and torques. The kinematics of cutting is modeled through a functional description of the cut surface which evolves as per a partial differential equation (PDE). Linearization of this model is straightforward as opposed to the traditional state-dependent delay (SDDE) model and both the approaches result in the same characteristic equation. A systematic study on the key system parameters influencing the stability characteristics reveals that torsional damping is very critical and stable drilling is, in general, not possible in its absence. The stable regime increases as the natural frequency of the axial mode approaches that of the torsional mode and a 1:1 internal resonance leads to a significant improvement in the system stability. Hence, from a practical point of view, a drill-string with 1:1 internal resonance is desirable to avoid vibrations during rotary drilling. For the non-resonant case, axial damping reduces the stable range of operating parameters while for the resonant case, an optimum value of axial damping (equal to the torsional damping) results in the largest stable regime. Interestingly, the resonant (tuned) system has a significant parameter regime corresponding to stable operation even in the absence of damping.

Catalysts for production of lower olefins from synthesis gas: A review

NARCIS (Netherlands)

Torres Galvis, H.M.; de Jong, K.P.

2013-01-01

C2 to C4 olefins are traditionally produced from steam cracking of naphtha. The necessity for alternative production routes for these major commodity chemicals via non-oil-based processes has driven research in past times during the oil crises. Currently, there is a renewed interest in producing

Metal-free oxidative olefination of primary amines with benzylic C-H bonds through direct deamination and C-H bond activation.

Science.gov (United States)

Gong, Liang; Xing, Li-Juan; Xu, Tong; Zhu, Xue-Ping; Zhou, Wen; Kang, Ning; Wang, Bin

2014-09-14

An oxidative olefination reaction between aliphatic primary amines and benzylic sp(3) C-H bonds has been achieved using N-bromosuccinimide as catalyst and tert-butyl hydroperoxide as oxidant. The olefination proceeds under mild metal-free conditions through direct deamination and benzylic C-H bond activation, and provides easy access to biologically active 2-styrylquinolines with (E)-configuration.

A new drilling method—Earthworm-like vibration drilling

Science.gov (United States)

Wang, Peng; Wang, Ruihe

2018-01-01

The load transfer difficulty caused by borehole wall friction severely limits the penetration rate and extended-reach limit of complex structural wells. A new friction reduction technology termed “earthworm-like drilling” is proposed in this paper to improve the load transfer of complex structural wells. A mathematical model based on a “soft-string” model is developed and solved. The results show that earthworm-like drilling is more effective than single-point vibration drilling. The amplitude and frequency of the pulse pressure and the installation position of the shakers have a substantial impact on friction reduction and load transfer. An optimization model based on the projection gradient method is developed and used to optimize the position of three shakers in a horizontal well. The results verify the feasibility and advantages of earthworm-like drilling, and establish a solid theoretical foundation for its application in oil field drilling. PMID:29641615

Substrate Trapping in Crystals of the Thiolase OleA Identifies Three Channels That Enable Long Chain Olefin Biosynthesis*

OpenAIRE

Goblirsch, Brandon R.; Jensen, Matthew R.; Mohamed, Fatuma A.; Wackett, Lawrence P.; Wilmot, Carrie M.

2016-01-01

Phylogenetically diverse microbes that produce long chain, olefinic hydrocarbons have received much attention as possible sources of renewable energy biocatalysts. One enzyme that is critical for this process is OleA, a thiolase superfamily enzyme that condenses two fatty acyl-CoA substrates to produce a β-ketoacid product and initiates the biosynthesis of long chain olefins in bacteria. Thiolases typically utilize a ping-pong mechanism centered on an active site cysteine residue. Reaction wi...

Surface science of single-site heterogeneous olefin polymerization catalysts

OpenAIRE

Kim, Seong H.; Somorjai, Gabor A.

2006-01-01

This article reviews the surface science of the heterogeneous olefin polymerization catalysts. The specific focus is on how to prepare and characterize stereochemically specific heterogeneous model catalysts for the Ziegler–Natta polymerization. Under clean, ultra-high vacuum conditions, low-energy electron irradiation during the chemical vapor deposition of model Ziegler–Natta catalysts can be used to create a “single-site” catalyst film with a surface structure that produces only isotactic ...

New optimized drill pipe size for deep-water, extended reach and ultra-deep drilling

Energy Technology Data Exchange (ETDEWEB)

Jellison, Michael J.; Delgado, Ivanni [Grant Prideco, Inc., Hoston, TX (United States); Falcao, Jose Luiz; Sato, Ademar Takashi [PETROBRAS, Rio de Janeiro, RJ (Brazil); Moura, Carlos Amsler [Comercial Perfuradora Delba Baiana Ltda., Rio de Janeiro, RJ (Brazil)

2004-07-01

A new drill pipe size, 5-7/8 in. OD, represents enabling technology for Extended Reach Drilling (ERD), deep water and other deep well applications. Most world-class ERD and deep water wells have traditionally been drilled with 5-1/2 in. drill pipe or a combination of 6-5/8 in. and 5-1/2 in. drill pipe. The hydraulic performance of 5-1/2 in. drill pipe can be a major limitation in substantial ERD and deep water wells resulting in poor cuttings removal, slower penetration rates, diminished control over well trajectory and more tendency for drill pipe sticking. The 5-7/8 in. drill pipe provides a significant improvement in hydraulic efficiency compared to 5-1/2 in. drill pipe and does not suffer from the disadvantages associated with use of 6-5/8 in. drill pipe. It represents a drill pipe assembly that is optimized dimensionally and on a performance basis for casing and bit programs that are commonly used for ERD, deep water and ultra-deep wells. The paper discusses the engineering philosophy behind 5-7/8 in. drill pipe, the design challenges associated with development of the product and reviews the features and capabilities of the second-generation double-shoulder connection. The paper provides drilling case history information on significant projects where the pipe has been used and details results achieved with the pipe. (author)

Radiation chemical addition of dimethylformamide to α-olefins

International Nuclear Information System (INIS)

Dederichs, B.; Saus, A.; Lennertz, A.M.

1977-10-01

With n-hexene-1, n-octene-1 and n-decene-1 the radiation-initiated addition of demethyl formamide to α-olefins is described for the fist time. N,N-dimethyl alkane carbonic acid amides and N-methyl-N-alkyl formamides are formed in a ratio of about 50:50. The addition reaction is investigated in depencence of a solvent, of the ratio of the reaction, temperature, reaction time and dose rate. Mechanistic considerations are performed by radiolysis experiments of dimethyl formamide. (orig.) [de

The Hans Tausen drill

DEFF Research Database (Denmark)

Johnsen, Sigfus Johann; Dahl-Jensen, Dorthe; Steffensen, Jørgen Peder

2007-01-01

In the mid-1990s, excellent results from the GRIP and GISP2 deep drilling projects in Greenland opened up funding for continued ice-coring efforts in Antarctica (EPICA) and Greenland (NorthGRIP). The Glaciology Group of the Niels Bohr Institute, University of Copenhagen, was assigned the task...... of providing drilling capability for these projects, as it had done for the GRIP project. The group decided to further simplify existing deep drill designs for better reliability and ease of handling. The drill design decided upon was successfully tested on Hans Tausen Ice Cap, Peary Land, Greenland, in 1995....... The 5.0 m long Hans Tausen (HT) drill was a prototype for the ~11 m long EPICA and NorthGRIP versions of the drill which were mechanically identical to the HT drill except for a much longer core barrel and chips chamber. These drills could deliver up to 4 m long ice cores after some design improvements...

Effects of aromatics, olefins and distillation temperatures (T50 & T90) on particle mass and number emissions from gasoline direct injection (GDI) vehicles

International Nuclear Information System (INIS)

Zhu, Rencheng; Hu, Jingnan; Bao, Xiaofeng; He, Liqiang; Zu, Lei

2017-01-01

Abstratct: Fuel quality is among the primary reasons for severe vehicle pollution. A limited understanding of the effects of gasoline properties on modern vehicle emissions is one obstacle for the establishment of stricter fuel standards in China. The goal of this study was to evaluate the effects of aromatic and olefin contents and T50 and T90 (defined as the 50%v and 90%v distillation temperatures) on tailpipe emissions from gasoline direct injection (GDI) vehicles compliant with China 4 standards. Both gaseous and particle emissions using different types of gasoline were measured. Changing aromatic and olefin contents had relatively small impacts on fuel consumption. Compared with olefins and T90, the regulated gaseous emissions were impacted more by aromatics and T50. Evident decreases of the particle mass (PM) and particle number (PN) emissions were noticed when the aromatic content and T90 decreased. Reducing the olefin content slightly decreased the PM emissions and increased the PN emissions. With decreasing T50, the PM emissions increased and the PN emissions slightly decreased. These results suggest that aromatic content and T90 should be decreased to reduce particle emissions from GDI vehicles. The information presented in this study provides some suggestions for how to improve gasoline quality in China. - Highlights: • Effect of aromatics, olefins, T50 and T90 on GDI vehicle emissions was investigated. • Aromatics and olefins had little impact on fuel consumption and CO 2 emissions. • Reducing the aromatic content and T90 significantly decreased PM and PN emissions. • Changing the olefin content and T50 had a minor impact on particle emissions. • Thresholds of aromatics and T90 should be tightened in future gasoline regulations.

Drilling contracts and incentives

International Nuclear Information System (INIS)

Osmundsen, Petter; Sorenes, Terje; Toft, Anders

2008-01-01

Shortages of rigs and personnel have encouraged discussion of designing incentive contracts in the drilling sector. However, for the drilling contracts, there are not a large variety of contract types in use. This article describes and analyses incentives for drilling contractors. These are directly represented by the compensation formats utilised in the present and in the consecutive drilling contracts. Indirectly, incentives are also provided by the evaluation criteria that oil companies use for awarding drilling assignments. Changes in contract format pose a number of relevant questions relating to resource management, and the article takes an in-depth look at some of these. Do evaluation criteria for awarding drilling assignments encourage the development of new technology and solutions? How will a stronger focus on drilling efficiency influence reservoir utilisation?

Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

International Nuclear Information System (INIS)

Castillo, N.; Perez, R.; Martinez-Ortiz, M.J.; Diaz-Barriga, L.; Garcia, L.; Conde-Gallardo, A.

2010-01-01

Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO 2 in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO 2 were prepared by wetness impregnation techniques at different concentrations of Pt and Pd ∼1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO 2 were characterized by N 2 physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO 2 (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt x -Pd (1-x) /TiO 2 based system was then conducted to study the effects of metals on the nanostructure of the materials.

Synthesis and characterization of new magnetically recoverable molybdenum nanocatalyst for epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of); Kashef, Z. [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of)

2012-04-15

New heterogeneous molybdenum catalyst was prepared through covalent attachment of a Schiff base ligand on the surface of silica coated magnetite nanoparticles via aminopropyl spacer and subsequent complexation with MoO{sub 2}(acac){sub 2}. The prepared nanocatalyst was characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies and vibrating sample magnetometry. Catalytic epoxidation of some olefins and allylic alcohols by prepared nanocatalyst using tert-butyl hydroperoxide and cumene hydroperoxide as oxidants was achieved with good activities and selectivities. - Highlights: Black-Right-Pointing-Pointer Silica coated magnetite nanoparticles were modified with a Schiff base ligand. Black-Right-Pointing-Pointer Next reaction with MoO{sub 2}(acac){sub 2} afforded magnetically recoverable nanocatalyst. Black-Right-Pointing-Pointer The prepared nanocatalyst catalyzed the epoxidation of olefins with TBHP.

A Wittig-olefination-Claisen-rearrangement approach to the 3-methylquinoline-4-carbaldehyde synthesis.

Science.gov (United States)

Kulkarni, Mukund G; Desai, Mayur P; Birhade, Deekshaputra R; Shaikh, Yunus B; Dhatrak, Ajit N; Gannimani, Ramesh

2012-01-01

Efficient syntheses are described for the synthetically important 3-methylquinoline-4-carbaldehydes 6a-h from o-nitrobenzaldehydes 1a-h employing a Wittig-olefination-Claisen-rearrangement protocol. The Wittig reaction of o-nitrobenzaldehydes with crotyloxymethylene triphenylphosphorane afforded crotyl vinyl ethers 2a-h, which on heating under reflux in xylene underwent Claisen rearrangement to give 4-pentenals 3a-h. Protection of the aldehyde group of the 4-pentenals as acetals 4a-h and subsequent oxidative cleavage of the terminal olefin furnished nitroaldehydes 5a-h. Reductive cyclization of these nitroaldehydes yielded the required 3-methylquinoline-4-carbaldehydes 6a-h in excellent yields. Therefore, an efficient method was developed for the preparation of 3-methylquinoline-4-carbaldehydes from o-nitrobenzaldehydes in a simple five-step procedure.

Prediction of properties of new halogenated olefins using two group contribution approaches

DEFF Research Database (Denmark)

Montagud, Maria E. Mondejar; Cignitti, Stefano; Abildskov, Jens

2017-01-01

The increasingly restrictive regulations for substances with high ozone depletion and global warming potentials are driving the search for new sustainable fluids with low environmental impact. Recent research works have pointed out the great potential of fluorine- and chlorine-based olefins as re...

Synthesis of 7-Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

DEFF Research Database (Denmark)

Håkansson, Anders Eckart; Palmelund, Anders; Holm, H.

2006-01-01

from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product....

Sustainable solid catalyst alkylation of commercial olefins by regeneration with supercritical isobutane

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

2005-12-01

Supercritical isobutane regeneration of a USY zeolite alkylation catalyst was examined in a continuous, automated reaction / regeneration system. Two feeds were studied; a synthetic isobutane / 2-butene blend, and a commercial refinery isoparaffin / olefin blend. The refinery blend was minimally treated, containing a variety of light olefins, and contaminants, including butadiene, oxygenates and sulfur, which are well known to cause severe catalyst deactivation. Synthetic feed experiments showed that high levels of butene conversion was maintained for more than 200 hours time on stream, and that product quality and catalyst maintenance was relatively stable over the course of the experiment using a 3 hour reaction / 3 hour regeneration cycle. Catalyst activity maintenance was lower when the commercial feed was employed. High levels of alkene conversion were maintained for 78 hours and 192 hours using a 3 hour reaction / 3 hour regeneration cycle and a 2 hour reaction / 2 hour regeneration cycle, respectively.

Study on drilling induced delamination of woven kenaf fiber reinforced epoxy composite using carbide drills

Science.gov (United States)

Suhaily, M.; Hassan, C. H. Che; Jaharah, A. G.; Azmi, H.; Afifah, M. A.; Khairusshima, M. K. Nor

2018-04-01

In this research study, it presents the influences of drilling parameters on the delamination factor during the drilling of woven kenaf fiber reinforced epoxy composite laminates when using the carbide drill bits. The purpose of this study is to investigate the influence of drilling parameters such as cutting speed, feed rate and drill sizes on the delamination produced when drilling woven kenaf reinforced epoxy composite using the non-coated carbide drill bits. The damage generated on the woven kenaf reinforced epoxy composite laminates were observed both at the entrance and exit surface during the drilling operation. The experiments were conducted according to the Box Behnken experimental designs. The results indicated that the drill diameter has a significant influence on the delamination when drilling the woven kenaf fiber reinforced epoxy composites.

NEW HIGH STRENGTH AND FASTER DRILLING TSP DIAMOND CUTTERS

Energy Technology Data Exchange (ETDEWEB)

Robert Radtke

2006-01-31

The manufacture of thermally stable diamond (TSP) cutters for drill bits used in petroleum drilling requires the brazing of two dissimilar materials--TSP diamond and tungsten carbide. The ENDURUS{trademark} thermally stable diamond cutter developed by Technology International, Inc. exhibits (1) high attachment (shear) strength, exceeding 345 MPa (50,000 psi), (2) TSP diamond impact strength increased by 36%, (3) prevents TSP fracture when drilling hard rock, and (4) maintains a sharp edge when drilling hard and abrasive rock. A novel microwave brazing (MWB) method for joining dissimilar materials has been developed. A conventional braze filler metal is combined with microwave heating which minimizes thermal residual stress between materials with dissimilar coefficients of thermal expansion. The process results in preferential heating of the lower thermal expansion diamond material, thus providing the ability to match the thermal expansion of the dissimilar material pair. Methods for brazing with both conventional and exothermic braze filler metals have been developed. Finite element modeling (FEM) assisted in the fabrication of TSP cutters controllable thermal residual stress and high shear attachment strength. Further, a unique cutter design for absorbing shock, the densification of otherwise porous TSP diamond for increased mechanical strength, and diamond ion implantation for increased diamond fracture resistance resulted in successful drill bit tests.

Drilling Performance of Rock Drill by High-Pressure Water Jet under Different Configuration Modes

Directory of Open Access Journals (Sweden)

Songyong Liu

2017-01-01

Full Text Available In the rock drilling progress, the resistant force results in tools failure and the low drilling efficiency; thus, it is necessary to reduce the tools failure and enhance the drilling efficiency. In this paper, different configuration modes of drilling performance assisted with water jet are explored based on the mechanism and experiment analysis of rock drilling assisted with water jet. Moreover, the rotary sealing device with high pressure is designed to achieve the axial and rotation movement simultaneously as well as good sealing effect under high-pressure water jet. The results indicate that the NDB and NFB have better effects on drilling performance compared with that of NSB. Moreover, the high-pressure water jet is helpful not only to reduce the drill rod deflection, but also to reduce the probability of drill rod bending and improve the drill rod service life.

Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

Science.gov (United States)

Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani

2016-08-18

A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

Access to Functionalized Steroid Side Chains via Modified Julia Olefination

Science.gov (United States)

Izgu, Enver Cagri; Burns, Aaron C.; Hoye, Thomas R.

2011-01-01

Various functionalized steroidal side chains were conveniently accessed by a modified Julia olefination strategy using a common sulfone donor and an appropriate α-branched aldehyde acceptor. For the coupling of these hindered classes of reaction partners (and in contrast to typically observed trends), the benzothiazolyl(BT)-sulfone anion gave superior outcomes compared to the phenyltetrazolyl(PT)-sulfone anion. PMID:21244047

Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization.

Science.gov (United States)

Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming

2018-03-02

A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

Drilling technologies in hydrogeological survey

OpenAIRE

Vorlíček, Petr

2014-01-01

This work deals with the drilling technologies used in hydrogeology. The main aim of the work is to explore types of drilling technologies used at hydrogeological drilling wells and modern technologies that could potentially be used in the future. The work also summarizes a historical development of drilling techniques, a drilling process procedure, information obtained from boreholes and the most common types of drilling fluids.

Design and Exploitation Problems of Drill String in Directional Drilling

Directory of Open Access Journals (Sweden)

Bednarz Stanislaw

2004-09-01

Full Text Available Drill string design for directional drilling requires accounting for a number of factors. First, types and expected values of loads should be determined. Then, elements of the drill string should be so selected as to enable realization of the plan at specified loads. Some of additional factors, e. g. purchase, exploitation cost, geological conditions in the bore-hole, washing of the bore-hole, stability, trajectory, rig parameters, accuracy of gauges, pumps parameters remain in conflict. Drill pipes are made of rolled pipes, upset and welded with tool joints to 9,5 m long; the shorter ones can be made of hot forged rods. Exploitation requirements, being a result of practical experience supported by theoretical and laboratory analyses should be a part of syllabuses of technical staff educational programs. Apart from designing the string, it is also vital to lower the risk of a drilling failure. The significance of these aspects seems to be unquestionable.

Diagnostic System of Drill Condition in Laminated Chipboard Drilling Process

Directory of Open Access Journals (Sweden)

Swiderski Bartosz

2017-01-01

Full Text Available The paper presents an on-line automatic system for recognition of the drill condition in a laminated chipboard drilling process. Two states of the drill are considered: the sharp enough (still able to drill holes acceptable for processing quality and worn out (excessive drill wear, not satisfactory from the quality point of view of the process. The automatic system requires defining the diagnostic features, which are used as the input attributes to the classifier. The features have been generated from 5 registered signals: feed force, cutting torque, noise, vibration and acoustic emission. The statistical parameters defined on the basis of the auto regression model of these signals have been used as the diagnostic features. The sequential step-wise feature selection is applied for choosing the most discriminative set of features. The final step of recognition is done by support vector machine classifier working in leave one out mode. The results of numerical experiments have confirmed good quality of the proposed diagnostic system.

Synthesis of interlocked molecules by olefin metathesis

Science.gov (United States)

Clark, Paul Gregory

A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic

Horizontal drilling under Lake Erie

Energy Technology Data Exchange (ETDEWEB)

Meller, R.

2001-07-01

Drilling oil wells under Lake Erie calls for horizontal drilling wells to be drilled from shore out into the pay-zone under the lake. The nature and characteristics of horizontal wells as compared to vertical wells are explored. Considerations that have to be taken into account in drilling horizontal wells are explained (the degree of curvature, drilling fluid quality, geosteering in the pay-zone, steering instrumentation, measurements while drilling (MWD), logging while drilling (LWD)). The concept and reasons for extended reach wells are outlined, along with characteristic features of multilateral wells.

Pd(II)-catalyzed di-o-olefination of carbazoles directed by the protecting N-(2-pyridyl)sulfonyl group.

Science.gov (United States)

Urones, Beatriz; Gómez Arrayás, Ramón; Carretero, Juan Carlos

2013-03-01

Despite the significance of carbazole in pharmacy and material science, examples of the direct C-H functionalization of this privileged unit are quite rare. The N-(2-pyridyl)sulfonyl group enables the Pd(II)-catalyzed ortho-olefination of carbazoles and related systems, acting as both a directing and readily removable protecting group. This method features ample structural versatility, affording typically the double ortho-olefination products (at C1 and C8) in satisfactory yields and complete regiocontrol. The application of this procedure to related heterocyclic systems, such as indoline, is also described.

Palladium(II)-Catalyzed meta-C-H Olefination: Constructing Multisubstituted Arenes through Homo-Diolefination and Sequential Hetero-Diolefination.

Science.gov (United States)

Bera, Milan; Maji, Arun; Sahoo, Santosh K; Maiti, Debabrata

2015-07-13

Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium-catalyzed synthesis of divinylbenzenes by meta-C-H olefination of sulfone-based arenes. Successful sequential olefinations in a position-selective manner provided a novel route for the synthesis of hetero-dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5-trialkenylated compounds can be generated upon successful removal of the directing group. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alteration in the IRDP drill hole compared with other drill holes in Iceland

Science.gov (United States)

Kristmannsdóttir, Hrefna

1982-08-01

The overall alteration pattern in the drill hole at Reydarfjördur is very similar to alteration patterns observed in Icelandic geothermal areas and in low-grade metamorphosed basalts in deep crustal sections elsewhere in Iceland. However more detail is obtained by the study of the IRDP drill core than by study of drill cuttings sampled in previous drill holes in Iceland. A comparatively high fossil thermal gradient is obtained at Reydarfjördur by a combination of mineral stability data and the observed occurence of secondary minerals. This high gradient is consistent with the measured dike dilation at the drill site and the location of the drill site adjacent to a central volcano.

A self propelled drilling system for hard-rock, horizontal and coiled tube drilling

Energy Technology Data Exchange (ETDEWEB)

Biglin, D.; Wassell, M.

1997-12-31

Several advancements are needed to improve the efficiency and reliability of both hard rock drilling and extended reach drilling. This paper will present a Self Propelled Drilling System (SPDS) which can grip the borehole wall in order to provide a stable platform for the application of weight on bit (WOB) and resisting the reactive torque created by the downhole drilling motor, bit and formation interaction. The system will also dampen the damaging effects of drill string vibration. This tool employs two hydraulically activated anchors (front and rear) to grip the borehole wall, and a two-way thrust mandrel to apply both the drilling force to the bit, and a retraction force to pull the drill string into the hole. Forward drilling motion will commence by sequencing the anchor pistons and thrust mandrel to allow the tool to walk in a stepping motion. The SPDS has a microprocessor to control valve timing, sensing and communication functions. An optional Measurement While Drilling (MWD) interface can provide two-way communication of critical operating parameters such as hydraulic pressure and piston location. This information can then be telemetered to the surface, or used downhole to autonomously control system parameters such as anchor and thrust force or damping characteristics.

Maximizing light olefins production in fluid catalytic cracking (FCC) units; Maximizacao de olefinas leves em unidades de craqueamento catalitico fluido

Energy Technology Data Exchange (ETDEWEB)

Pimenta, Ricardo D.M.; Pinho, Andrea de Rezende [PETROBRAS, Rio de Janeiro, RJ (Brazil)

2004-07-01

The Fluid Catalytic Cracking (FCC) process is widely spread over the ten PETROBRAS refineries in its thirteen industrial units. The importance of the FCC process resides on its high gasoline output, being the main supplier of this important product to the system. Additionally, FCC process is the main source of light hydrocarbons in the LPG range, including light olefins. The increasing demand for ethylene, propylene and butylenes was encouraging to concentrate the research efforts on studies about alternatives for the traditional FCC process. In the present work, the proposals from main licensors (UOP, KBR, Stone and Webster) for a light-olefins-driven FCC process (Petrochemical FCC) will be compared. Furthermore, the catalytic route for light olefins production in FCC units is also described. An additive based on ZSM- 5 zeolite, which is produced following a PETROBRAS proprietary technology, is being largely applied into the catalyst inventories of all FCC units. An analysis of different scenarios was performed to estimate the maximum potential of light olefins production from the highest possible ZSM-5 additive usage. More specifically for the case of ethylene, which production is also boosted by the same type of additive, studies are being conducted with the objective of recovering it from a C2 stream using specific units to do the splitting (UPGR). The search for increasing light olefins production in the refining processes is in line with PETROBRAS strategic plan which targeted for the company a more intense activity in the Brazilian petrochemical market (author)

Beyond 2013 - The Future of European Scientific Drilling Research - An introduction.

Science.gov (United States)

Camoin, G.; Stein, R.

2009-04-01

The Integrated Ocean Drilling Program (IODP) is funded for the period 2003-2013, and is now starting to plan the future of ocean drilling beyond 2013, including the development of new technologies, new emerging research fields as and the societal relevance of this programme. In this context an interdisciplinary and multinational (USA, Europe, Japan, Asian and Oceanian countries), key conference - INVEST IODP New Ventures in Exploring Scientific Targets - addressing all international IODP partners is therefore planned for September 23rd-25th 2009 in Bremen, Germany (more information at http://www.iodp.org and http://marum.de/iodp-invest.html) to discuss future directions of ocean drilling research and related aspects such as ventures with related programmes or with industry. The first critical step of INVEST is to define the scientific research goals of the second phase of the Integrated Ocean Drilling Program (IODP), which is expected to begin in late 2013. INVEST will be open to all interested scientists and students and will be the principal opportunity for the international science community to help shape the future of scientific ocean drilling. The outcome of the conference will be the base to draft a science plan in 2010 and to define new goals and strategies to effectively meet the challenges of society and future ocean drilling. The current EGU Session and the related two days workshop which will be held at the University of Vienna will specifically address the future of European scientific drilling research. The major objectives of those two events are to sharpen the European interests in the future IODP and to prepare the INVEST Conference and are therefore of prime importance to give weight to the European propositions in the program renewal processes, both on science, technology and management, and to provide the participants with information about the status/process of ongoing discussions and negotiations regarding program structure, and provide them

Modeling pellet impact drilling process

Science.gov (United States)

Kovalyov, A. V.; Ryabchikov, S. Ya; Isaev, Ye D.; Ulyanova, O. S.

2016-03-01

The paper describes pellet impact drilling which could be used to increase the drilling speed and the rate of penetration when drilling hard rocks. Pellet impact drilling implies rock destruction by metal pellets with high kinetic energy in the immediate vicinity of the earth formation encountered. The pellets are circulated in the bottom hole by a high velocity fluid jet, which is the principle component of the ejector pellet impact drill bit. The experiments conducted has allowed modeling the process of pellet impact drilling, which creates the scientific and methodological basis for engineering design of drilling operations under different geo-technical conditions.

Remarks on residual stress measurement by hole-drilling and electronic speckle pattern interferometry.

Science.gov (United States)

Barile, Claudia; Casavola, Caterina; Pappalettera, Giovanni; Pappalettere, Carmine

2014-01-01

Hole drilling is the most widespread method for measuring residual stress. It is based on the principle that drilling a hole in the material causes a local stress relaxation; the initial residual stress can be calculated by measuring strain in correspondence with each drill depth. Recently optical techniques were introduced to measure strain; in this case, the accuracy of the final results depends, among other factors, on the proper choice of the area of analysis. Deformations are in fact analyzed within an annulus determined by two parameters: the internal and the external radius. In this paper, the influence of the choice of the area of analysis was analysed. A known stress field was introduced on a Ti grade 5 sample and then the stress was measured in correspondence with different values of the internal and the external radius of analysis; results were finally compared with the expected theoretical value.

1-acetylvinyl acrylates: new captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions

International Nuclear Information System (INIS)

Herrera, Rafael; Universidad Michoacana de San Nicolas de Hidalgo, Morelia, Mich.; Jimenez-Vazquez, Hugo A.; Delgado, Francisco; Tamariz, Joaquin; Soederberg, Bjoern C.G.

2005-01-01

The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemo selectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/6-311G(d,p) calculations. (author)

Efficient and Selective Syntheses of (all-E)- and (6E,10Z)-2′-O-Methylmyxalamides D via Pd-Catalyzed Alkenylation—Carbonyl Olefination Synergy

Science.gov (United States)

Wang, Guangwei; Huang, Zhihong; Negishi, Ei-ichi

2008-01-01

Highly efficient and selective syntheses of both (all-E) and (6E,10Z)-isomers of 2′-O-methylmyxalamide D (2 and 3), in which the crucial conjugated pentaene moieties were assembled in ≥98% stereoselectivity through the use of two Pd-catalyzed alkenylation reactions, the Horner—Wadsworth—Emmons (HWE) olefination, and either the Corey—Schlessinger—Mills modified (CSM-modified) Peterson olefination for 2 or the Still—Gennari olefination for 3, are reported. Either 2 or 3 was prepared in 16% yield in seven steps from propargyl alcohol. PMID:18593171

500.000 years of environmental history in Eastern Anatolia: The PALEOVAN drilling project

DEFF Research Database (Denmark)

Litt, Thomas; Anselmetti, Flavio; Baumgarten, Henrike

2012-01-01

International Continental Scientific Drilling Program (ICDP) drilled a complete succession of the lacustrine sediment sequence deposited during the last ~500,000 years in Lake Van, Eastern Anatolia (Turkey). Based on a detailed seismic site survey, two sites at a water depth of up to 360 m were...... drilled in summer 2010, and cores were retrieved from sub-lake-floor depths of 140 m (Northern Basin) and 220 m (Ahlat Ridge). To obtain a complete sedimentary section, the two sites were multiple-cored in order to investigate the paleoclimate history of a sensitive semi-arid region between the Black...

Structural analysis of platinum-palladium nanoparticles dispersed on titanium dioxide to evaluate cyclo-olefines reactivity

Energy Technology Data Exchange (ETDEWEB)

Castillo, N., E-mail: necastillo@yahoo.co [Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Edificio B, 04510 Mexico DF (Mexico); Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico); Perez, R. [Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico, Campus Morelos, 62251 Cuernavaca Morelos (Mexico); Martinez-Ortiz, M.J.; Diaz-Barriga, L. [Instituto Politecnico Nacional - ESIQIE, UPALM Edif. 7, 07738 Mexico DF (Mexico); Garcia, L. [Instituto Politecnico Nacional - ESIT, UPALM, 07738 Mexico DF (Mexico); Conde-Gallardo, A. [Centro de Investigacion y de Estudios Avanzados del IPN, Depto. de Fisica, Av. IPN 2508, C.P. 07360, Mexico DF (Mexico)

2010-04-16

Structural and chemical properties were correlated to explain catalytic behavior of Pt-Pd/TiO{sub 2} in a cyclo-olefin reaction. Bimetallic nanoparticles supported on TiO{sub 2} were prepared by wetness impregnation techniques at different concentrations of Pt and Pd {approx}1 metallic wt%. The physicochemical properties of these metallic nanoparticles supported on TiO{sub 2} were characterized by N{sub 2} physisorption (Brunauer-Emmett-Teller-BET), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The relationship between chemical composition, physicochemical properties and particle size on the cyclo-olefin reaction was then studied. XRD and TEM results show that these nanoparticles are composed of Pt-Pd with FFC structure (a = 0.389-0.391 nm) supported on TiO{sub 2} (anatase-like structure), and the materials present tetragonal structure nanoparticles (a = 0.37842, b = 0.37842, c = 0.95146 nm). Samples with higher contents of platinum and particle sizes of 4.2 nm show the highest catalytic conversion in cyclo-olefins reaction. Finally, structural examinations of Pt{sub x}-Pd{sub (1-x)}/TiO{sub 2} based system was then conducted to study the effects of metals on the nanostructure of the materials.

An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4.

Science.gov (United States)

Nicolaou, K C; Adsool, Vikrant A; Hale, Christopher R H

2010-04-02

PhI(OAc)(2) in the presence of OsO(4) (cat.) and 2,6-lutidine cleaves olefinic bonds to yield the corresponding carbonyl compounds, albeit, in some cases, with alpha-hydroxy ketones as byproduct. A more practical and clean protocol to effect oxidative cleavage of olefinic bonds involves NMO, OsO(4) (cat.), 2,6-lutidine, and PhI(OAc)(2).

Seize the data (Carpe data) : wave of computerized data capture technology sweeps drilling industry

Energy Technology Data Exchange (ETDEWEB)

Mahoney, J.

1999-02-01

The computerization of all aspects of the monitoring and collection of well drilling information is discussed. Global Link International Inc. of Calgary, has developed a computerized system for tracking and recording drilling data. This operations recording database is named the Electronic Tour Book (ETB). It is similar to the Electronic Tour Sheet (ETS) developed by Chimo Equipment Ltd. of Alberta. Both Windows-based systems represent computerized reporting mechanisms for operators, producers, loggers and rig-managers. Another Alberta company, Ryan Energy Technologies Inc., has begun marketing the Tru Vu Fusion system of hardware and software, yet another system for gathering and recording drilling data. Tru Vu Fusion can capture data and display it in a format that everybody at the wellsite can use for decision making. Another drilling data management system, entitled INSITE (for Integrated System for Information Technology and Engineering) is marketed by Sperry-Sun Drilling Services. While INSITE is intended primarily for offshore drilling applications, it can be used onshore with equal success. 4 figs.

Recent Multidisciplinary Research Initiatives and IODP Drilling in the South China Sea

Science.gov (United States)

Lin, J.; Li, C. F.; Wang, P.; Kulhanek, D. K.

2016-12-01

The South China Sea (SCS) is the largest low-latitude marginal sea in the world. Its formation and evolution are linked to the complex continental-oceanic tectonic interaction of the Eurasian, Pacific, and Indo-Australian plates. Despite its relatively small size and short history, the SCS has undergone nearly a complete Wilson cycle from continental break-up to seafloor spreading to subduction, serving as a natural laboratory for studying the linkages between tectonic, volcanic, and oceanic processes. The last several years have witnessed significant progress in investigation of the SCS through comprehensive research programs using multidisciplinary approaches and enhanced international collaboration. The International Ocean Discovery Program (IODP) Expedition 349 drilled and cored five sites in the SCS in 2014. The expedition successfully obtained the first basaltic rock samples of the SCS relict spreading center, discovered large and frequent deep-sea turbidity events, and sampled multiple seamount volcaniclastic layers. In addition, high-resolution near-seafloor magnetic surveys were conducted in the SCS with survey lines passing near some of the IODP drilling sites. Together the IODP drilling and deep-tow magnetic survey results confirmed, for the first time, that the entire SCS basin might have stopped seafloor spreading at similar ages in early Miocene, providing important constraints on marginal sea geodynamic models. In 2007, IODP Expeditions 367 and 368 will drill the northern margin of the SCS to investigate the mechanisms of rifting to spreading processes. Meanwhile, major progress in studying the SCS processes has also been made through comprehensive multidisciplinary programs, for example, the eight-year-long "South China Sea Deep" initiative, which also supports and encourages strong international collaboration. This presentation will highlight the recent multidisciplinary research initiatives in investigation of the SCS and the important role of

Drilling a better pair : new technologies in SAGD directional drilling

Energy Technology Data Exchange (ETDEWEB)

Zimmer, C.; Richter, D. [Statoil Canada Ltd., Calgary, AB (Canada); Person, J.; Tilley, J.; Bittar, M. [Halliburton Energy Services, Calgary, AB (Canada)

2010-07-01

The Leismer Demonstration Project (LDP) is the first of 8 proposed major steam assisted gravity drainage (SAGD) projects for Statoil's Kai Kos Dehseh (KKD) asset in the Athabasca oil sands deposit. The bitumen resources are expected to produce approximately 2.2 billion barrels of oil over approximately 35 years with a peak production of 220,000 bbl/day. To date, 23 well pairs have been drilled on 4 drilling pads. The precise placement of well pairs is among the most important factors in a successful SAGD drilling program. The producer well must be placed in relation to the reservoir boundaries. It must also be accurately twinned with the injector well. A strong focus on technological innovation is needed in order to deliver on these high expectations in unconsolidated formations, such as the McMurray oil sands. Lateral SAGD pairs are often drilled with conventional steerable mud motors and logging-while-drilling (LWD) resistivity measurements, but this combination imposes certain limitations in terms of wellbore quality and placement. Several industry firsts were successfully implemented at the Statoil LDP, including a combination of the newest and most cutting-edge directional, measurement, and LWD technology. The keystone of these industry firsts was the use of a soft formation modified, point-the-bit rotary steerable system (RSS), used on 20 horizontal wells. The RRS was combined with an ultra deep azimuthal resistivity sensor to provide precise geosteering along the bottom bed boundary in the producer wells, resulting in improved reservoir capture and reservoir characterization. This paper described the new drilling system and its impact on the progressive future of directional drilling in SAGD. 8 refs., 1 tab., 22 figs.

WETTABILITY AND PREDICTION OF OIL RECOVERY FROM RESERVOIRS DEVELOPED WITH MODERN DRILLING AND COMPLETION FLUIDS

Energy Technology Data Exchange (ETDEWEB)

Jill S. Buckley; Norman R. Morrow

2004-05-01

We report on progress in three areas. In part one, the wetting effects of synthetic base oils are reported. Part two reports progress in understanding the effects of surfactants of known chemical structures, and part three integrates the results from surface and core tests that show the wetting effects of commercial surfactant products used in synthetic and traditional oil-based drilling fluids. An important difference between synthetic and traditional oil-based muds (SBM and OBM, respectively) is the elimination of aromatics from the base oil to meet environmental regulations. The base oils used include dearomatized mineral oils, linear alpha-olefins, internal olefins, and esters. We show in part one that all of these materials except the esters can, at sufficiently high concentrations, destabilize asphaltenes. The effects of asphaltenes on wetting are in part related to their stability. Although asphaltenes have some tendency to adsorb on solid surfaces from a good solvent, that tendency can be much increased near the onset of asphaltene instability. Tests in Berea sandstone cores demonstrate wetting alteration toward less water-wet conditions that occurs when a crude oil is displaced by paraffinic and olefinic SBM base oils, whereas exposure to the ester products has little effect on wetting properties of the cores. Microscopic observations with atomic forces microscopy (AFM) and macroscopic contact angle measurements have been used in part 2 to explore the effects on wetting of mica surfaces using oil-soluble polyethoxylated amine surfactants with varying hydrocarbon chain lengths and extent of ethoxylation. In the absence of water, only weak adsorption occurs. Much stronger, pH-dependent adsorption was observed when water was present. Varying hydrocarbon chain length had little or no effect on adsorption, whereas varying extent of ethoxylation had a much more significant impact, reducing contact angles at nearly all conditions tested. Preequilibration of

Lake Eĺ gygytgyn Drilling under way: State of the operation and first results

Science.gov (United States)

Melles, M.; Brigham-Grette, J.; Minyuk, P.; Koeberl, C.; Scientific Party, EĺGygytgyn

2009-04-01

Lake Eĺgygytgyn, located in central Chukotka, NE Siberia, was formed 3.6 million years ago by a meteorite impact and has never been glaciated or desiccated. This makes Lake Eĺgygytgyn a unique target of an interdisciplinary, multi-national drilling campaign, which currently is carried out as part of the International Continental Drilling Program (ICDP). Drilling operations started in Nov./Dec. 2008, when a 142 m long sediment core was retrieved from the permafrost deposits in the western lake catchment by the local drilling company Chaun Mine Geological Company (CGE). The core penetrated coarse-grained, ice-rich alluvial sediments with variable contents of fine-grained material. It will be investigated for the environmental history, including potential lake-level changes, and the permafrost characteristics, in order to learn more about the influences of catchment changes on the lake sedimentation. Besides, the hole was permanently instrumented for future ground temperature monitoring as part of the Global Terrestrial Network for Permafrost (www.gtnp.org/index_e.html). The major drilling effort will commence in Febr. 2009, when two sites in the central part of Lake Eĺgygytgyn shall be drilled down to 630 m below the lake floor. Drilling will be carried out by DOSECC, using a new GLAD 800 system that will be operated from an enclosed platform on the lake ice. Drilling objectives include replicate overlapping cores from the up to 420 m thick lake sediment fill. The cores promise to yield the longest, most continuous record of climate change in the terrestrial Arctic, extending back one million years prior to the intensification of the Northern Hemisphere Glaciation at the Pliocene/Pleistocene boundary, thus offering unique insight into the climatic and environmental history of the Arctic and its comparison with records from lower latitude marine and terrestrial sites to better understand hemispheric and global climate change. Coring shall be continued up to 300 m

Methods to ensure optimal off-bottom and drill bit distance under pellet impact drilling

Science.gov (United States)

Kovalyov, A. V.; Isaev, Ye D.; Vagapov, A. R.; Urnish, V. V.; Ulyanova, O. S.

2016-09-01

The paper describes pellet impact drilling which could be used to increase the drilling speed and the rate of penetration when drilling hard rock for various purposes. Pellet impact drilling implies rock destruction by metal pellets with high kinetic energy in the immediate vicinity of the earth formation encountered. The pellets are circulated in the bottom hole by a high velocity fluid jet, which is the principle component of the ejector pellet impact drill bit. The paper presents the survey of methods ensuring an optimal off-bottom and a drill bit distance. The analysis of methods shows that the issue is topical and requires further research.

75 FR 34974 - Drill Pipe From the People's Republic of China: Alignment of Final Countervailing Duty...

Science.gov (United States)

2010-06-21

... DEPARTMENT OF COMMERCE International Trade Administration [C-570-966] Drill Pipe From the People's... duty investigation of drill pipe from the People's Republic of China (PRC) with the final determination....S. Department of Commerce, Room 4014, 14th Street and Constitution Avenue, NW., Washington, DC 20230...

Ultrasonically assisted drilling of rocks

Science.gov (United States)

Mikhailova, N. V.; Onawumi, P. Y.; Roy, A.; Silberschmidt, V. V.

2018-05-01

Conventional drilling of rocks can generate significant damage in the drilled material; a material layer is often split off a back surface of a sample during drilling, negatively affecting its strength. To improve finish quality, ultrasonically assisted drilling (UAD) was employed in two rocks - sandstone and marble. Damage areas in both materials were reduced in UAD when compared to conventional drilling. Reductions in a thrust force and a torque reduction were observed only for UAD in marble; ultrasonic assistance in sandstone drilling did not result in improvements in this regard.

Conceptual design of coke-oven gas assisted coal to olefins process for high energy efficiency and low CO2 emission

International Nuclear Information System (INIS)

Man, Yi; Yang, Siyu; Zhang, Jun; Qian, Yu

2014-01-01

Highlights: • A novel coke-oven gas assisted coal to olefins (GaCTO) process is proposed. • GaCTO has higher energy efficiency and emits less CO 2 compared to coal-to-olefins process. • GaCTO proposes an idea of using redundant coke-oven gas for producing value added products. - Abstract: Olefins are one of the most important platform chemicals. Developing coal-to-olefins (CTO) processes is regarded as one of promising alternatives to oil-to-olefins process. However, CTO suffers from high CO 2 emission due to the high carbon contents of coal. In China, there is 7 × 10 10 m 3 coke-oven gas (COG) produced in coke plants annually. However, most of the hydrogen-rich COG is utilized as fuel or discharged directly into the air. Such situation is a waste of precious hydrogen resource and serious economic loss, which causes serious environmental pollution either. This paper proposes a novel co-feed process of COG assist CTO in which CH 4 of COG reacts with CO 2 in a Dry Methane Reforming unit to reduce emissions, while the Steam Methane Reforming unit produces H 2 -rich syngas. H 2 of COG can adjust the H/C ratio of syngas. The analysis shows that the energy efficiency of the co-feed process increases about 10%, while at the same time, life cycle carbon footprint is reduced by around 85% in comparison to the conventional CTO process. The economic sustainability of the co-feed process will be reached when the carbon tax would be higher than 150 CNY/t CO 2

Aerobic Pd-Catalyzed sp3 C–H Olefination: A Route to Both N-Heterocyclic Scaffolds and Alkenes

Science.gov (United States)

Stowers, Kara J.; Fortner, Kevin C.

2011-01-01

This communication describes a new method for the Pd/polyoxometalate-catalyzed aerobic olefination of unactivated sp3 C–H bonds. Nitrogen heterocycles serve as directing groups, and air is used as the terminal oxidant. The products undergo reversible intramolecular Michael addition, which protects the mono-alkenylated product from over-functionalization. Hydrogenation of the Michael adducts provides access to bicyclic nitrogen-containing scaffolds that are prevalent in alkaloid natural products. Additionally, the cationic Michael adducts undergo facile elimination to release α,β-unsaturated olefins, which can be elaborated in numerous C–C and C–heteroatom bond-forming reactions. PMID:21476513

Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

Energy Technology Data Exchange (ETDEWEB)

Wienand, A.; Reissig, H.U. (Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany))

1990-12-01

The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

Ether-Directed ortho-C–H Olefination with a PdII/MPAA Catalyst**

Science.gov (United States)

Li, Gang; Leow, Dasheng; Wan, Li; Yu, Jin-Quan

2013-01-01

Weak coordination is powerful! A PdII-catalyzed olefination of ortho-C–H bonds of arenes directed by weakly coordinating ethers is developed using mono-protected amino acid (MPAA) ligands. This finding provides a method for chemically modifying ethers, which are abundant in natural products and drug molecules. PMID:23239120

Remarks on Residual Stress Measurement by Hole-Drilling and Electronic Speckle Pattern Interferometry

Directory of Open Access Journals (Sweden)

Claudia Barile

2014-01-01

Full Text Available Hole drilling is the most widespread method for measuring residual stress. It is based on the principle that drilling a hole in the material causes a local stress relaxation; the initial residual stress can be calculated by measuring strain in correspondence with each drill depth. Recently optical techniques were introduced to measure strain; in this case, the accuracy of the final results depends, among other factors, on the proper choice of the area of analysis. Deformations are in fact analyzed within an annulus determined by two parameters: the internal and the external radius. In this paper, the influence of the choice of the area of analysis was analysed. A known stress field was introduced on a Ti grade 5 sample and then the stress was measured in correspondence with different values of the internal and the external radius of analysis; results were finally compared with the expected theoretical value.

Review of casing while drilling technology

Directory of Open Access Journals (Sweden)

Pavković Bojan

2016-01-01

Full Text Available Conventional drilling methods have been plagued with huge operational and financial challenges, such as cost of purchasing, inspecting, handling, transporting the drill equipment and most importantly, tripping in-and-out of the drill string whenever the Bottom Hole Assembly (BHA needs a replacement, needs of wiper trip or when total depth is reached. The tripping in-and-out of the drill string not only contributes to Non Productive Time (NPT but also leads to well control difficulties including wellbore instability and lost circulation. All this has led Oil and Gas industry, as well as any other engineering industry, to seek for new ways and methods in order to reduce these problems. Thanks to the advances in technical solutions and constant improvements of conventional drilling methods, a new drilling method - casing while drilling has been developed. Casing Drilling encompasses the process of simultaneously drilling and casing a well, using the active casing and thus optimizes the production. This paper presents a review of casing while drilling method (CwD and its practical usage in drilling wells. The comparison of conventional drilling method and casing while drilling is also presented. The CwD method achieves significantly better results than conventional drilling method.

Deepwater drilling; Jakten paa de store dyp

Energy Technology Data Exchange (ETDEWEB)

NONE

2003-07-01

Recent technological development has made it possible to drill for oil and gas at the impressive depth of 3000 metres. An increasing part of the world's oil and gas discoveries are made in deep or ultra deep waters. Ultra deep waters are those exceeding 1500 metres. Since drilling at more than 500 metres started at the end of the 1970s, 32 discoveries of about 500 million barrels of extractable oil or gas have been made. These finds amount to almost 60 thousand millions barrels of oil equivalents. Most of the effort has been made in the coasts between Brazil, West Africa and the Gulf of Mexico. Deepwater projects have been a field of priority for Norwegian oil companies in their search for international commissions. It is frequently time-consuming, expensive and technologically challenging to drill at great depths. The article describes the Atlantis concept, which may reduce the complexities and costs of deepwater activities. This involves making an artificial sea bottom, which in the form of an air-filled buoy is anchored at a depth of 200 - 300 metres. Production wells or exploration wells and risers are extended from the real bottom to the artificial one.

Deep drilling KLX 02. Drilling and documentation of a 1700 m deep borehole at Laxemar, Sweden

Energy Technology Data Exchange (ETDEWEB)

Andersson, O [VBB VIAK AB, Malmoe (Sweden)

1994-08-01

In this report the preparation and execution of the deep core drilling KLX 02 is described. The hole was drilled with the wireline methods, NQ dimension (diameter 76 mm), to a final depth of 1700.5 m. Prior to core drilling a diameter 215 mm pilot hole was pre drilled to 200 m with controlled hammer drilling (DTH). In this hole casing and air-lift equipment was installed with the aim to support the circulation of drilling fluid. During core drilling there was a measurement of major drilling parameters and drilling fluid in and out of hole. As a fluid tracer uranine was used. Each 300 m of core drilling air-lift pump tests were performed. After completion a flow-meter log was run to finalize the project phase. It can be concluded that both the pre drilling and core drilling methods used proved to be successful. No severe technical problem occurred. However, potential risks have been pointed at in the report. The air-lift system functioned only partly and has to be modified for further use. Also the technique for monitoring of drilling parameters needs improvement as does the method for air-lift pump tests with packer. The organisation model for planning and realization functioned satisfactory and can be recommended for similar future projects. 9 refs, numerous tabs and figs.

Deep drilling KLX 02. Drilling and documentation of a 1700 m deep borehole at Laxemar, Sweden

International Nuclear Information System (INIS)

Andersson, O.

1994-08-01

In this report the preparation and execution of the deep core drilling KLX 02 is described. The hole was drilled with the wireline methods, NQ dimension (diameter 76 mm), to a final depth of 1700.5 m. Prior to core drilling a diameter 215 mm pilot hole was pre drilled to 200 m with controlled hammer drilling (DTH). In this hole casing and air-lift equipment was installed with the aim to support the circulation of drilling fluid. During core drilling there was a measurement of major drilling parameters and drilling fluid in and out of hole. As a fluid tracer uranine was used. Each 300 m of core drilling air-lift pump tests were performed. After completion a flow-meter log was run to finalize the project phase. It can be concluded that both the pre drilling and core drilling methods used proved to be successful. No severe technical problem occurred. However, potential risks have been pointed at in the report. The air-lift system functioned only partly and has to be modified for further use. Also the technique for monitoring of drilling parameters needs improvement as does the method for air-lift pump tests with packer. The organisation model for planning and realization functioned satisfactory and can be recommended for similar future projects. 9 refs, numerous tabs and figs

Drilling subsurface wellbores with cutting structures

Science.gov (United States)

Mansure, Arthur James; Guimerans, Rosalvina Ramona

2010-11-30

A system for forming a wellbore includes a drill tubular. A drill bit is coupled to the drill tubular. One or more cutting structures are coupled to the drill tubular above the drill bit. The cutting structures remove at least a portion of formation that extends into the wellbore formed by the drill bit.

Performance of Partially-Hydrolyzed Polyacrylamide in Water Based Drilling Fluids

Directory of Open Access Journals (Sweden)

Ali Reza Nasiri*

2013-05-01

Full Text Available Fluid properties with constant improvement in efficiency have been noticeable as important criteria in drilling operation. The main drilling fluid properties highly depend on utilization of new polymers with high efficiency in drilling fluid composition. In this paper, the performance of a new polymer, called partially hydrolyzed polyacrylamide polymer (PHPA, is studied which has recently entered the drilling fluids industry in Iran. Hence viscosity property, fluid loss control and shale inhibition of this polymer have been evaluated based on an international standard method of API-13-I by considering the drilling and operational priorities of thecountry. Then the thermal effect, salt contaminants such as sodium chloride, calcium chloride, magnesium chloride and pH tolerance effect as major pollution indicators are also investigated in relation to polymeric fluid properties. The results obtained by the tests show that furthermore polymer PHPA increases rheological properties (apparent viscosity, plastic fluidity and yield point and it plays important role in increases in fluid loss. This polymer has also demonstrated acceptable resistance toward sodium chloride contaminants, but its efficiency decreases toward calcium and magnesium ion contaminants. The thermal tests show that polymer PHPA has high thermal stability up to 150°C. This polymer improves shale inhibition property and by encapsulation mechanism prevents dispersion of shale cuttings into the drilling fluid system as it stops any changes in fluid properties which will finally results inwellbore stability.

To drill or not to drill? An econometric analysis of US public opinion

International Nuclear Information System (INIS)

Mukherjee, Deep; Rahman, Mohammad Arshad

2016-01-01

Offshore drilling in the United States (US) has been the subject of public and political discourse due to multiple reasons which include economic impact, energy security, and environmental hazard. Consequently, several polls have been conducted over time to gauge public attitude towards offshore drilling. Nevertheless, the economic literature on this issue is sparse. This paper contributes to the literature and analyzes support for offshore drilling based on demographic, economic, social, belief, and shock (e.g. spill) factors. The data is taken from ten nationwide surveys conducted before, during and after the British Petroleum (BP) oil spill and analyzed within the framework of discrete choice model. The results from an ordinal probit model demonstrate that age, annual household income, affiliation to Republican Party, and residence in oil-rich states positively affect the probability of strong support and reduce the probability of strong opposition for offshore drilling. In contrast, the female gender, higher education, association to Democratic Party, and environmental concern affect opinion in opposite direction. Marginal effects show that belief about environmental consequences of drilling has the highest impact on opinion. Binary probit model also yields a similar result and suggests that BP oil disaster resulted in a transient decrease in support for offshore drilling. - Highlights: •US public opinion on offshore drilling is analyzed based on ten national polls. •Ordinal and binary probit models are utilized to identify the underlying factors that shape public opinion. •Belief about environmental cost of drilling and educational attainment have the highest negative impact on opinion. •Age, income, affiliation to Republican party and oil-rich states positively affect support for drilling. •BP oil spill resulted in a transient decrease in support for offshore drilling.

Percussive Augmenter of Rotary Drills for Operating as a Rotary-Hammer Drill

Science.gov (United States)

Aldrich, Jack Barron (Inventor); Bar-Cohen, Yoseph (Inventor); Sherrit, Stewart (Inventor); Badescu, Mircea (Inventor); Bao, Xiaoqi (Inventor); Scott, James Samson (Inventor)

2014-01-01

A percussive augmenter bit includes a connection shaft for mounting the bit onto a rotary drill. In a first modality, an actuator percussively drives the bit, and an electric slip-ring provides power to the actuator while being rotated by the drill. Hammering action from the actuator and rotation from the drill are applied directly to material being drilled. In a second modality, a percussive augmenter includes an actuator that operates as a hammering mechanism that drives a free mass into the bit creating stress pulses that fracture material that is in contact with the bit.

Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

Science.gov (United States)

Kim, Pilho; Barry, Clifton E.; Dowd*, Cynthia S.

2006-01-01

Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of desired product to deformylated product. PMID:16699591

In-process and post-process measurements of drill wear for control of the drilling process

Science.gov (United States)

Liu, Tien-I.; Liu, George; Gao, Zhiyu

2011-12-01

Optical inspection was used in this research for the post-process measurements of drill wear. A precision toolmakers" microscope was used. Indirect index, cutting force, is used for in-process drill wear measurements. Using in-process measurements to estimate the drill wear for control purpose can decrease the operation cost and enhance the product quality and safety. The challenge is to correlate the in-process cutting force measurements with the post-process optical inspection of drill wear. To find the most important feature, the energy principle was used in this research. It is necessary to select only the cutting force feature which shows the highest sensitivity to drill wear. The best feature selected is the peak of torque in the drilling process. Neuro-fuzzy systems were used for correlation purposes. The Adaptive-Network-Based Fuzzy Inference System (ANFIS) can construct fuzzy rules with membership functions to generate an input-output pair. A 1x6 ANFIS architecture with product of sigmoid membership functions can in-process measure the drill wear with an error as low as 0.15%. This is extremely important for control of the drilling process. Furthermore, the measurement of drill wear was performed under different drilling conditions. This shows that ANFIS has the capability of generalization.

Comprehensive borehole management for shorter drilling time; Umfassendes Bohrfortschrittsmanagement zur Verkuerzung der Bohrprojektdauer

Energy Technology Data Exchange (ETDEWEB)

Roehrlich, M. [ExxonMobil Production Deutschland GmbH, Hannover (Germany)

2007-09-13

In 2006, the trademarked ExxonMobil Fast Drill Process (FDP) was introduced also in the German ExxonMobil boreholes. The process is to maximize the drilling speed for every meter drilled. The process makes it possible to ensure borehole management on the basis of quantitative data and in consideration of all phases that are relevant for sinking a borehole. The FDP is used world-wide in all ExxonMobil drilling departments. More than 1.35 million meters are drilled annually in many different boreholes with different geological conditions, drilling profiles and international sites. The results were similar in many cases, with a significant increase in ROP and drill bit life, and with less damage caused by vibrations. FDP was developed on the basis of real time monitoring of the specific mechanical energy (MSE) required for drilling. MSE monitoring was found to be an effective tool dor detecting inefficient functioning of the drill bit and the overall system. To make operation more efficient, the causes must be identified and measures must be taken accordingly, taking into account the potential risks involved in such measures. MSE monitoring is a tool while FDPL is a broad management process ensuring that MSE and many other data sources are used effectively for optimisation of the ROP. Consequent implementation of the process resulted in a significant increase of the ROP. The major elements required for achieving this goal are discussed. (orig.)

Technical performance of drilling operations of wells Erslev 1 and 2 on Mors Salt Dome

International Nuclear Information System (INIS)

Gomm, H.

1982-01-01

This paper deals strictly with the performance of the drilling itself. The wells were designed and drilled by an international team of experts, using a Cabot Franks Explorer 900 rig. The two exploration wells were located in the top area of the Mors Saltdome after geological and geophysical investigations at a distance of about 1 100 m. (EG)

OsO(4) in ionic liquid [Bmim]PF(6): a recyclable and reusable catalyst system for olefin dihydroxylation. remarkable effect of DMAP.

Science.gov (United States)

Yao, Qingwei

2002-06-27

[reaction: see text] The combination of the ionic liquid [bmim]PF(6) and DMAP provides a most simple and practical approach to the immobilization of OsO(4) as catalyst for olefin dihydroxylation. Both the catalyst and the ionic liquid can be repeatedly recycled and reused in the dihydroxylation of a variety of olefins with only a very slight drop in catalyst activity.

Active Suppression of Drilling System Vibrations For Deep Drilling

Energy Technology Data Exchange (ETDEWEB)

Raymond, David W.; Blankenship, Douglas A.; Buerger, Stephen; Mesh, Mikhail; Radigan, William Thomas; Su, Jiann-Cherng

2015-10-01

The dynamic stability of deep drillstrings is challenged by an inability to impart controllability with ever-changing conditions introduced by geology, depth, structural dynamic properties and operating conditions. A multi-organizational LDRD project team at Sandia National Laboratories successfully demonstrated advanced technologies for mitigating drillstring vibrations to improve the reliability of drilling systems used for construction of deep, high-value wells. Using computational modeling and dynamic substructuring techniques, the benefit of controllable actuators at discrete locations in the drillstring is determined. Prototype downhole tools were developed and evaluated in laboratory test fixtures simulating the structural dynamic response of a deep drillstring. A laboratory-based drilling applicability demonstration was conducted to demonstrate the benefit available from deployment of an autonomous, downhole tool with self-actuation capabilities in response to the dynamic response of the host drillstring. A concept is presented for a prototype drilling tool based upon the technical advances. The technology described herein is the subject of U.S. Patent Application No. 62219481, entitled "DRILLING SYSTEM VIBRATION SUPPRESSION SYSTEMS AND METHODS", filed September 16, 2015.

Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

Science.gov (United States)

Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

2013-03-06

A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

Biomimetic Aerobic C-H Olefination of Cyclic Enaminones at Room Temperature: Development toward the Synthesis of 1,3,5-Trisubstituted Benzenes.

Science.gov (United States)

Yu, Yi-Yun; Georg, Gunda I

2014-04-14

A green and mild protocol for the dehydrogenative olefination of cyclic enaminones was devised via palladium catalysis at room temperature using oxygen as the terminal oxidant. The synthetic utility of the olefinated cyclic enaminones afforded a series of unique 1,3,5-trisubstituted benzenes via an unanticipated Diels-Alder tandem reaction. The broad substrate scope and good yields achieved with this new protocol provide an alternative pathway for arene functionalization.

Pneumatically Powered Drilling of Carbon Fibre Composites Using Synthetic Biodegradable Lubricating Oil: An Experimental Study

Directory of Open Access Journals (Sweden)

Corydon M. J. Morrell

2018-01-01

Full Text Available Carbon fibre composites are a key component of aircraft structures because of their enhanced material properties such as favourable strength to weight ratios when compared to metal alloys. During the assembly process of an aircraft, carbon fibre components are joined to other structures using rivets, bolts, and fasteners, and as part of the joining process, the components will need to be machined or drilled. Unlike metal alloys, composites are sensitive to heat and are vulnerable to internal structural damage from machining tools. They are also susceptible to a reduction in strength when fibres are exposed to moisture. In the machining process, carbon fibre composites may be drilled using oils to lubricate carbide machining tools. In this study, a description of the experimental apparatus is provided along with an investigation to determine the influence synthetic biodegradable lubricating oil has on drill rotational speed, drilling load, and drilling temperature when using a pneumatic drill to machine carbon fibre composite material.

A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

Energy Technology Data Exchange (ETDEWEB)

Doshi, B.M.

1978-01-01

A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

Drilling for scientific purpose

Energy Technology Data Exchange (ETDEWEB)

Tanaka, Shoichi

1987-09-01

Drilling for scientific purpose is a process of conducting geophysical exploration at deep underground and drilling for collecting crust samples directly. This is because earth science has advanced to get a good understanding about the top of the crust and has shifted its main interest to the lower layer of the crust in land regions. The on-land drilling plan in Japan has just started, and the planned drilling spots are areas around the Minami River, Hidaka Mts., kinds of the Mesozoic and Cenozoic granite in outside zone, the extension of Japan Sea, Ogasawara Is., Minami-Tori Is., and active volcanos. The paper also outlines the present situation of on-land drilling in the world, focusing on the SG-3rd super-deep well SG-3 on the Kola Peninsula, USSR, Satori SG-1st well SG-1 in Azerbaidzhan S.S.R, V.S.S.R, Sweden's wells, Cyprus' wells, Bayearn well Plan in West Germany, and Salton Sea Scientific Drilling Program in the U.S. At its end, the paper explains the present situation and the future theme of the Japanese drilling technique and points out the necessity of developing equipment, and techniques. (14 figs, 5 tabs, 26 refs)

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martínez, Juan Pablo

2016-04-10

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

2016-01-01

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase III Drilling Operations at the Long Valley Exploratory Well (LVF 51-20)

Energy Technology Data Exchange (ETDEWEB)

Finger, J.T.; Jacobson, R.D.

1999-06-01

During July-September, 1998, a jointly funded drilling operation deepened the Long Valley Exploratory Well from 7178 feet to 9832 feet. This was the third major drilling phase of a project that began in 1989, but had sporadic progress because of discontinuities in tiding. Support for Phase III came from the California Energy Commission (CEC), the International Continental Drilling Program (ICDP), the US Geological Survey (USGS), and DOE. Each of these agencies had a somewhat different agenda: the CEC wants to evaluate the energy potential (specifically energy extraction from magma) of Long Valley Caldera; the ICDP is studying the evolution and other characteristics of young, silicic calderas; the USGS will use this hole as an observatory in their Volcano Hazards program; and the DOE, through Sandia, has an opportunity to test new geothermal tools and techniques in a realistic field environment. This report gives a description of the equipment used in drilling and testing; a narrative of the drilling operations; compiled daily drilling reports; cost information on the project; and a brief summary of engineering results related to equipment performance and energy potential. Detailed description of the scientific results will appear in publications by the USGS and other researchers.

Ultrasonic rotary-hammer drill

Science.gov (United States)

Bar-Cohen, Yoseph (Inventor); Badescu, Mircea (Inventor); Sherrit, Stewart (Inventor); Bao, Xiaoqi (Inventor); Kassab, Steve (Inventor)

2010-01-01

A mechanism for drilling or coring by a combination of sonic hammering and rotation. The drill includes a hammering section with a set of preload weights mounted atop a hammering actuator and an axial passage through the hammering section. In addition, a rotary section includes a motor coupled to a drive shaft that traverses the axial passage through the hammering section. A drill bit is coupled to the drive shaft for drilling by a combination of sonic hammering and rotation. The drill bit includes a fluted shaft leading to a distal crown cutter with teeth. The bit penetrates sampled media by repeated hammering action. In addition, the bit is rotated. As it rotates the fluted bit carries powdered cuttings helically upward along the side of the bit to the surface.

Photochemical reactions of electron-deficient olefins with N,N,N',N'-tetramethylbenzidine via photoinduced electron-transfer

Energy Technology Data Exchange (ETDEWEB)

Pan Yang [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Zhao Junshu [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Ji Yuanyuan [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yan Lei [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China); Yu Shuqin [Laboratory of Bond-selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, No. 96 of Jinzhai Road, Hefei, Anhui 230026 (China)], E-mail: sqyu@ustc.edu.cn

2006-01-05

Photoinduced electron transfer reactions of several electron-deficient olefins with N,N,N',N'-tetramethylbenzidine (TMB) in acetonitrile solution have been studied by using laser flash photolysis technique and steady-state fluorescence quenching method. Laser pulse excitation of TMB yields {sup 3}TMB* after rapid intersystem crossing from {sup 1}TMB*. The triplet which located at 480 nm is found to undergo fast quenching with the electron acceptors fumaronitrile (FN), dimethyl fumarate (DMF), diethyl fumarate (DEF), cinnamonitrile (CN), {alpha}-acetoxyacrylonitrile (AAN), crotononitrile (CrN) and 3-methoxyacrylonitrile (MAN). Substituents binding to olefin molecule own different electron-donating/withdrawing powers, which determine the electron-deficient property ({pi}-cloud density) of olefin molecule as well as control the electron transfer rate constant directly. The detection of ion radical intermediates in the photolysis reactions confirms the proposed electron transfer mechanism, as expected from thermodynamics. The quenching rate constants of triplet TMB by these olefins have been determined at 510 nm to avoid the disturbance of formed TMB cation radical around 475 nm. All the k{sub q}{sup T} values approach or reach to the diffusion-controlled limit. In addition, fluorescence quenching rate constants k{sub q}{sup S} have been also obtained by calculating with Stern-Volmer equation. A correlation between experimental electron transfer rate constants and free energy changes has been explained by Marcus theory of adiabatic outer-sphere electron transfer. Disharmonic k{sub q} values for CN and CrN in endergonic region may be the disturbance of exciplexs formation. e of exciplex formation.

30 CFR 57.7052 - Drilling positions.

Science.gov (United States)

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Drilling positions. 57.7052 Section 57.7052... SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-UNDERGROUND METAL AND NONMETAL MINES Drilling and Rotary Jet Piercing Drilling-Surface and Underground § 57.7052 Drilling positions. Persons shall not drill...

Single Piezo-Actuator Rotary-Hammering Drill

Science.gov (United States)

Sherrit, Stewart; Bao, Xiaoqi; Badescu, Mircea; Bar-Cohen, Yoseph

2011-01-01

This innovation comprises a compact drill that uses low-axial preload, via vibrations, that fractures the rock under the bit kerf, and rotates the bit to remove the powdered cuttings while augmenting the rock fracture via shear forces. The vibrations fluidize the powered cuttings inside the flutes around the bit, reducing the friction with the auger surface. These combined actions reduce the consumed power and the heating of the drilled medium, helping to preserve the pristine content of the produced samples. The drill consists of an actuator that simultaneously impacts and rotates the bit by applying force and torque via a single piezoelectric stack actuator without the need for a gearbox or lever mechanism. This reduces the development/fabrication cost and complexity. The piezoelectric actuator impacts the surface and generates shear forces, fragmenting the drilled medium directly under the bit kerf by exceeding the tensile and/or shear strength of the struck surface. The percussive impact action of the actuator leads to penetration of the medium by producing a zone of finely crushed rock directly underneath the struck location. This fracturing process is highly enhanced by the shear forces from the rotation and twisting action. To remove the formed cuttings, the bit is constructed with an auger on its internal or external surface. One of the problems with pure hammering is that, as the teeth become embedded in the sample, the drilling efficiency drops unless the teeth are moved away from the specific footprint location. By rotating the teeth, they are moved to areas that were not fragmented, and thus the rock fracturing is enhanced via shear forces. The shear motion creates ripping or chiseling action to produce larger fragments to increase the drilling efficiency, and to reduce the required power. The actuator of the drill consists of a piezoelectric stack that vibrates the horn. The stack is compressed by a bolt between the backing and the horn in order to

HYDRATE CORE DRILLING TESTS

Energy Technology Data Exchange (ETDEWEB)

John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

2002-11-01

The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate

Catalytic Upgrading of Bio-Oil by Reacting with Olefins and Alcohols over Solid Acids: Reaction Paths via Model Compound Studies

Directory of Open Access Journals (Sweden)

Qingwen Wang

2013-03-01

Full Text Available Catalytic refining of bio-oil by reacting with olefin/alcohol over solid acids can convert bio-oil to oxygen-containing fuels. Reactivities of groups of compounds typically present in bio-oil with 1-octene (or 1-butanol were studied at 120 °C/3 h over Dowex50WX2, Amberlyst15, Amberlyst36, silica sulfuric acid (SSA and Cs2.5H0.5PW12O40 supported on K10 clay (Cs2.5/K10, 30 wt. %. These compounds include phenol, water, acetic acid, acetaldehyde, hydroxyacetone, d-glucose and 2-hydroxymethylfuran. Mechanisms for the overall conversions were proposed. Other olefins (1,7-octadiene, cyclohexene, and 2,4,4-trimethylpentene and alcohols (iso-butanol with different activities were also investigated. All the olefins and alcohols used were effective but produced varying product selectivities. A complex model bio-oil, synthesized by mixing all the above-stated model compounds, was refined under similar conditions to test the catalyst’s activity. SSA shows the highest hydrothermal stability. Cs2.5/K10 lost most of its activity. A global reaction pathway is outlined. Simultaneous and competing esterification, etherfication, acetal formation, hydration, isomerization and other equilibria were involved. Synergistic interactions among reactants and products were determined. Acid-catalyzed olefin hydration removed water and drove the esterification and acetal formation equilibria toward ester and acetal products.

30 CFR 56.7052 - Drilling positions.

Science.gov (United States)

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Drilling positions. 56.7052 Section 56.7052... SAFETY AND HEALTH SAFETY AND HEALTH STANDARDS-SURFACE METAL AND NONMETAL MINES Drilling and Rotary Jet Piercing Drilling § 56.7052 Drilling positions. Persons shall not drill from— (a) Positions which hinder...

Synthesis and essay of an Ionomer like catalyst of olefins epoxidation

International Nuclear Information System (INIS)

Boyaca Mendivelso, Alejandro; Tempesti, Ezio

1995-01-01

The purpose of the present work is the preparation of an ionomer with base in Molybdenum and to evaluate its activity like catalyst of olefins epoxidation like alternative of synthesis of catalysts of the Hawk process. A polymer is synthesized with available functional groups to stabilize the metal starting from sodium molybdate; the characterization is made by atomic absorption, spectroscopy to GO, and X.P.S. The characterization indicates that indeed it is possible to stabilize the Mo in the main polymeric. The evaluation in reaction in liquid phase allows similar conversions to those of a homogeneous catalyst. The selective epoxidation of olefins for alkyl hydroperoxides, it has acquired great importance inside the industrial processes obtaining of propylene oxide due to the recent use of the terbutilic alcohol (co-produced together with the epoxide), as preservative in gasoline free of lead. In the environment of these processes, and in particular in the Hawk process possibilities of technological innovation, in the concerning to the heterogenization of conventional catalysts, at the moment used in homogeneous phase. The present work collaborate to some tentative that look for to generate alternative of preparation of catalysts for the process Hawk, synthesizing and testing the activity of an ionomer like epoxidation catalyst, which tries to reproduce the chemical structure of the complexes organ-metallic pear to suppress the separation stages and necessary recovery facilitating its recurrent reutilization with eventual economic repercussions in the industrial process. It is described the procedure of synthesis of the ionomer, the characterization and the evaluation of the activity in reaction under diverse conditions. Of the made characterization it comes off that the heterogenization of catalysts for olefins epoxidation, according to the Hawk process, is possible by means of the preparation of polymers modified appropriately. Likewise the evaluation in

Exploring new generations of ruthenium olefin metathesis catalysts: The reactivity of a bis-ylidene ruthenium complex by DFT

KAUST Repository

Poater, Albert; Credendino, Raffaele; Slugovc, Christian; Cavallo, Luigi

2013-01-01

Density functional theory calculations were used to predict the behaviour of a potential novel architecture of olefin metathesis catalysts, in which one of the neutral ligands of classical Ru-based catalysts, e.g. a phosphine or an N-heterocyclic carbene, is replaced by an alkylidene group. Introduction of a second alkylidene ligand favors dissociation of the remaining phosphine and the overall energy profile for the metathesis using ethylene as the probe substrate reveals that the proposed bis-alkylidene complexes might match the requirements of a good performing olefin metathesis catalyst. © 2013 The Royal Society of Chemistry.

Olefin polymerization from single site catalysts confined within porous media

Science.gov (United States)

Kasi, Rajeswari M.

Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

Biomimetic Aerobic C–H Olefination of Cyclic Enaminones at Room Temperature: Development toward the Synthesis of 1,3,5-Trisubstituted Benzenes

Science.gov (United States)

Yu, Yi-Yun

2014-01-01

A green and mild protocol for the dehydrogenative olefination of cyclic enaminones was devised via palladium catalysis at room temperature using oxygen as the terminal oxidant. The synthetic utility of the olefinated cyclic enaminones afforded a series of unique 1,3,5-trisubstituted benzenes via an unanticipated Diels-Alder tandem reaction. The broad substrate scope and good yields achieved with this new protocol provide an alternative pathway for arene functionalization. PMID:25071423

Sandia's Geothermal Advanced Drill Rig Instrumentation Assists Critical Oil and Gas Drilling Operation

International Nuclear Information System (INIS)

Staller, George E.; Whitlow, Gary

1999-01-01

On November 23, 1998, an 18,000-foot-deep wild-cat natural gas well being drilled near Bakersfield, CA blew out and caught fire. All attempts to kill this well failed, and the well continues to flow under limited control, producing large volumes of natural gas, salt water, and some oil. The oil and some of the water is being separated and trucked off site, and the remaining gas and water is being burned at the well head. A relief well is being drilled approximately one-quarter mile away in an attempt to intercept the first well. If the relief well is successful, it will be used to cement in and kill the first well. Epoch Wellsite Services, Inc., the mud-logging company for the initial well and the relief well, requested Sandia's rolling float meter (RFM) for these critical drilling operations. The RFM is being used to measure the mud outflow rate and detect kicks while drilling the relief well, which will undoubtedly encounter reservoir conditions similar to those responsible for the blow out. Based on its prior experience with the RFM, Epoch believes that it is the only instrument capable of providing the level of accuracy and response to mudflow needed to quickly detect kicks and minimize the risk of a blowout on this second critical well. In response to the urgent request from industry, Sandia and Epoch technicians installed the RFM on the relief well return line, and completed its initial calibration. The data from the RFM is displayed in real-time for the driller, the companyman, and the toolpusher via Epochs RIGWATCH Drilling Instmmentation System. The RFM has already detected several small kicks while drilling toward the annulus of the blown out well. A conventional paddle meter is located downstream of the RFM to provide redundancy and the opportunity to compare the two meters in an actual drilling operation, The relief well is nearing 14,000 feet deep, targeting an intercept of the first well near 17,600 feet. The relief well is expected to be completed in

30 CFR 33.34 - Drilling test.

Science.gov (United States)

2010-07-01

... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Drilling test. 33.34 Section 33.34 Mineral... MINING PRODUCTS DUST COLLECTORS FOR USE IN CONNECTION WITH ROCK DRILLING IN COAL MINES Test Requirements § 33.34 Drilling test. (a) A drilling test shall consist of drilling a set of 10 test holes, without...

Catalyst Design and Development for the Direct Production of Lower Olefins from Synthesis Gas

NARCIS (Netherlands)

Xie, J.

2017-01-01

The increase in global demand for lower olefins (ethylene, propylene, and butylenes) coupled with the regional diversification of carbon raw materials bring about opportunities and challenges for emerging technologies. Crude oil has been the primary carbon feedstock for the past 50 years, but

Transmissive Olefination Route to Putative “Morinol I” Lignans

Science.gov (United States)

Yao, Lihua; Pitta, Bhaskar; Ravikumar, P. C.; Purzycki, Matthew; Fleming, Fraser F.

2012-01-01

A series of morinol-type lignans were rapidly assembled using a Grignard-based transmissive olefination. In combination with palladium-catalyzed arylations, the strategy provides stereoselective access to (7Z, 7′E), (7E, 7′E), (7E, 7′Z) morinol diastereomers and the (7Z, 8′E) and (7E, 8′E) conjugated analogs. Critical for the E/Z-stereoselectivity is a new, general method for converting alkenenitriles to alkenemethanols that circumvents the enal E/Z isomerization commonly encountered during conventional i-Bu2AlH reduction. PMID:22432777

Homogeneous dihydroxylation of olefins catalyzed by OsO(4)(2-) immobilized on a dendritic backbone with a tertiary nitrogen at its core position.

Science.gov (United States)

Fujita, Ken-Ichi; Inoue, Kensuke; Tsuchimoto, Teruhisa; Yasuda, Hiroyuki

2012-01-01

OsO(4)(2-) immobilized on a poly(benzyl ether) dendrimer with a tertiary nitrogen at its core position efficiently catalyzed the homogeneous dihydroxylation of olefins with a low level of osmium leaching. The dendritic osmium catalyst could be applied to the wide range of olefins. Furthermore, the dendritic osmium catalyst was recovered by reprecipitation and then reused up to five times.

Economic environmental management of drilling operations

International Nuclear Information System (INIS)

Longwell, H.J.; Akers, T.J.

1992-01-01

This paper presents significant environmental and regulatory initiatives developed by Exxon's New Orleans Drilling Organization. Specifically, the paper will cover drilling waste minimization techniques and disposal options, recycling of drilling waste streams, and environmentally managed drilling location design considerations. The implementation of some of these initiatives at Exxon's Chalkley field land locations have resulted in a fifty percent reduction in drilling location waste management costs. Some of these same initiatives have been successfully applied to Exxon's barge drilling locations. For operations at the environmentally sensitive Mobile Bay, Exxon contracted with a local company and assisted in the development of an economically and environmentally superior drilling waste disposal and treatment system. In summary, it is possible for drilling operators to pro-actively manage escalating environmental and regulatory challenges through the implementation of economic and practical initiatives

Newberry exploratory slimhole: Drilling and testing

Energy Technology Data Exchange (ETDEWEB)

Finger, J.T.; Jacobson, R.D.; Hickox, C.E.

1997-11-01

During July--November, 1995, Sandia National Laboratories, in cooperation with CE Exploration, drilled a 5,360 feet exploratory slimhole (3.895 inch diameter) in the Newberry Known Geothermal Resource Area (KGRA) near Bend, Oregon. This well was part of Sandia`s program to evaluate slimholes as a geothermal exploration tool. During and after drilling the authors performed numerous temperature logs, and at the completion of drilling attempted to perform injection tests. In addition to these measurements, the well`s data set includes: over 4,000 feet of continuous core (with detailed log); daily drilling reports from Sandia and from drilling contractor personnel; daily drilling fluid record; and comparative data from other wells drilled in the Newberry KGRA. This report contains: (1) a narrative account of the drilling and testing, (2) a description of equipment used, (3) a brief geologic description of the formation drilled, (4) a summary and preliminary interpretation of the data, and (5) recommendations for future work.

Microgravity Drill and Anchor System

Science.gov (United States)

Parness, Aaron; Frost, Matthew A.; King, Jonathan P.

2013-01-01

This work is a method to drill into a rock surface regardless of the gravitational field or orientation. The required weight-on-bit (WOB) is supplied by a self-contained anchoring mechanism. The system includes a rotary percussive coring drill, forming a complete sampling instrument usable by robot or human. This method of in situ sample acquisition using micro - spine anchoring technology enables several NASA mission concepts not currently possible with existing technology, including sampling from consolidated rock on asteroids, providing a bolt network for astronauts visiting a near-Earth asteroid, and sampling from the ceilings or vertical walls of lava tubes and cliff faces on Mars. One of the most fundamental parameters of drilling is the WOB; essentially, the load applied to the bit that allows it to cut, creating a reaction force normal to the surface. In every drilling application, there is a minimum WOB that must be maintained for the system to function properly. In microgravity (asteroids and comets), even a small WOB could not be supported conventionally by the weight of the robot or astronaut. An anchoring mechanism would be needed to resist the reactions, or the robot or astronaut would push themselves off the surface and into space. The ability of the system to anchor itself to a surface creates potential applications that reach beyond use in low gravity. The use of these anchoring mechanisms as end effectors on climbing robots has the potential of vastly expanding the scope of what is considered accessible terrain. Further, because the drill is supported by its own anchor rather than by a robotic arm, the workspace is not constrained by the reach of such an arm. Yet, if the drill is on a robotic arm, it has the benefit of not reflecting the forces of drilling back to the arm s joints. Combining the drill with the anchoring feet will create a highly mobile, highly stable, and highly reliable system. The drilling system s anchor uses hundreds of

Influence of Drilling Parameters on Torque during Drilling of GFRP Composites Using Response Surface Methodology

Science.gov (United States)

Mohan, N. S.; Kulkarni, S. M.

2018-01-01

Polymer based composites have marked their valuable presence in the area of aerospace, defense and automotive industry. Components made of composite, are assembled to main structure by fastener, which require accurate, precise high quality holes to be drilled. Drilling the hole in composite with accuracy require control over various processes parameters viz., speed, feed, drill bit size and thickens of specimen. TRIAC VMC machining center is used to drill the hole and to relate the cutting and machining parameters on the torque. MINITAB 14 software is used to analyze the collected data. As a function of cutting and specimen parameters this method could be useful for predicting torque parameters. The purpose of this work is to investigate the effect of drilling parameters to get low torque value. Results show that thickness of specimen and drill bit size are significant parameters influencing the torque and spindle speed and feed rate have least influence and overlaid plot indicates a feasible and low region of torque is observed for medium to large sized drill bits for the range of spindle speed selected. Response surface contour plots indicate the sensitivity of the drill size and specimen thickness to the torque.

Control procedure for well drilling operations

Energy Technology Data Exchange (ETDEWEB)

Bourdon, J C

1988-09-09

A control procedure of rotary drilling operations is proposed. It uses the Drill off test. The drill-off test permits to determine the rock drill speed variation as a function of the wright applied on the top of the pipe. We can deduce from that a rock drill wear parameter. The method permits to prevent a rupture and its grave economic consequences.

Multi-state autonomous drilling for lunar exploration

Directory of Open Access Journals (Sweden)

Chen Chongbin

2016-10-01

Full Text Available Due to the lack of information of subsurface lunar regolith stratification which varies along depth, the drilling device may encounter lunar soil and lunar rock randomly in the drilling process. To meet the load safety requirements of unmanned sampling mission under limited orbital resources, the control strategy of autonomous drilling should adapt to the indeterminable lunar environments. Based on the analysis of two types of typical drilling media (i.e., lunar soil and lunar rock, this paper proposes a multi-state control strategy for autonomous lunar drilling. To represent the working circumstances in the lunar subsurface and reduce the complexity of the control algorithm, lunar drilling process was categorized into three drilling states: the interface detection, initiation of drilling parameters for recognition and drilling medium recognition. Support vector machine (SVM and continuous wavelet transform were employed for the online recognition of drilling media and interface, respectively. Finite state machine was utilized to control the transition among different drilling states. To verify the effectiveness of the multi-state control strategy, drilling experiments were implemented with multi-layered drilling media constructed by lunar soil simulant and lunar rock simulant. The results reveal that the multi-state control method is capable of detecting drilling state variation and adjusting drilling parameters timely under vibration interferences. The multi-state control method provides a feasible reference for the control of extraterrestrial autonomous drilling.

Cyclic olefin homopolymer-based microfluidics for protein crystallization and in situ X-ray diffraction

International Nuclear Information System (INIS)

Emamzadah, Soheila; Petty, Tom J.; De Almeida, Victor; Nishimura, Taisuke; Joly, Jacques; Ferrer, Jean-Luc; Halazonetis, Thanos D.

2009-01-01

A cyclic olefin homopolymer-based microfluidics system has been established for protein crystallization and in situ X-ray diffraction. Microfluidics is a promising technology for the rapid identification of protein crystallization conditions. However, most of the existing systems utilize silicone elastomers as the chip material which, despite its many benefits, is highly permeable to water vapour. This limits the time available for protein crystallization to less than a week. Here, the use of a cyclic olefin homopolymer-based microfluidics system for protein crystallization and in situ X-ray diffraction is described. Liquid handling in this system is performed in 2 mm thin transparent cards which contain 500 chambers, each with a volume of 320 nl. Microbatch, vapour-diffusion and free-interface diffusion protocols for protein crystallization were implemented and crystals were obtained of a number of proteins, including chicken lysozyme, bovine trypsin, a human p53 protein containing both the DNA-binding and oligomerization domains bound to DNA and a functionally important domain of Arabidopsis Morpheus’ molecule 1 (MOM1). The latter two polypeptides have not been crystallized previously. For X-ray diffraction analysis, either the cards were opened to allow mounting of the crystals on loops or the crystals were exposed to X-rays in situ. For lysozyme, an entire X-ray diffraction data set at 1.5 Å resolution was collected without removing the crystal from the card. Thus, cyclic olefin homopolymer-based microfluidics systems have the potential to further automate protein crystallization and structural genomics efforts

Optimum fluid design for drilling and cementing a well drilled with coil tubing technology

Energy Technology Data Exchange (ETDEWEB)

Swendsen, O.; Saasen, A.; Vassoy, B. [Statoil (Norway); Skogen, E.; Mackin, F.; Normann, S. H.

1998-12-31

The strategy, design and drilling fluid and cementing operations in the first two wells drilled with coil tubing technology in the Gullfaks field in the Tampen Spur Area of the Norwegian sector of the North Sea are discussed. The drilling fluid use was a solids-free potassium formate/polymer brine-based fluid with a density of 1,50-1.56 g/cc, with flow properties characterized by very low fluid loss due to high extensional viscosity, a low viscosity at all shear rates, and a low degree of shear-thinning. The low viscous drilling fluid is considered to have been the major contributing factor in achieving excellent hole cleaning, no differential sticking, successful setting of cement kick-off plugs, problem-free running of the liner, and excellent zonal isolation when cementing the liner. These experiences led the authors to conclude that it is possible to formulate a brine-based solids-free drilling fluid with low viscosity and fluid loss properties for most formation pressure regimes, and that such a drilling fluid is well suited to drilling highly deviated slim hole wells where hole cleaning and differential sticking present special challenges. 12 refs., 2 tabs., 3 figs.

The effect of gas and fluid flows on nonlinear lateral vibrations of rotating drill strings

Science.gov (United States)

Khajiyeva, Lelya; Kudaibergenov, Askar; Kudaibergenov, Askat

2018-06-01

In this work we develop nonlinear mathematical models describing coupled lateral vibrations of a rotating drill string under the effect of external supersonic gas and internal fluid flows. An axial compressive load and a torque also affect the drill string. The mathematical models are derived by the use of Novozhilov's nonlinear theory of elasticity with implementation of Hamilton's variation principle. Expressions for the gas flow pressure are determined according to the piston theory. The fluid flow is considered as added mass inside the curved tube of the drill string. Using an algorithm developed in the Mathematica computation program on the basis of the Galerkin approach and the stiffness switching method the numerical solution of the obtained approximate differential equations is found. Influences of the external loads, drill string angular speed of rotation, parameters of the gas and fluid flows on the drill string vibrations are shown.

Fragmentation of delta-diketones by electron impact. Olefin elimination and formation of an enol acetate ion

International Nuclear Information System (INIS)

Morizur, J.P.; Mercier, J.; Casals, P.F.

1985-01-01

Under electron impact delta-diketones lose an olefin. The mechanism and structure of the resulting ion have been established by several techniques: substitution, Mike and Cid spectra and thermochemical data [fr

Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

KAUST Repository

Fava, Eleonora

2016-07-21

A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

Photoredox-Catalyzed Ketyl–Olefin Coupling for the Synthesis of Substituted Chromanols

KAUST Repository

Fava, Eleonora; Nakajima, Masaki; Nguyen, Anh L. P.; Rueping, Magnus

2016-01-01

A visible light photoredox-catalyzed aldehyde olefin cyclization is reported. The method represents a formal hydroacylation of alkenes and alkynes and provides chromanol derivatives in good yields. The protocol takes advantage of the double role played by trialkylamines (NR3) which act as (i) electron donors for reducing the catalyst and (ii) proton donors to activate the substrate via a proton-coupled electron transfer. © 2016 American Chemical Society.

Heat generated by dental implant drills during osteotomy-a review: heat generated by dental implant drills.

Science.gov (United States)

Mishra, Sunil Kumar; Chowdhary, Ramesh

2014-06-01

Osseointegration is the more stable situation and results in a high success rate of dental implants. Heat generation during rotary cutting is one of the important factors influencing the development of osseointegration. To assess the various factors related to implant drills responsible for heat generation during osteotomy. To identify suitable literature, an electronic search was performed using Medline and Pubmed database. Articles published in between 1960 to February 2013 were searched. The search is focused on heat generated by dental implant drills during osteotomy. Various factors related to implant drill such effect of number of blades; drill design, drill fatigue, drill speed and force applied during osteotomies which were responsible for heat generation were reviewed. Titles and abstracts were screened, and literature that fulfilled the inclusion criteria was selected for a full-text reading. The initial literature search resulted in 299 articles out of which only 70 articles fulfils the inclusion criteria and were included in this systematic review. Many factors related to implant drill responsible for heat generation were found. Successful preparation of an implant cavity with minimal damage to the surrounding bone depends on the avoidance of excessive temperature generation during surgical drilling. The relationship between heat generated and implant drilling osteotomy is multifactorial in nature and its complexity has not been fully studied. Lack of scientific knowledge regarding this issue still exists. Further studies should be conducted to determine the various factors which generate less heat while osteotomy such as ideal ratio of force and speed in vivo, exact time to replace a drill, ideal drill design, irrigation system, drill-bone contact area.

Technology strategy for cost-effective drilling and intervention; Technology Target Areas; TTA4 - Cost effective drilling and intervention

Energy Technology Data Exchange (ETDEWEB)

2007-07-01

The main goals of the OG21 initiative are to (1) develop new technology and knowledge to increase the value creation of Norwegian oil and gas resources and (2) enhance the export of Norwegian oil and gas technology. The OG21 Cost-effective Drilling and Intervention (CEDI) Technology Target Area (TTA) has identified some key strategic drilling and well intervention needs to help meet the goals of OG21. These key strategic drilling and well intervention needs are based on a review of present and anticipated future offshore-Norway drilling and well intervention conditions and the Norwegian drilling and well intervention industry. A gap analysis has been performed to assess the extent to which current drilling and well intervention research and development and other activities will meet the key strategic needs. Based on the identified strategic drilling and well intervention needs and the current industry res each and development and other activities, the most important technology areas for meeting the OG21 goals are: environment-friendly and low-cost exploration wells; low-cost methods for well intervention/sidetracks; faster and extended-reach drilling; deep water drilling, completion and intervention; offshore automated drilling; subsea and sub-ice drilling; drilling through basalt and tight carbonates; drilling and completion in salt formation. More specific goals for each area: reduce cost of exploration wells by 50%; reduce cost for well intervention/sidetracks by 50%; increase drilling efficiency by 40%; reduce drilling cost in deep water by 40 %; enable offshore automated drilling before 2012; enable automated drilling from seabed in 2020. Particular focus should be placed on developing new technology for low-cost exploration wells to stem the downward trends in the number of exploration wells drilled and the volume of discovered resources. The CEDI TTA has the following additional recommendations: The perceived gaps in addressing the key strategic drilling and

Enhanced catalytic performance for light-olefins production from chloromethane over hierarchical porous ZSM-5 zeolite synthesized by a growth-inhibition strategy

Science.gov (United States)

Liu, Qing; Wen, Dafen; Yang, Yanran; Fei, Zhaoyang; Zhang, Zhuxiu; Chen, Xian; Tang, Jihai; Cui, Mifen; Qiao, Xu

2018-03-01

Hierarchical porous ZSM-5 (HP-ZSM-5) zeolites were synthesized by hydrothermal crystallization method adding triethoxyvinylsilane as the growth-inhibitor at different hydrothermal crystallized temperatures. The properties of the obtained samples were characterized by XRD, SEM, N2-sorption, uptake of ethylene, 27Al MAS NMR, NH3-TPD, and Py-IR. It was found that the mesopore was introduced and the acidity was adjusted over HP-ZSM-5 samples successfully. The hydrothermal crystallized temperature had an important influence on the porous structure and surface properties. The catalytic performance for chloromethane to light-olefins (CMTO) were also investigated. Compared with ZSM-5 samples, HP-ZSM-5 samples exhibited enhanced stability and increased selectivity of light-olefins for CMTO reaction because of the introduction of the abundant mesopore and appropriate acidity. The lifetime (the duration of chloromethane conversion >98%) and selectivity of light-olefins reached 115 h and 69.3%, respectively.

The Auto-Gopher Deep Drill

Science.gov (United States)

Badescu, Mircea

2014-01-01

Subsurface penetration by coring, drilling or abrading is of great importance for a large number of space and earth applications. An Ultrasonic/Sonic Drill/Corer (USDC) has been in development at JPL's Nondestructive Evaluation and Advanced Actuators (NDEAA) lab as an adaptable tool for many of these applications. The USDC uses a novel drive mechanism to transform the high frequency ultrasonic or sonic vibrations of the tip of a horn into a lower frequency sonic hammering of a drill bit through an intermediate free-flying mass. The USDC device idea has been implemented at various scales from handheld drills to large diameter coring devices. A series of computer programs that model the function and performance of the USDC device were developed and were later integrated into an automated modeling package. The USDC has also evolved from a purely hammering drill to a rotary hammer drill as the design requirements increased form small diameter shallow drilling to large diameter deep coring. A synthesis of the Auto-Gopher development is presented in this paper.

Surface functionalization of cyclic olefin copolymer (COC) with evaporated TiO{sub 2} thin film

Energy Technology Data Exchange (ETDEWEB)

El Fissi, Lamia, E-mail: lamia.elfissi@uclouvain.be [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium); Vandormael, Denis [SIRRIS Liege Science Park, 4102 Seraing (Belgium); Houssiau, Laurent [Research Centre in Physics of Matter and Radiation (PMR), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Francis, Laurent A. [ICTEAM Institute, Université catholique du Louvain, place de Levant 3, 1348 Louvain-la-Neuve (Belgium)

2016-02-15

Highlights: • TiO{sub 2}/COC (cyclic olefin copolymer) hybrid material for BioMEMS applications. • Thin layer of TiO{sub 2} was deposed on cyclic olefin copolymer using physical vapor deposition (PVD) technique. • The coating possess the highest level of adhesion with an excellent morphology of the hybrid material (TiO{sub 2}/COC). - Abstract: Cyclic olefin copolymer (COC) is a new class of thermoplastic polymers used for a variety of applications ranging from bio-sensing to optics. However, the hydrophobicity of native COC hampers the further development and application of this material [1]. In this work, we report the structural, morphological, and optical properties of the TiO{sub 2}/COC hybrid material, which provides a desirable substrate for optical devices and subsequent surface modifications. The TiO{sub 2} film on COC substrate was deposited by the evaporation method, and it was characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), profilometry and atomic force microscope (AFM). Using an UV-vis spectrophotometer, we found that the transmittance of the TiO{sub 2}/COC hybrid material in the visible domain reached 80%. The TiO{sub 2}/COC hybrid appeared to be stable in most of the assessed polar solvents and acid/basic solutions. The new TiO{sub 2}/COC hybrid material and the robust fabrication method are expected to enable a variety of BioMEMS applications.

Pd(II)-Catalyzed Olefination of Electron-Deficient Arenes Using 2,6-Dialkylpyridine Ligands

Science.gov (United States)

Zhang, Yang-Hui; Shi, Bing-Feng; Yu, Jin-Quan

2009-01-01

Pd(II)-catalyzed meta-olefination of highly electron deficient arenes is achieved through the use of a rationally designed mutually repulsive ligand. The combination of directed and non-directed C–H functionalization of arenes provides a versatile route for the synthesis of highly sought-after 1,2,4-trisubstituted arenes. PMID:19296661

Heteropolytungstate nanoparticles: Microemulsion-mediated preparation and investigation of their catalytic activity in the epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com; Ghorbani, M.

2016-04-15

Highlights: • Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles were synthesized by using microemulsion system. • The nanoparticles have uniform size of about 25 nm and spherical morphologies. • The prepared nanoparticles act as reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}. - Abstract: Keggin type Q{sub 3}PW{sub 12}O{sub 40} nanoparticles (Q = cetyltrimethylammonium cation) were synthesized in water-in-oil (w/o) microemulsion consisted of water/cetyltrimethylammonium bromide/n-butanol/isooctane. Reaction of Na{sub 2}WO{sub 4}, Na{sub 2}HPO{sub 4} and hydrochloric acid within water containing nanoreactors of reverse micelles resulted in the preparation of Q{sub 3}PW{sub 12}O{sub 40} nanoparticles. The resultant nanoparticles were analyzed by physicochemical methods such as FT-IR spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, thermogravimetric analyses (TGA-DTA), scanning and transmission electron microscopy and atomic force microscopy which show nearly uniform spherical nanoparticles with size of about 15 nm. Finally, catalytic activity of the Q{sub 3}PW{sub 12}O{sub 40} nanoparticles was examined in the epoxidation of olefins with H{sub 2}O{sub 2}. The prepared nanoparticles acted as recoverable and reusable catalyst in the epoxidation of olefins with H{sub 2}O{sub 2}.

Evacuation drill at CMS

CERN Multimedia

Niels Dupont-Sagorin and Christoph Schaefer

2012-01-01

Training personnel, including evacuation guides and shifters, checking procedures, improving collaboration with the CERN Fire Brigade: the first real-life evacuation drill at CMS took place on Friday 3 February from 12p.m. to 3p.m. in the two caverns located at Point 5 of the LHC.   CERN personnel during the evacuation drill at CMS. Evacuation drills are required by law and have to be organized periodically in all areas of CERN, both above and below ground. The last drill at CMS, which took place in June 2007, revealed some desiderata, most notably the need for a public address system. With this equipment in place, it is now possible to broadcast audio messages from the CMS control room to the underground areas.   The CMS Technical Coordination Team and the GLIMOS have focused particularly on preparing collaborators for emergency situations by providing training and organizing regular safety drills with the HSE Unit and the CERN Fire Brigade. This Friday, the practical traini...

Stakeholder acceptance analysis ResonantSonic drilling

International Nuclear Information System (INIS)

Peterson, T.

1995-12-01

This report presents evaluations, recommendations, and requirements concerning ResonantSonic Drilling (Sonic Drilling), derived from a three-year program of stakeholder involvement. Sonic Drilling is an innovative method to reach contamination in soil and groundwater. The resonant sonic drill rig uses counter-rotating weights to generate energy, which causes the drill pipe to vibrate elastically along its entire length. In the resonant condition, forces of up to 200,000 pounds are transmitted to the drill bit face to create a cutting action. The resonant energy causes subsurface materials to move back into the adjacent formation, permitting the drill pipe to advance. This report is for technology developers and those responsible for making decisions about the use of technology to remediate contamination by volatile organic compounds. Stakeholders' perspectives help those responsible for technology deployment to make good decisions concerning the acceptability and applicability of sonic drilling to the remediation problems they face

Drilling of bone: A comprehensive review

Science.gov (United States)

Pandey, Rupesh Kumar; Panda, S.S.

2013-01-01

Background Bone fracture treatment usually involves restoring of the fractured parts to their initial position and immobilizing them until the healing takes place. Drilling of bone is common to produce hole for screw insertion to fix the fractured parts for immobilization. Orthopaedic drilling during surgical process causes increase in the bone temperature and forces which can cause osteonecrosis reducing the stability and strength of the fixation. Methods A comprehensive review of all the relevant investigations carried on bone drilling is conducted. The experimental method used, results obtained and the conclusions made by the various researchers are described and compared. Result Review suggests that the further improvement in the area of bone drilling is possible. The systematic review identified several consequential factors (drilling parameters and drill specifications) affecting bone drilling on which there no general agreement among investigators or are not adequately evaluated. These factors are highlighted and use of more advanced methods of drilling is accentuated. The use of more precise experimental set up which resembles the actual situation and the development of automated bone drilling system to minimize human error is addressed. Conclusion In this review, an attempt has been made to systematically organize the research investigations conducted on bone drilling. Methods of treatment of bone fracture, studies on the determination of the threshold for thermal osteonecrosis, studies on the parameters influencing bone drilling and methods of the temperature measurement used are reviewed and the future work for the further improvement of bone drilling process is highlighted. PMID:26403771

Influence of drill helical direction on exit damage development in drilling carbon fiber reinforced plastic

Science.gov (United States)

Bai, Y.; Jia, Z. Y.; Wang, F. J.; Fu, R.; Guo, H. B.; Cheng, D.; Zhang, B. Y.

2017-06-01

Drilling is inevitable for CFRP components’ assembling process in the aviation industry. The exit damage frequently occurs and affects the load carrying capacity of components. Consequently, it is of great urgency to enhance drilling exit quality on CFRP components. The article aims to guide the reasonable choice of drill helical direction and effectively reduce exit damage. Exit observation experiments are carried out with left-hand helical, right-hand helical and straight one-shot drill drilling T800S CFRP laminates separately. The development rules of exit damage and delamination factor curves are obtained. Combined with loading conditions and fracture modes of push-out burrs, and thrust force curves, the influence of drill helical direction on exit damage development is derived. It is found that the main fracture modes for left-hand helical, right-hand helical, and straight one-shot drill are mode I, extrusive fracture, mode III respectively. Among them, mode III has the least effect on exit damage development. Meanwhile, the changing rate of thrust force is relative slow for right-hand helical and straight one-shot drill in the thrust force increasing phase of stage II, which is disadvantaged for exit damage development. Therefore, straight one-shot drill’s exit quality is the best.

Heat accumulation during sequential cortical bone drilling.

Science.gov (United States)

Palmisano, Andrew C; Tai, Bruce L; Belmont, Barry; Irwin, Todd A; Shih, Albert; Holmes, James R

2016-03-01

Significant research exists regarding heat production during single-hole bone drilling. No published data exist regarding repetitive sequential drilling. This study elucidates the phenomenon of heat accumulation for sequential drilling with both Kirschner wires (K wires) and standard two-flute twist drills. It was hypothesized that cumulative heat would result in a higher temperature with each subsequent drill pass. Nine holes in a 3 × 3 array were drilled sequentially on moistened cadaveric tibia bone kept at body temperature (about 37 °C). Four thermocouples were placed at the center of four adjacent holes and 2 mm below the surface. A battery-driven hand drill guided by a servo-controlled motion system was used. Six samples were drilled with each tool (2.0 mm K wire and 2.0 and 2.5 mm standard drills). K wire drilling increased temperature from 5 °C at the first hole to 20 °C at holes 6 through 9. A similar trend was found in standard drills with less significant increments. The maximum temperatures of both tools increased from drill sizes was found to be insignificant (P > 0.05). In conclusion, heat accumulated during sequential drilling, with size difference being insignificant. K wire produced more heat than its twist-drill counterparts. This study has demonstrated the heat accumulation phenomenon and its significant effect on temperature. Maximizing the drilling field and reducing the number of drill passes may decrease bone injury. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

You say you want a revolution: casing drilling targets 30 per cent well-cost saving

Energy Technology Data Exchange (ETDEWEB)

Polczer, S.; Marsters, S.

1999-10-01

Casing drilling is a new method of drilling that eliminates drill strings by using standard casing to simultaneously drill and case wells. Tesco Corporation of Calgary acquired patent rights to casing drilling technology in 1995. The company now offers a conversion kit for existing drill rigs as well a new compact casing drilling rig for shallow markets. The single derrick will be rated at 1,500 meters, but initially it will be used to drill 700-800 meter gas wells in southeast Alberta. Some cost savings will be realized at these shallow depths, but the real cost saving advantages will be realized on deep holes. In the meantime, improvements are planned to the cutting structures of the under-rimming bit to increase safety and withstand higher torque loads. It will be also necessary to adapt techniques such as directional drilling and logging to the casing drilling conveyance mechanism which has been only partially successful thus far, especially in the retrieving mode. Another challenge already met, involved ensuring that casing could be run in high-compression loads without damage to connections. Despite these problems, the system attracted considerable attention with several international companies placing orders for immediate delivery. Another system, this one developed by Sperry-Sun Drilling Services and known as a 'casing while drilling' (CWD) system, is strictly a downhole assembly and is targeted for offshore use and deeper vertical holes. This system is currently being tested in two commercial operations in offshore Indonesia for Unocal Corporation. Despite numerous problems to fill casing with fluid during connections, penetration rates of 300-400 feet per hour were achieved.

Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary.

Science.gov (United States)

Yao, Qi-Jun; Zhang, Shuo; Zhan, Bei-Bei; Shi, Bing-Feng

2017-06-01

Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98 %) with excellent enantioselectivities (95 to >99 % ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99 % ee, s-factor up to 600). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A method for producing light olefines

Energy Technology Data Exchange (ETDEWEB)

Kavada, N.; Katsuno, K.

1982-11-04

A method is proposed for producing light olefins from MeOH in the presence of a catalyst (Kt), a crystalline silicate which includes silicon, an alkaline and or alkaline earth metal, titanium(4+) and phosphorus(5+), whose composition is described by the formula p(019 plus or minus 0.3)M2/mO with pZ4/nO2 with SiO2, where M is the alkaline or alkaline earth metal, Z = titanium(4+) or phosphorus(5+), m is the valency of the metal, n is the valency of Z and O is less than p is less than or equal to 0.1. A high selectivity of MeOH to C2 to C4 olefins is achieved in the presence of the catalyst. Silicon powder, silica gel, colloidal silicon, liquid glass or silicates of alkaline metals in a ratio of SiO2 to M2O of 1 to 5 is used as the source of the first component. Hydroxides or silicates of potassium and sodium (best sodium) and nitrates or chlorides of alkaline earth metals (best calcium) are used as the source of the second component. Water soluble compounds of titanium(4+) (best Ti(SO4)2, TiBr4 and TiI4) and phosphorus(5+) (best H3PO4, Na3PO4) are used as the source of the third component. Heterocyclic compounds (best morpholine, oxazolidine and their derivatives, which are taken in a molar ratio of crystallization agent to SiO2 of 0.01 to 50 (best at 0.1 to 10), are used as the crystallization agent (ArK). The catalyst is prepared through heating in an autoclave at a temperature of 80 to 300 degrees (best at 120 to 200 degrees) at atmospheric pressure for 10 to 50 hours with mixing of the mixture of the three components, water and the crystallization agent. The forming crystalline product is cooled, poured off, washed with water, dried for several hours at a temperature of at least 100 degrees and roasted in air for 2 to 48 hours at 300 to 700 degrees.

RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.

Science.gov (United States)

In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

Mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid

Energy Technology Data Exchange (ETDEWEB)

Baiburskii, V.L.; Khadzhiev, S.N.; Ovsyannikov, V.P.

1992-05-10

The authors attempted here to examine the mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid in terms of an initial stage of activation of isoparaffin. The version of formation of tert-alkyl cations and the role of the catalyst in this stage were analyzed. 10 refs., 1 fig., 1 tab.

Quality in drilling operations

Energy Technology Data Exchange (ETDEWEB)

Duncan, E; Gervais, I [Sedco Forex Jacintoport Facility, Channelview, TX (United States); Le Moign, Y; Pangarkar, S; Stibbs, B [Sedco Forex, Montrouge (France); McMorran, P [Sedco Forex, Pau (France); Nordquist, E [Dubai Petroleum Company, Dubai (United Arab Emirates); Pittman, T [Sedco Forex, Perth (Australia); Schindler, H [Sedco Forex, Dubai (United Arab Emirates); Scott, P [Woodside Offshore Petroleum Pty. Ltd., Perth (Australia)

1997-12-31

Driven by cost and profitability pressures, quality has taken on new meaning and importance in the oil field during the past decade. In drilling operations, new initiatives have led to cooperative team efforts between operators and drilling contractors to enhance quality. In this article examples are given of how one drilling contractor, by adopting a quality culture, is reaping major benefits for its clients as well as its employees. 22 figs., 19 refs.

Quality in drilling operations

Energy Technology Data Exchange (ETDEWEB)

Duncan, E.; Gervais, I. [Sedco Forex Jacintoport Facility, Channelview, TX (United States); Le Moign, Y.; Pangarkar, S.; Stibbs, B. [Sedco Forex, Montrouge (France); McMorran, P. [Sedco Forex, Pau (France); Nordquist, E. [Dubai Petroleum Company, Dubai (United Arab Emirates); Pittman, T. [Sedco Forex, Perth (Australia); Schindler, H. [Sedco Forex, Dubai (United Arab Emirates); Scott, P. [Woodside Offshore Petroleum Pty. Ltd., Perth (Australia)

1996-12-31

Driven by cost and profitability pressures, quality has taken on new meaning and importance in the oil field during the past decade. In drilling operations, new initiatives have led to cooperative team efforts between operators and drilling contractors to enhance quality. In this article examples are given of how one drilling contractor, by adopting a quality culture, is reaping major benefits for its clients as well as its employees. 22 figs., 19 refs.

Drilling history of core hole DB-15

International Nuclear Information System (INIS)

Diediker, L.D.; Ledgerwood, R.K.

1980-09-01

This core hole was drilled to obtain hydrologic and chemical data on the permeable zones of the Saddle Mountains and Wanapum Formations. These data were obtained by testing the zones that were penetrated during drilling. This testing-as-drilled method reduced the potential problems of interflow and water contamination. This report summarizes the drilling and coring operations; geologic logging, hydrologic testing, and geophysical logging activities; and cementing operations of DB-15 during drilling. The successful completion of DB-15 demonstrated that hydrologic testing can be conducted during core drilling operations. More reliable head measurements and uncontaminated representative water samples from isolated permeable zones, which have not been exposed to potential open borehole cross-flow and head equilibration problems, were benefits derived from the testing-as-drilled method. Disadvantages of the technique were a longer time to complete the borehole caused by time required for testing and increased drilling costs due to rig standby time during testing. Extension of the testing-as-drilled method to the drilling of future core holes is recommended. An evaluation should be made of the required hydrologic data and expected borehole stratigraphy before and during drilling to allow uninterrupted drilling in zones of low permeability that can be tested after drilling is complete

Mesoporous catalysts for the synthesis of clean diesel fuels by oligomerisation of olefins

Energy Technology Data Exchange (ETDEWEB)

Catani, Roberto; Rossini, Stefano [Snamprogetti SpA, Via F. Maritano 26, 20092 , MI S. Donato Milanese (Italy); Mandreoli, Monica; Vaccari, Angelo [Dipartimento di Chimica Industriale e dei Materiali, Universita di Bologna, INSTM-UdR di Bologna, Viale del Risorgimento 4, 40136 Bologna (Italy)

2002-07-03

Si/Al MCM-41 type mesoporous compounds, as such or containing small amounts of metal (Ni, Rh or Pt), were investigated in the synthesis of clean diesel fuels by oligomerisation of orphan olefin streams. Very good catalytic performances were obtained with C{sub 4} and C{sub 5} olefins, while almost no conversion occurred with ethylene. The activity increased with increasing reaction pressure, temperature and contact time, while high Si/Al ratios had a negative effect on both activity and catalyst stability. The presence of small amount of metal inside the mesoporous structure did not significantly modify the catalytic activity, although specific effects were detected for each element. Since the evaluation of the cetane number by H-NMR gave rise to values about 20% lower than the actual value, a new and more complex algorithm is proposed to calculate the cetane number. Using the proposed algorithm, a good correlation index was found between calculated and motor values for pure compounds. Further study is necessary to move from pure compounds to experimental mixtures.

A vision for drilling

Energy Technology Data Exchange (ETDEWEB)

Millheim, K. [Montanuniversitaet Leoben (Austria)

1995-12-31

The future of drilling lies in its relationship with the oil and gas industry. This paper examines how the future of drilling is seen from the view point of the exploration manager, the drilling contractor, the drilling engineer and the company president or managing director. The various pressures on the oil and gas industry are examined, such as environmental issues, alternative energy sources, and the price of oil which determines how companies are run. Exploration activity is driven by the price of oil and gas. The development of wells with multiple horizontal wells or multiple horizontal wells with tributaries will reduce the cost of exploration. Companies will rely less and less on reservoir simulation and more on cheap well-bores, multi-lateral well-bores and will exploit oil that could not be exploited before. The cost of exploratory drilling will need to be kept down so that in the future the industry will get better at economically finding fields at the 10 million to 20 million barrel range that would not have been possible before. The future is expected to see drilling contractors tunnelling, making sewerage lines and drilling 10,000 foot wells with purpose built rigs. Franchising will become a feature of the industry as will the use of databases to answer key technical questions. Offshore platforms will be built to be moveable and disposable. The industry is capable of solving problems, meeting challenges and making ideas work, providing much hope for the future. 10 figs., 1 photo.

Deep-Time drilling in the Australian Archean: the Agouron Institute geobiological drilling project. (Invited)

Science.gov (United States)

Buick, R.

2010-12-01

The Agouron Institute has sponsored deep-time drilling across the South African Archean-Proterozoic boundary, investigating the rise of oxygen over an onshore-offshore environmental transect. It is now supporting a drilling program in the Australian Archean of the Pilbara Craton, addressing a similar theme but with the added goal of resolving controversy over the age and origin of hydrocarbon biomarker molecules in ancient kerogenous shales. As these have been claimed to provide evidence for the evolution of oxygenic photosynthesis long before the rise of atmospheric oxygen to persistently high levels during the ~2.3 Ga “Great Oxidation Event”, their syngenesis with their host shales is thus of critical importance for the interpretation of Earth’s early oxygenation history. During the first drilling season, 3 holes were drilled using techniques and equipment to minimize organic geochemical contamination (new drill-string components cleaned before drilling potentially biomarker-bearing rocks, pre-contamination of drilling fluid with a synthetic organic compound of similar geochemical characteristics to biomarkers, sterile cutting and storage of samples immediately upon retrieval from the core-barrel). The initial hole was a blank control for organic geochemistry, drilled into rocks too metamorphosed to retain biomarker molecules. These rocks, cherts, carbonates and pelites of the 3.52 Ga Coucal Formation, Coonterunah Group, have been metamorphosed to upper greenschist facies at temperatures near 500°C and so should have had any ancient soluble hydrocarbons destroyed. However, because they contain both carbonate and organic carbon, these rocks can instead provide isotopic information about the earliest evolution of biological metabolism as they possess residues of both the reactant and product sides of the carbon-fixation reaction. The second hole sampled an on-shore section of carbonates and kerogenous shales in the ~2.65 Ga Carawine Dolomite and Lewin Shale

Drilling miniature holes, Part III

Energy Technology Data Exchange (ETDEWEB)

Gillespie, L.K.

1978-07-01

Miniature components for precision electromechanical mechanisms such as switches, timers, and actuators typically require a number of small holes. Because of the precision required, the workpiece materials, and the geometry of the parts, most of these holes must be produced by conventional drilling techniques. The use of such techniques is tedious and often requires considerable trial and error to prevent drill breakage, minimize hole mislocation and variations in hole diameter. This study of eight commercial drill designs revealed that printed circuit board drills produced better locational and size repeatability than did other drills when centerdrilling was not used. Boring holes 1 mm in dia, or less, as a general rule did not improve hole location in brass or stainless steel. Hole locations of patterns of 0.66-mm holes can be maintained within 25.4-..mu..m diametral positional tolerance if setup misalignments can be eliminated. Size tolerances of +- 3.8 ..mu..m can be maintained under some conditions when drilling flat plates. While these levels of precision are possible with existing off-the-shelf drills, they may not be practical in many cases.

Horizontal Directional Drilling-Length Detection Technology While Drilling Based on Bi-Electro-Magnetic Sensing

Directory of Open Access Journals (Sweden)

Yudan Wang

2017-04-01

Full Text Available The drilling length is an important parameter in the process of horizontal directional drilling (HDD exploration and recovery, but there has been a lack of accurate, automatically obtained statistics regarding this parameter. Herein, a technique for real-time HDD length detection and a management system based on the electromagnetic detection method with a microprocessor and two magnetoresistive sensors employing the software LabVIEW are proposed. The basic principle is to detect the change in the magnetic-field strength near a current coil while the drill stem and drill-stem joint successively pass through the current coil forward or backward. The detection system consists of a hardware subsystem and a software subsystem. The hardware subsystem employs a single-chip microprocessor as the main controller. A current coil is installed in front of the clamping unit, and two magneto resistive sensors are installed on the sides of the coil symmetrically and perpendicular to the direction of movement of the drill pipe. Their responses are used to judge whether the drill-stem joint is passing through the clamping unit; then, the order of their responses is used to judge the movement direction. The software subsystem is composed of a visual software running on the host computer and a software running in the slave microprocessor. The host-computer software processes, displays, and saves the drilling-length data, whereas the slave microprocessor software operates the hardware system. A combined test demonstrated the feasibility of the entire drilling-length detection system.

Effects of implant drilling parameters for pilot and twist drills on temperature rise in bone analog and alveolar bones.

Science.gov (United States)

Chen, Yung-Chuan; Hsiao, Chih-Kun; Ciou, Ji-Sih; Tsai, Yi-Jung; Tu, Yuan-Kun

2016-11-01

This study concerns the effects of different drilling parameters of pilot drills and twist drills on the temperature rise of alveolar bones during dental implant procedures. The drilling parameters studied here include the feed rate and rotation speed of the drill. The bone temperature distribution was analyzed through experiments and numerical simulations of the drilling process. In this study, a three dimensional (3D) elasto-plastic dynamic finite element model (DFEM) was proposed to investigate the effects of drilling parameters on the bone temperature rise. In addition, the FE model is validated with drilling experiments on artificial human bones and porcine alveolar bones. The results indicate that 3D DFEM can effectively simulate the bone temperature rise during the drilling process. During the drilling process with pilot drills or twist drills, the maximum bone temperature occurred in the region of the cancellous bones close to the cortical bones. The feed rate was one of the important factors affecting the time when the maximum bone temperature occurred. Our results also demonstrate that the elevation of bone temperature was reduced as the feed rate increased and the drill speed decreased, which also effectively reduced the risk region of osteonecrosis. These findings can serve as a reference for dentists in choosing drilling parameters for dental implant surgeries. Copyright © 2016 IPEM. Published by Elsevier Ltd. All rights reserved.

Pushing the limits : from better bits to faster coil, companies leverage technology to ramp up onshore drilling performance

Energy Technology Data Exchange (ETDEWEB)

Smith, M.

2009-06-15

Horizontal drilling and drilling with coiled tubing are two well drilling techniques that have steadily gained ground in the drilling industry. Most of the techniques evolved in western Canada and Alaska, but are now being successfully used south of the border. This article discussed the leveraging of technology by drilling companies in order to ramp up onshore drilling performance. Calgary-based Xtreme Coil Drilling Corp. leveraged its unique coil over top drive rigs in order to score more speed records and set new marks in both the United States Rockies and Mexico. This article also referred to other companies and their wells that have set records, including CNX Gas Corporation and the Marcellus Shale prospect; Smith International and its horizontal turbodrilling of a Pennsylvanian reservoir; and Baker Oil Tools' new rotating, self-aligning multilateral (RAM) system. For each of these examples, the article described the technology and the challenges encountered by the companies as well as the objectives of the project, and results of the drilling efforts. 2 figs.

Steam cracking and methane to olefins: Energy use, CO2 emissions and production costs

NARCIS (Netherlands)

Ren, T.; Patel, M.K.|info:eu-repo/dai/nl/18988097X; Blok, K.|info:eu-repo/dai/nl/07170275X

2008-01-01

While most olefins (e.g., ethylene and propylene) are currently produced through steam cracking routes, they can also possibly be produced from natural gas (i.e., methane) via methanol and oxidative coupling routes. We reviewed recent data in the literature and then compared the energy use, CO2

Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling.

Science.gov (United States)

Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun

2017-12-01

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

Olefins and chemical regulation in Europe: REACH.

Science.gov (United States)

Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

2015-11-05

REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

The effect of drilling parameters for surface roughness in drilling of AA7075 alloy

Directory of Open Access Journals (Sweden)

Yaşar Nafiz

2017-01-01

Full Text Available AA7075 aluminum alloy has been very popular significantly interest in the production of structural components in automotive and aviation applications due to its high strength, low density, good plasticity and better machinability comparable to many metals. Particularly, final products must have uniformly high quality to ensure essential safety standards in the aircraft industry. The optimization of hole quality which can variable according to tool geometry and drilling parameters is important in spite of high machinability rate of AA7075 alloy. In this study, the effects of drilling parameters on average surface roughness (Ra has been investigated in drilling of AA7075 with tungsten carbide drills. Machining experiments were performed with three different drill point angles and three different levels of cutting parameters (feed rate, cutting speed. The effects of drilling parameters on thrust force has been determined with ANOVA in %95 confidence level. Feed rate was determined as the most important factor on Ra according to ANOVA results. Moreover, it was shown that increasing feed rate leads to increase of Ra while increasing drill point angle leads to decrease of Ra. The optimum surface roughness was obtained with point angle of 130°, cutting speed of 40 m/min and feed rate of 0.1 mm/rev, thereby the validity of optimization was confirmed with Taguchi method.

Performance of engine-driven rotary endodontic instruments with a superimposed bending deflection: V. Gates Glidden and Peeso drills.

Science.gov (United States)

Brantley, W A; Luebke, N H; Luebke, F L; Mitchell, J C

1994-05-01

A laboratory study was performed on Gates Glidden and Peeso drills to determine the incidence of shaft fracture when a bending deflection was superimposed on the rotating drills. Samples of sizes #1 to #6 stainless steel Gates Glidden drills, sizes #1 to #6 stainless steel and carbon steel-type P Peeso drills, and sizes #009 to #023 carbon steel-type B-1 Peeso drills from each of two manufacturers were evaluated with a unique apparatus that applied a 2-mm bending deflection while rotating the instruments. The apparatus did not restrict movement of the bur head during rotation. The test drills were rotated at 2500, 4000, and 7000 revolutions per minute, and the number of revolutions at failure was recorded. Scanning electron microscopic observations established that the stainless steel Gates Glidden and Peeso drills failed by ductile fracture, whereas the carbon steel Peeso drills failed by brittle fracture. Instrument fracture was always near the handpiece shank with this test, and the length of the fractured drills was measured from the working tip. It is recommended that this additional test be adopted to determine fatigue properties of engine-driven rotary endodontic instruments in establishing international performance standards.

Radiation-chemical alkylation of olefines with adamantane

International Nuclear Information System (INIS)

Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

1977-01-01

Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

3D Model Optimization of Four-Facet Drill for 3D Drilling Simulation

Directory of Open Access Journals (Sweden)

Buranský Ivan

2016-09-01

Full Text Available The article is focused on optimization of four-facet drill for 3D drilling numerical modelling. For optimization, the process of reverse engineering by PowerShape software was used. The design of four-facet drill was created in NumrotoPlus software. The modified 3D model of the drill was used in the numerical analysis of cutting forces. Verification of the accuracy of 3D models for reverse engineering was implemented using the colour deviation maps. The CAD model was in the STEP format. For simulation software, 3D model in the STEP format is ideal. STEP is a solid model. Simulation software automatically splits the 3D model into finite elements. The STEP model was therefore more suitable than the STL model.

Drilling technology advances on four fronts

Energy Technology Data Exchange (ETDEWEB)

Budd, G.

2002-01-01

Trends and advances in drilling technology are discussed. Four different major trends have been identified. One of these is proprietary case drilling which is said to allow operators to simultaneously drill, case, and evaluate oil and gas wells. In proprietary case drilling, the well is drilled with standard oil field casing which remains in the hole all the time, eliminating the need for tripping. Drill bits and other downhole tools are lowered via wireline inside the casing and latched to the last joint of casing. Wells are drilled either by rotating the casing or by using a downhole mud motor for steering, using conventional directional tools. This technology was introduced by Tesco and is marketed in 25 countries along with a full range of drilling products and services. Super single rigs are an other trend which, owing to their versatility, combined with relatively small environmental footprint have become the rig of choice in a growing number of drilling programs. Super single rigs use 45-ft. joints of drill pipe, more versatile top drives and they have an automated pipe handling system. Super singles can be used on both vertical and slant wells and offer advantages of lower costs, higher efficiencies and greater drilling depths. Given their low environmental impact hydraulic capability, super singles also find application where zero disturbance rules are in effect, as for example, in some parts of southern Alberta. Directional drilling and MWD are most associated with SAGD projects but they also have been used and made significant difference in other spheres of oil recovery as well. The fact is that about 35 percent of wells drilled today are drilled with some form of directional drilling; this will stimulate the growth of ever more advanced MWD technology. Northern rigs are in a class of their own in that here the emphasis is on keeping the crew warm, as opposed to lots of gadgets. The most immediately-visible heat-conserving modification is the 60-ft wind

Drillings at Veitsivaara in Hyrynsalmi

International Nuclear Information System (INIS)

Hinkkanen, H.; Oehberg, A.

1990-04-01

According to Governmen's decision in principle Teollisuuden Voima Oy is obliged to make bedrock investigations for the final disposal of the spent fuel produced by its power plant in Olkiluoto. Areas in Kuhmo, Hyrynsalmi, Sievi, Konginkangas and Olkiluoto were selected for the preliminary site investigations to be carried out during years 1987-1992. In Veitsivaara, Hyrynsalmi the investigation program was started in April 1987. During years 1987-1988 a deep borehole (1002 m) and 4 and 500 m deep additional boreholes were core drilled in the area. Various parameters were measured from the flushing water during the drilling. Corelogging included collecting detailed data of fractures and determining the weathering degree and petrographical properties. Rock mechanical properties, uniaxial compressive strength, Young's modulus and Poisso's ratio were measured from core samples. The flushing water needed in the drillings was pumped from 100 m deep borehole wells drilled with down-the-hole method in the vicinity of the borehole. The water was labeled with 2 tracers before use. About 75 m deep hole was percussion drilled near the borehole KR1. The spreading of the flushing water in the upper part of bedrock and the quality off the ground of the groundwater were studied by taking watersamples from the hole. 30 vertical holes were core drilled down to the depth of 10 m in bedrock with a light drilling unit. Drilling was carried out in order to determine the thickness of the overburden, to investigate the geophysical anomaly sources and to support geological mapping in areas covered with overburden. Groundwater hydraulics is one of the main subjects during the preliminary site investigation phase. For that reason 7 multilevel piezometers were installed on the site to monitore hydraulic head in 3 levels in the uppermost part of bedrock. The work consisted of borehole drillings to the depth of 100 m, geophysical borehole loggings and installation of piezometers. In addition

Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

Energy Technology Data Exchange (ETDEWEB)

Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.; Ramasamy, Karthikeyan K.; Kovarik, Libor; Bowden, Mark E.; Onfroy, Thomas; Dagle, Robert A.

2016-04-01

In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found to produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship between

Palladium-Catalyzed Tandem Oxidative Arylation/Olefination of Aromatic Tethered Alkenes/Alkynes.

Science.gov (United States)

Gao, Yang; Gao, Yinglan; Wu, Wanqing; Jiang, Huanfeng; Yang, Xiaobo; Liu, Wenbo; Li, Chao-Jun

2017-01-18

We describe herein a palladium-catalyzed tandem oxidative arylation/olefination reaction of aromatic tethered alkenes/alkynes for the synthesis of dihydrobenzofurans and 2 H-chromene derivatives. This reaction features a 1,2-difunctionalization of C-C π-bond with two C-H bonds using O 2 as terminal oxidant at room temperature. The products obtained are valuable synthons and important scaffolds in biological agents and natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Casing drilling - first experience in Brazil; Casing drilling - primeira experiencia no Brasil

Energy Technology Data Exchange (ETDEWEB)

Placido, Joao Carlos Ribeiro; Medeiros, Fernando; Lucena, Humberto; Medeiros, Joao Carlos Martins de; Costa, Vicente Abel Soares Rosa da; Silva, Paulo Roberto Correa da [PETROBRAS, Rio de Janeiro, RJ (Brazil); Alves, Renato J.M. [Tesco, London (United Kingdom)

2004-07-01

This paper describes the 'Casing Drilling' technology and its first experience in Brazil. This new process of casing while drilling was first developed to reduce costs. This system integrates the drilling process and casing running in one operation, promoting a more efficient well construction system, reducing trip time and costs of drill pipes and their transportation. Besides, this methodology intends to eliminate hole problems related to trouble zones with abnormal pressure with loss circulation, to overcome zones with wellbore instabilities, and to facilitate well control. Two companies have been identified using this technology: Tesco and Weatherford. However, there are differences between the techniques used by these companies, which are described in this paper. In the first experience in Brazil, it was decided to field test the technology developed by Tesco. This paper describes the preparation, the operation and the results of this first test. (author)

A computational mechanistic study of Pd(ii)-catalyzed γ-C(sp3)-H olefination/cyclization of amines: the roles of bicarbonate and ligand effect.

Science.gov (United States)

Liu, Jian-Biao; Tian, Ying-Ying; Zhang, Xin; Wang, Lu-Lin; Chen, De-Zhan

2018-04-03

The detailed mechanism of palladium-catalyzed γ-C(sp3)-H olefination/cyclization of triflyl-protected amines was investigated by density functional theory (DFT) calculations. The olefinated intermediate was initially formed in the first catalytic cycle involving ligand exchange, bicarbonate-assisted C(sp3)-H bond cleavage, alkene insertion and 'reductive β-hydride elimination'. The following syn-addition and reductive elimination furnish the aza-Wacker product. The first step of reductive elimination is the rate-determining step. The mechanism unveils the important roles of bicarbonate: aiding the C-H activation and abstracting the β-proton in the second step of reductive elimination. The parallel bridging mode in the metal-olefin intermediate facilitates the syn-addition, explaining the experimentally observed stereoselectivity. The effect of the monodentate pyridine-based ligands is also discussed.

Slant rigs offer big payoffs in shallow drilling

International Nuclear Information System (INIS)

Smith, J.; Edwards, B.

1992-01-01

Slant hole drilling technology can result in considerable savings over conventionally drilled deviated holes because mud motors and deviation control with measurement while drilling tools are usually unnecessary. The benefits of using slant hole rigs for development drilling improve after the bit walk tendencies and the correct bottom hole assemblies have been determined for a particular area. This article discusses three recent drilling operations that successfully used slant drilling technology on land-based projects: drilling for heavy oil in Alberta, drilling for gas in Alberta, and drilling a river crossing for a gas pipeline in British Columbia. These examples demonstrate the flexibility of slant drilling technology

Drillings at Kivetty in Konginkangas

International Nuclear Information System (INIS)

Hinkkanen, H.; Oehberg, A.

1990-05-01

According to Government's decision in principle Teollisuuden Voima Oy is obliged to make bedrock investigations for the final disposal of the spent fuel produced by its power plant in Olkiluoto. Areas in Kuhmo, Hyrynsalmi, Sievi, Konginkangas and Olkiluoto were selected for the preliminary site investigations to be carried out during years 1987-1992. In Kivetty, Konginkangas the investigation program was started in spring 1988. During years 1988-1989 a deep borehole (1019 m) and 4 about 500 m deep additional boreholes were core drilled in the area. The structure of the holes makes it possible to carry out many investigations in the holes. Various parameters were measured from the flushing water during the drilling. Corelogging included collecting detailed data of fractures and determining the weathering degree and petrographical properties. Rock mechanical properties, uniaxial compressive strength, Young's modulus and Poisson's ratio were measured from core samples. The flushing water needed in the drillings was pumped from 100 m deep borehole wells drilled with down-the-hole method in the vicinity of the borehole. The water was labeled with 2 tracers before use. 30 vertical holes were core drilled down to the depth of 10 m in bedrock with a light drilling unit. Drilling was carried out in order to determine the thickness of the overburden to investigate the geophysical anomaly sources and to support geological mapping in areas covered with overburden. Groundwater hydraulics is one of the main subjects during the preliminary site investigation phase. For that reason 7 multilevel piezometers were installed on the site to monitore hydraulic head in 3 levels in the uppermost part of bedrock. The work consisted of borehole drillings to the depth of 100 m, geophysical borehole loggings and installation of piezometers. In addition about 65 shotholes were drilled for VSP-, tubewave and seismic measurements

Drillings at Syyry in Sievi

International Nuclear Information System (INIS)

Hinkkanen, H.; Oehberg, A.

1990-10-01

According to Government's decision in principle Teollisuuden Voima Oy is obliged to make bedrock investigations for the final disposal of the spent fuel produced by its power plant in Olkiluoto. Areas in Kuhmo, Hyrynsalmi, Sievi, Konginkangas and Olkiluoto were selected for the preliminary site investigations to be carried out during years 1987-1992. In Syyry, Sievi the investigation program was started in spring 1988. During years 1988-1989 a deep borehole (1022 m) and 4 about 500-700 m deep additional boreholes were core drilled in the area. The structure of the holes makes it possible to carry out many investigations in the holes. Various parameters were measured from the flushing water during the drilling. Corelogging included collecting detailed data of fractures and determining the weathering degree and petrographical properties. Rock mechanical properties, uniaxial compressive strength, Young's modulus and Poisson's ratio were measured from core samples. The flushing water needed in the drillings was pumped from 100 m deep borehole wells drilled with down-the-hole method in the vicinity of the borehole. The water was labeled with 2 tracers before use. 35 vertical holes were core drilled down to the depth of 10-20 m in bedrock with a light drilling unit. Drilling was carried out in order to determine the thickness of the overburden, to investigate the geophysical anomaly sources and to support geological mapping in areas covered with overburden. Groundwater hydraulics is one of the main subjects during the preliminary site investigation phase. For that reason 7 multilevel piezometers were installed on the site to monitore hydraulic head in 3 levels in the uppermost part of bedrock. The work consisted of borehole drillings to the depth of 100 m, geophysical borehole loggings and installation of piezometers. In addition about 85 shotholes were drilled for VSP-, tubewave and seismic measurements

Drilling rig

Energy Technology Data Exchange (ETDEWEB)

Galiopa, A A; Yegorov, E K

1981-01-04

A drilling rig is proposed which contains a tower, lifter in the form of n infinite chain, and mobile rotator with holding device connected to the chain, and pipe holder. In order to accelerate the auxiliary operations to move the drilling string and unloaded rotator, the rotator is equipped with a clamp with means for transverse connection of it to both branches of the chain, while the pipe holders equipped with a clamp with means of connecting it to one of the branches of the chain.

Rhenium-catalyzed dehydrogenative olefination of C(sp(3))-H bonds with hypervalent iodine(III) reagents.

Science.gov (United States)

Gu, Haidong; Wang, Congyang

2015-06-07

A dehydrogenative olefination of C(sp(3))-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

Borata-Wittig olefination reactions of ketones, carboxylic esters and amides with bis(pentafluorophenyl)borata-alkene reagents.

Science.gov (United States)

Wang, Tongdao; Kohrt, Sonja; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

2017-08-07

The strongly electrophilic borane derivative amino-CH 2 CH 2 CH 2 -B(C 6 F 5 ) 2 6 was α-CH deprotonated with LiTMP to give the borata-alkene {[amino-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ][Li + ]} 2 9 which underwent facile [2 + 2] cycloaddition reactions with benzophenone or fluorenone to yield the respective 1,2-oxaboretanides 11a,b. Compounds 9 and 11 were characterized by the X-ray diffraction. Thermolysis or hydrolysis of compounds 11a,b gave the corresponding borata-Wittig olefination products 12a,b. A variety of R-CH 2 -CH 2 -B(C 6 F 5 ) 2 boranes (conveniently generated by hydroboration of terminal alkenes R-CH[double bond, length as m-dash]CH 2 with Piers' borane [HB(C 6 F 5 ) 2 ]) were analogously deprotonated to give the respective borata-alkenes 16a-e (R: Ph-CH 2 -, n C 4 H 9 , t Bu, Cy, PhCH 2 CH 2 -). They underwent "non-classical" borata-Wittig olefination reactions with ethylformate to give the respective enolether carbonylation products, or their C 1 -elongated aldehydes (after hydrolysis). The borata-alkene [Ph-(CH 2 ) 2 -CH[double bond, length as m-dash]B(C 6 F 5 ) 2 - ] [Li + HTMP] (16a) gave the respective "non-classical" borata-Wittig olefination products, the enolethers 25a,b and 27, respectively, upon treatment with methyl- or ethyl acetate or γ-butyrolactone.

Ozone impact minimization through coordinated scheduling of turnaround operations from multiple olefin plants in an ozone nonattainment area

Science.gov (United States)

Ge, Sijie; Wang, Sujing; Xu, Qiang; Ho, Thomas

2018-03-01

Turnaround operations (start-up and shutdown) are critical operations in olefin plants, which emit large quantities of VOCs, NOx and CO. The emission has great potentials to impact the ozone level in ozone nonattainment areas. This study demonstrates a novel practice to minimize the ozone impact through coordinated scheduling of turnaround operations from multiple olefin plants located in Houston, Texas, an ozone nonattainment area. The study considered two olefin plants scheduled to conduct turnaround operations: one start-up and one shutdown, simultaneously on the same day within a five-hour window. Through dynamic simulations of the turnaround operations using ASPEN Plus Dynamics and air quality simulations using CAMx, the study predicts the ozone impact from the combined effect of the two turnaround operations under different starting-time scenarios. The simulations predict that the ozone impact from planned turnaround operations ranges from a maximum of 11.4 ppb to a minimum of 1.4 ppb. Hence, a reduction of up to 10.0 ppb can be achieved on a single day based on the selected two simulation days. This study demonstrates a cost-effective and environmentally benign ozone control practice for relevant stakeholders, including environmental agencies, regional plant operators, and local communities.

Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron-Deficient η(5) -Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions.

Science.gov (United States)

Takahama, Yuji; Shibata, Yu; Tanaka, Ken

2015-06-15

The oxidative olefination of sp(2) C-H bonds of anilides with both activated and unactivated alkenes using an (electron-deficient η(5) -cyclopentadienyl)rhodium(III) complex is reported. In contrast to reactions using this electron-deficient rhodium(III) catalyst, [Cp*RhCl2 ]2 showed no activity against olefination with unactivated alkenes. In addition, the deuterium kinetic isotope effect (DKIE) study revealed that the C-H bond cleavage step is thought to be the turnover-limiting step. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neurosurgical robotic arm drilling navigation system.

Science.gov (United States)

Lin, Chung-Chih; Lin, Hsin-Cheng; Lee, Wen-Yo; Lee, Shih-Tseng; Wu, Chieh-Tsai

2017-09-01

The aim of this work was to develop a neurosurgical robotic arm drilling navigation system that provides assistance throughout the complete bone drilling process. The system comprised neurosurgical robotic arm navigation combining robotic and surgical navigation, 3D medical imaging based surgical planning that could identify lesion location and plan the surgical path on 3D images, and automatic bone drilling control that would stop drilling when the bone was to be drilled-through. Three kinds of experiment were designed. The average positioning error deduced from 3D images of the robotic arm was 0.502 ± 0.069 mm. The correlation between automatically and manually planned paths was 0.975. The average distance error between automatically planned paths and risky zones was 0.279 ± 0.401 mm. The drilling auto-stopping algorithm had 0.00% unstopped cases (26.32% in control group 1) and 70.53% non-drilled-through cases (8.42% and 4.21% in control groups 1 and 2). The system may be useful for neurosurgical robotic arm drilling navigation. Copyright © 2016 John Wiley & Sons, Ltd.

Constructing Multiply Substituted Arenes Using Sequential Pd(II)-Catalyzed C–H Olefination**

Science.gov (United States)

Engle, Keary M.; Wang, Dong-Hui; Yu, Jin-Quan

2011-01-01

Complementary catalytic systems have been developed in which the reactivity/selectivity balance in Pd(II)-catalyzed ortho-C–H olefination can be modulated through ligand control. This allows for sequential C–H functionalization for the rapid preparation of 1,2,3-trisubstituted arenes. Additionally, a rare example of iterative C–H activation, in which a newly installed functional group directs subsequent C–H activation has been demonstrated. PMID:20632344

Extended Reach Drilling on the example of Reelwell Drilling Method: Influence examination of different drill pipes on drilling performance on Idun field on the Norwegian Continental Shelf by PGNiG Norway AS.

OpenAIRE

Krol, Dariusz Pawel

2011-01-01

Master's thesis in Petroleum engineering Horizontal or extended reach drilling is incredibly fast growing technology. Although in some areas of the world ERD is still novelty, most of oil companies have been using the technology reliably and successfully for dozens of years. And those companies want to improve well-worn solutions to obtain better performance, thereby reducing costs. One of the main aspects that affects drilling performance and efficiency is adequate choice of drill pipe...

Internal deformation in layered Zechstein-III K-Mg salts. Structures formed by complex deformation and high contrasts in viscosity observed in drill cores.

Science.gov (United States)

Raith, Alexander; Urai, Janos L.

2016-04-01

During the evaporation of a massive salt body, alternations of interrupted and full evaporation sequences can form a complex layering of different lithologies. Viscosity contrasts of up to five orders of magnitude between these different lithologies are possible in this environment. During the late stage of an evaporation cycle potassium and magnesium (K-Mg) salts are precipitated. These K-Mg salts are of economic interest but also a known drilling hazard due to their very low viscosity. How up to 200m thick layers of these evaporites affect salt deformation at different scales is not well known. A better understanding of salt tectonics with extreme mechanical stratification is needed for better exploration and production of potassium-magnesium salts and to predict the internal structure of potential nuclear waste repositories in salt. To gain a better understanding of the internal deformation of these layers we analyzed K-Mg salt rich drill cores out of the Zechstein III-1b subunit from the Veendam Pillow 10 km southeast of Groningen, near the city Veendam in the NE Netherlands. The study area has a complex geological history with multiple tectonic phases of extension and compression forming internal deformation in the pillow but also conserving most of the original layering. Beside halite the most common minerals in the ZIII-1b are carnallite, kieserite, anhydrite and bischofite alternating in thin layers of simple composition. Seismic interpretation revealed that the internal structure of the Veendam Pillow shows areas, in which the K-Mg salt rich ZIII 1b layer is much thicker than elsewhere, as a result of salt deformation. The internal structure of the ZIII-1b on the other hand, remains unknown. The core analysis shows a strong strain concentration in the weaker Bischofite (MgCl2*6H20) and Carnallite (KMgCl3*6H20) rich layers producing tectonic breccias and highly strained layers completely overprinting the original layering. Layers formed by alternating beds

Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

Science.gov (United States)

2015-01-01

Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids. PMID:24666182

STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

Science.gov (United States)

2013-03-28

production of polyethylene (PE) and polypropylene (PP) topped 53 billion pounds in 2011.1 This extreme demand has ensured that olefin polymerization...is an ideal starting monomer as it is a liquid at room temperature facilitating rapid screening and data collection without the need for cumbersome...elastomers, binders, thermoplastic elastomers, rheology modifiers, permeation selective membranes, and high strength, light-weight structural materials

Trends in the Drilling Waste Management

Directory of Open Access Journals (Sweden)

Lucyna Czekaj

2006-10-01

Full Text Available Petroleum Industry is trying to achieve sustainable development goals. Each year new solutions are implemented to minimize the environmental impact of drilling operations. The paper presents trends in the drilling waste management caused by introducing the sustainable development into the petroleum industry. Old solutions such as the drilling waste disposal at the waste dump or dumping ground are not acceptable from the environmental point of view. The paper presents an analysis of new solutions as the sustainable solutions. The most important problem is the chemical pollution in cuttings and the waste drilling mud. The industrial solutions as well as the laboratory research on the pollution removing from drilling wastes are analysed. The most promising method seems to be the recycling and design for the environment of drilling mud.

H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

Czech Academy of Sciences Publication Activity Database

Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

2017-01-01

Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol-to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

Ru-Based Complexes with Quaternary Ammonium Tags Immobilized on Mesoporous Silica as Olefin Metathesis Catalysts

Czech Academy of Sciences Publication Activity Database

Pastva, Jakub; Skowerski, K.; Czarnocki, S. J.; Žilková, Naděžda; Čejka, Jiří; Bastl, Zdeněk; Balcar, Hynek

2014-01-01

Roč. 4, č. 9 (2014), s. 3227-3236 ISSN 2155-5435 R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : olefin metathesis * heterogeneous catalysts * mesoporous molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.312, year: 2014

H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

Czech Academy of Sciences Publication Activity Database

Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

2017-01-01

Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol -to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

CFPL installs products pipeline with directional drilling

International Nuclear Information System (INIS)

Anon.

1996-01-01

Central Florida Pipeline Company (CFPL), a subsidiary of GATX Terminals Corp., Tampa, FL, has used directional drilling under seven water bodies in Hillsborough, Polk and Osceola Counties in constructing its new pipeline from Tampa to Orlando. Primary reason for using directional drilling is to protect the environment by minimizing water turbidity while the 16-inch diameter, 109-mile refined petroleum products pipeline is being installed. Total cost of the project is pegged at $68.5 million. Directional drilling enabled the pipe to be placed about 20 feet below the bottom of: The Alafia River in Riverview with 999 feet drilled; Port Sutton Channel near the Port of Tampa with 2,756 feet drilled; Reedy Creek Swamp at the intersection of Interstate 4 and Highway 192 which had 1,111 feet drilled; Wetland number-sign 70 southwest of Lake Wales with 1,575 feet drilled; Peace River south of Bartow had 2,470 feet drilled; Bonnet Creek west of Kissimmee had 693 feet drilled. Shingle Creek near the borders of Osceola and Orange Counties with 1,700 feet drilled. This paper reviews the design plans for construction and the emergency response plans should a rupture occur in the line

Aerated drilling cutting transport analysis in geothermal well

Science.gov (United States)

Wakhyudin, Aris; Setiawan, Deni; Dwi Marjuan, Oscar

2017-12-01

Aeratad drilling widely used for geothermal drilling especially when drilled into predicted production zone. Aerated drilling give better performance on preventing lost circulation problem, improving rate of penetration, and avoiding drilling fluid invasion to productive zone. While well is drilled, cutting is produced and should be carried to surface by drilling fluid. Hole problem, especially pipe sticking will occur while the cutting is not lifted properly to surface. The problem will effect on drilling schedule; non-productive time finally result more cost to be spent. Geothermal formation has different characteristic comparing oil and gas formation. Geothermal mainly has igneous rock while oil and gas mostly sedimentary rock. In same depth, formation pressure in geothermal well commonly lower than oil and gas well while formation temperature geothermal well is higher. While aerated drilling is applied in geothermal well, Igneous rock density has higher density than sedimentary rock and aerated drilling fluid is lighter than water based mud hence minimum velocity requirement to transport cutting is larger than in oil/gas well drilling. Temperature and pressure also has impact on drilling fluid (aerated) density. High temperature in geothermal well decrease drilling fluid density hence the effect of pressure and temperature also considered. In this paper, Aerated drilling cutting transport performance on geothermal well will be analysed due to different rock and drilling fluid density. Additionally, temperature and pressure effect on drilling fluid density also presented to merge.

Methanol to olefin Conversion on HSAPO-34 zeolite from periodic density functional theory calculations: a complete cycle of side chain hydrocarbon pool mechanism

Energy Technology Data Exchange (ETDEWEB)

Wang, C.M.; Wang, Y.D.; Xie, Z.K.; Liu, Z.P. [SINOPEC, Shanghai (China)

2009-03-15

For its unique position in the coal chemical industry, the methanol to olefin (MTO) reaction has been a hot topic in zeolite catalysis. Due to the complexities of catalyst structure and reaction networks, many questions such as how the olefin chain is built from methanol remain elusive. On the basis of periodic density functional theory calculations, this work establishes the first complete catalytic cycle for MTO reaction via hexamethylbenzene (HMB) trapped in HSAPO-34 zeolite based on the so-called side chain hydrocarbon pool mechanism. The cycle starts from the methylation of HMB that leads to heptamethylbenzenium ion (heptaMB{sup +}) intermediate. This is then followed by the growth of side chain via repeated deprotonation of benzenium ions and methylation of the exocyclic double bond. Ethene and propene can finally be released from the side ethyl and isopropyl groups of benzenium ions by deprotonation and subsequent protonation steps. We demonstrate that (i) HMB/HSAPO-34 only yields propene as the primary product based on the side chain hydrocarbon pool mechanism and (ii) an indirect proton-shift step mediated by water that is always available in the system is energetically more favorable than the traditionally regarded internal hydrogen-shift step. Finally, the implications of our results toward understanding the effect of acidity of zeolite on MTO activity are also discussed.

Propagation of Measurement-While-Drilling Mud Pulse during High Temperature Deep Well Drilling Operations

OpenAIRE

Li, Hongtao; Meng, Yingfeng; Li, Gao; Wei, Na; Liu, Jiajie; Ma, Xiao; Duan, Mubai; Gu, Siman; Zhu, Kuanliang; Xu, Xiaofeng

2013-01-01

Signal attenuates while Measurement-While-Drilling (MWD) mud pulse is transmited in drill string during high temperature deep well drilling. In this work, an analytical model for the propagation of mud pulse was presented. The model consists of continuity, momentum, and state equations with analytical solutions based on the linear perturbation analysis. The model can predict the wave speed and attenuation coefficient of mud pulse. The calculated results were compared with the experimental dat...

Cortical bone drilling: An experimental and numerical study.

Science.gov (United States)

Alam, Khurshid; Bahadur, Issam M; Ahmed, Naseer

2014-12-16

Bone drilling is a common surgical procedure in orthopedics, dental and neurosurgeries. In conventional bone drilling process, the surgeon exerts a considerable amount of pressure to penetrate the drill into the bone tissue. Controlled penetration of drill in the bone is necessary for safe and efficient drilling. Development of a validated Finite Element (FE) model of cortical bone drilling. Drilling experiments were conducted on bovine cortical bone. The FE model of the bone drilling was based on mechanical properties obtained from literature data and additionally conducted microindentation tests on the cortical bone. The magnitude of stress in bone was found to decrease exponentially away from the lips of the drill in simulations. Feed rate was found to be the main influential factor affecting the force and torque in the numerical simulations and experiments. The drilling thrust force and torque were found to be unaffected by the drilling speed in numerical simulations. Simulated forces and torques were compared with experimental results for similar drilling conditions and were found in good agreement.CONCLUSIONS: FE schemes may be successfully applied to model complex kinematics of bone drilling process.

Numerical Modeling of Foam Drilling Hydraulics

Directory of Open Access Journals (Sweden)

Ozcan Baris

2007-12-01

Full Text Available The use of foam as a drilling fluid was developed to meet a special set of conditions under which other common drilling fluids had failed. Foam drilling is defined as the process of making boreholes by utilizing foam as the circulating fluid. When compared with conventional drilling, underbalanced or foam drilling has several advantages. These advantages include: avoidance of lost circulation problems, minimizing damage to pay zones, higher penetration rates and bit life. Foams are usually characterized by the quality, the ratio of the volume of gas, and the total foam volume. Obtaining dependable pressure profiles for aerated (gasified fluids and foam is more difficult than for single phase fluids, since in the former ones the drilling mud contains a gas phase that is entrained within the fluid system. The primary goal of this study is to expand the knowledge-base of the hydrodynamic phenomena that occur in a foam drilling operation. In order to gain a better understanding of foam drilling operations, a hydrodynamic model is developed and run at different operating conditions. For this purpose, the flow of foam through the drilling system is modeled by invoking the basic principles of continuum mechanics and thermodynamics. The model was designed to allow gas and liquid flow at desired volumetric flow rates through the drillstring and annulus. Parametric studies are conducted in order to identify the most influential variables in the hydrodynamic modeling of foam flow.

Chemical Speciation of Chromium in Drilling Muds

International Nuclear Information System (INIS)

Taguchi, Takeyoshi; Yoshii, Mitsuru; Shinoda, Kohzo

2007-01-01

Drilling muds are made of bentonite and other clays, and/or polymers, mixed with water to the desired viscosity. Without the drilling muds, corporations could not drill for oil and gas and we would have hardly any of the fuels and lubricants considered essential for modern industrial civilization. There are hundreds of drilling muds used and some kinds of drilling muds contain chromium. The chemical states of chromium in muds have been studied carefully due to concerns about the environmental influence. However it is difficult to determine the chemical state of chromium in drilling muds directly by conventional analytical methods. We have studied the chemical form of chromium in drilling muds by using a laboratory XAFS system and a synchrotron facility

Accuracy of linear drilling in temporal bone using drill press system for minimally invasive cochlear implantation.

Science.gov (United States)

Dillon, Neal P; Balachandran, Ramya; Labadie, Robert F

2016-03-01

A minimally invasive approach for cochlear implantation involves drilling a narrow linear path through the temporal bone from the skull surface directly to the cochlea for insertion of the electrode array without the need for an invasive mastoidectomy. Potential drill positioning errors must be accounted for to predict the effectiveness and safety of the procedure. The drilling accuracy of a system used for this procedure was evaluated in bone surrogate material under a range of clinically relevant parameters. Additional experiments were performed to isolate the error at various points along the path to better understand why deflections occur. An experimental setup to precisely position the drill press over a target was used. Custom bone surrogate test blocks were manufactured to resemble the mastoid region of the temporal bone. The drilling error was measured by creating divots in plastic sheets before and after drilling and using a microscope to localize the divots. The drilling error was within the tolerance needed to avoid vital structures and ensure accurate placement of the electrode; however, some parameter sets yielded errors that may impact the effectiveness of the procedure when combined with other error sources. The error increases when the lateral stage of the path terminates in an air cell and when the guide bushings are positioned further from the skull surface. At contact points due to air cells along the trajectory, higher errors were found for impact angles of [Formula: see text] and higher as well as longer cantilevered drill lengths. The results of these experiments can be used to define more accurate and safe drill trajectories for this minimally invasive surgical procedure.

Seismic Prediction While Drilling (SPWD: Looking Ahead of the Drill Bit by Application of Phased Array Technology

Directory of Open Access Journals (Sweden)

Marco Groh

2010-04-01

Full Text Available Geophysical exploration is indispensable for planning deep drilling. Usually 2D- or 3D-seismics investigations are applied and, depending on the resulting geologic model for the underground, the drill site and drilling path are determined. In recent years the focus of exploration has shifted towards small-scale geological structures such as local layers and faults. Depending on the source frequencies and the target depth, 2D- or 3D-seismics from surface cannot always resolve such structures in particular at larger depths. In general, signal frequencies of about 30–70 Hz are typical for surface seismic methods. The deeper and smaller the sought-after structures are, the worse will be the resolution. Therefore, borehole seismic measurements like Vertical Seismic Profile (VSP or Seismic While Drilling (SWD have been developed (Fig. 1. For the VSP method geophones are normally integrated in the borehole, while the seismicsource generates seismic waves at the surface. The SWD method uses the drill bit as the seismic source. Hence, the quality of the seismic signals is highly dependent on the drilled rock and the type of drill bit, but even well-suited rock conditions and adequate drilling may not provide sufficient data quality.

Differing opinions about natural gas drilling in two adjacent counties with different levels of drilling activity

International Nuclear Information System (INIS)

Kriesky, J.; Goldstein, B.D.; Zell, K.; Beach, S.

2013-01-01

The pace of development of shale gas plays varies greatly among US states and globally. Through analysis of telephone survey responses, we explore support for natural gas drilling in residents of Washington County (WC), PA (n=502) vs. residents of Allegheny County (AC), PA (n=799). WC has had intense Marcellus Shale (MS) drilling activity, in comparison to adjacent AC, which has had little drilling activity. WC residents are marginally more supportive of MS drilling than are AC residents (p=0.0768). Residents of WC are more likely to perceive MS as an economic opportunity than are AC residents (p=0.0015); to be in a family that has signed a MS lease (p<0.0001); to follow the MS issue closely (p=0.0003); to get MS information from neighbors, friends, and relatives (p<0.0001); and are marginally less likely to perceive MS as an environmental threat (p=0.1090). WC leaseholders are significantly more supportive of MS drilling than WC non-leaseholders and AC non-leaseholders (p=0.0024). Mediation analyses show that county-based differences in support of MS drilling are due to WC residents seeing more of an economic opportunity in the MS and their greater likelihood of having a family-held lease. - Highlights: • Telephone survey analysis of sources of support for Marcellus Shale drilling. • Perceived positive economic impact of drilling drives support among respondents. • Mineral rights leaseholders are significantly more supportive than non-leaseholders

Experimental Analysis of Temperature Differences During Implant Site Preparation: Continuous Drilling Technique Versus Intermittent Drilling Technique.

Science.gov (United States)

Di Fiore, Adolfo; Sivolella, Stefano; Stocco, Elena; Favero, Vittorio; Stellini, Edoardo

2018-02-01

Implant site preparation through drilling procedures may cause bone thermonecrosis. The aim of this in vitro study was to evaluate, using a thermal probe, overheating at implant sites during osteotomies through 2 different drilling methods (continuous drilling technique versus intermittent drilling technique) using irrigation at different temperatures. Five implant sites 13 mm in length were performed on 16 blocks (fresh bovine ribs), for a total of 80 implant sites. The PT-100 thermal probe was positioned 5 mm from each site. Two physiological refrigerant solutions were used: one at 23.7°C and one at 6.0°C. Four experimental groups were considered: group A (continuous drilling with physiological solution at 23.7°C), group B (intermittent drilling with physiological solution at 23.7°C), group C (continuous drilling with physiological solution at 6.0°C), and group D (intermittent drilling with physiological solution at 6.0°C). The Wilcoxon rank-sum test (2-tailed) was used to compare groups. While there was no difference between group A and group B (W = 86; P = .45), statistically significant differences were observed between experimental groups A and C (W = 0; P =.0001), B and D (W = 45; P =.0005), and C and D (W = 41; P = .003). Implant site preparation did not affect the overheating of the bone. Statistically significant differences were found with the refrigerant solutions. Using both irrigating solutions, bone temperature did not exceed 47°C.

Drilling rig mast

Energy Technology Data Exchange (ETDEWEB)

Bulgakov, E.S.; Barashkov, V.A.; Lebedev, A.I.; Panin, N.M.; Sirotkin, N.V.

1981-01-07

A drilling rig mast is proposed that contains a portal with a carrier shaft hinged to it and struts with stays. In order to decrease the time expended in the assembly and dessembly of the drilling rig, the portal is constructed from mobile and immobile parts that are connected together by a ball pivot; the immobile section of the portal has a T-shaped recess for directing the mobile section.

The Marskhod Egyptian Drill Project

Science.gov (United States)

Shaltout, M. A. M.

We describe a possible participation of Egypt in a future Mars rover Mission. It was suggested that Egypt participate through involvement in the design, building and testing of a drill to obtain sub-surface samples. The Space Research Institute of the Russian Academy of Sciences (IKI), formally invited the Egyptian Ministry of Scientific Research to study the concept for potential use on the Russian Mars 2001 Mission. As one of the objectives of the Marskhod mission was the analysis of sub-surface samples, a drilling mechanism in the payload would be essential. The Egyptian expertise in drill development is associated with the archaeological exploration of the Pyramids. A sophisticated drilling system perforated limestone to a depth of 2 m without the use of lubricants or cooling fluids that might have contaminated the Pit's environment. This experience could have been applied to a drill development Mars 2001 mission, which was unfortunately canceled due to economic problems.

Drilling mud

Energy Technology Data Exchange (ETDEWEB)

Rusayev, A A; Bibikov, K V; Simonenkov, I D; Surkova, K I

1982-01-01

Drilling mud is proposed which contains clay, water, water output reducer, pH regulator, viscosity reducer and hydrogen sulfide absorber. In order to improve the absorbing capacity of the drilling mud with pH 8-11 and simultaneously preservation of the technological properties of the mud, it contains as the absorber of hydrogen sulfide pyrite cinders with the following ratio of components, % by mass: clay 5.0-35.0; water output reducer 0.2-2.0; pH regulator 0.05-0.25; viscosity reducer 0.1-1.0; pyrite cinders 0.5-4.0; water--the rest.

Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae.

Science.gov (United States)

Jongedijk, Esmer; Cankar, Katarina; Ranzijn, Jorn; van der Krol, Sander; Bouwmeester, Harro; Beekwilder, Jules

2015-01-01

Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a (+)-limonene synthase from Citrus limon. Both proteins were expressed either with their native plastid targeting signal or in a truncated form in which the plastidial sorting signal was removed. The yeast host strain for expression was AE9 K197G, which expresses a mutant Erg20 enzyme. This enzyme catalyses the formation of geranyl diphosphate, which is the precursor for monoterpenes. Several methods were tested to capture limonene produced by the yeast. Extraction from the culture medium by pentane, or by the addition of CaCl2 followed by solid-phase micro-extraction, did not lead to detectable limonene, indicating that limonene is rapidly lost from the culture medium. Volatile terpenes such as limonene may also be trapped in a dodecane phase added to the medium during fermentation. This method resulted in recovery of 0.028 mg/l (+)-limonene and 0.060 mg/l (-)-limonene in strains using the truncated Citrus and Perilla synthases, respectively. Trapping the headspace during culture of the limonene synthase-expressing strains resulted in higher titres, at 0.12 mg/l (+)-limonene and 0.49 mg/l (-)-limonene. These results show that the volatile properties of the olefins produced require specific methods for efficient recovery of these molecules from biotechnological production systems. Copyright © 2014 John Wiley & Sons, Ltd.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas

2017-09-25

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

High Temperature 300°C Directional Drilling System

Energy Technology Data Exchange (ETDEWEB)

Chatterjee, Kamalesh [Baker Hughes Oilfield Operations, Houston, TX (United States); Aaron, Dick [Baker Hughes Oilfield Operations, Houston, TX (United States); Macpherson, John [Baker Hughes Oilfield Operations, Houston, TX (United States)

2015-07-31

Many countries around the world, including the USA, have untapped geothermal energy potential. Enhanced Geothermal Systems (EGS) technology is needed to economically utilize this resource. Temperatures in some EGS reservoirs can exceed 300°C. To effectively utilize EGS resources, an array of injector and production wells must be accurately placed in the formation fracture network. This requires a high temperature directional drilling system. Most commercial services for directional drilling systems are rated for 175°C while geothermal wells require operation at much higher temperatures. Two U.S. Department of Energy (DOE) Geothermal Technologies Program (GTP) projects have been initiated to develop a 300°C capable directional drilling system, the first developing a drill bit, directional motor, and drilling fluid, and the second adding navigation and telemetry systems. This report is for the first project, “High Temperature 300°C Directional Drilling System, including drill bit, directional motor and drilling fluid, for enhanced geothermal systems,” award number DE-EE0002782. The drilling system consists of a drill bit, a directional motor, and drilling fluid. The DOE deliverables are three prototype drilling systems. We have developed three drilling motors; we have developed four roller-cone and five Kymera® bits; and finally, we have developed a 300°C stable drilling fluid, along with a lubricant additive for the metal-to-metal motor. Metal-to-metal directional motors require coatings to the rotor and stator for wear and corrosion resistance, and this coating research has been a significant part of the project. The drill bits performed well in the drill bit simulator test, and the complete drilling system has been tested drilling granite at Baker Hughes’ Experimental Test Facility in Oklahoma. The metal-to-metal motor was additionally subjected to a flow loop test in Baker Hughes’ Celle Technology Center in Germany, where it ran for more than 100

HORIZONTAL WELL DRILL-IN FLUIDS

Directory of Open Access Journals (Sweden)

Nediljka Gaurina-Međimurec

1998-12-01

Full Text Available Main objective of horizontal driling is to place a drain-hole for a long distance within the pay zone to enhance productivity or injectivity. In drilling horizontal wells, more serious problems appear than in drilling vertical wells. These problems are: poor hole cleaning, excessive torque and drag, hole filling, pipe stucking, wellbore instability, loss of circulation, formation damage, poor cement job, and difficulties at logging jobs. From that reason, successful drilling and production of horizontal well depends largely on the fluid used during drilling and completion phases. Several new fluids, that fulfill some or all of required properties (hole cleaning, cutting suspension, good lubrication, and relative low formation damage, are presented in this paper.

30 CFR 250.1605 - Drilling requirements.

Science.gov (United States)

2010-07-01

... deposit. (2) Inclinational surveys shall be obtained on all vertical wells at intervals not exceeding 1... to that leaseholder. (f) Fixed drilling platforms. Applications for installation of fixed drilling... removed or have been otherwise immobilized are classified as fixed bottom founded drilling platforms. (g...

Milton Hydro's Energy Drill Program : demand response based on behavioural responses to price signals

International Nuclear Information System (INIS)

Thorne, D.; Heeney, D.

2006-01-01

The Energy Drill Program is a demand response tool and economic instrument based on a fire drill protocol. The aim of the program is to reduce peak demand and emissions and improve system reliability and price volatility. This presentation provided details of an Energy Drill pilot program, conducted in Milton, Ontario. Customized approaches were used in the buildings partaking in the drill, which included the Milton Hydro Headquarters, the Robert Baldwin Public School, and a leisure centre. Building assessments inventoried building systems and equipment usage patterns. Pilot monitoring and evaluation was conducted through the use of checklists completed by marshals and building coordinators. Energy use data was tracked by Milton Hydro, and report cards were sent after each drill. A short-term drop in demand was observed in all the buildings, as well as overall reductions in peak period demand. Energy consumption data for all the buildings were provided. Results of the pilot program suggested that rotating the drills among participating buildings may prove to be a more effective strategy for the program to adopt in future. A greater emphasis on energy efficiency was also recommended. It was concluded that the eventual roll-out strategy should carefully consider the number and types of buildings involved in the program; internal commitment to the program; available resources; and timing for implementation. refs., tabs., figs

Device for storing drilling pipes

Energy Technology Data Exchange (ETDEWEB)

Kolasinski, A; Wedrychowicz, J

1981-02-16

The patented device contains a profiled arch 14 (see figure) installed in the upper part of the drilling rig 15. On base 16 of the drilling unit, there is bin 1 which is installed on frame 2 to which it is hinge connected with the help of pin 3. On the other side, the bin rests on rollers 4 which are attached to lever 5 of lifting mechanism 6. Bin 1 is a series of parallel-arranged guides rigidly connected by transverse beams. Frame 2 contains the collapsible support 10. During operation of the device, the hydraulic lifter 6 with the help of frame 5 and rollers 4 lifts bin 1 with drilling pipes installed on it, giving it an angle of 4/sup 0/ in relation to the plane of frame 2. The collapsible support 10 is installed in a vertical position and holds bin 1. This position of bin 1 is the most suitable for movement of the vertically installed drilling pipes on the guides. The distinguishing feature of the patented device is the possibility of convenient arrangement of the drilling pipes on the guides of bin 1. Because of this, the time spent on lifting and lowering the drill apparatus is considerably reduced.

Rock melting technology and geothermal drilling

Science.gov (United States)

Rowley, J. C.

1974-01-01

National awareness of the potential future shortages in energy resources has heightened interest in exploration and utilization of a variety of geothermal energy (GTE) reservoirs. The status of conventional drilling of GTE wells is reviewed briefly and problem areas which lead to higher drilling costs are identified and R and D directions toward solution are suggested. In the immediate future, an expanded program of drilling in GTE formations can benefit from improvements in drilling equipment and technology normally associated with oil or gas wells. Over a longer time period, the new rock-melting drill bits being developed as a part of the Los Alamos Scientific Laboratory's Subterrene Program offer new solutions to a number of problems which frequently hamper GTE drilling, including the most basic problem - high temperature. Two of the most favorable characteristics of rock-melting penetrators are their ability to operate effectively in hot rock and produce glass linings around the hole as an integral part of the drilling process. The technical advantages to be gained by use of rock-melting penetrators are discussed in relation to the basic needs for GTE wells.