DOCSLIB.ORG

View U.S. Patent No. 10207960 in PDF

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
View U.S. Patent No. 10207960 in PDF I 1111111111111111 1111111111 1111111111 111111111111111 11111 111111111111111111 USO 10207960B2 c12) United States Patent (IO) Patent No.: US 10,207,960 B2 Dumesic et al. (45) Date of Patent: Feb.19,2019 (54) SELECTIVE CATALYTIC PRODUCTION OF (56) References Cited LINEAR ALPHA OLEFINS FROM LACTONES AND UNSATURATED U.S. PATENT DOCUMENTS CARBOXYLIC ACIDS 4,996,384 A * 2/1991 Pelrine et al. ................ 585/530 5,004,815 A 4/1991 Danheiser et al. (71) Applicant: Wisconsin Alumni Research 5,164,497 A * 11/1992 King ........................ B0lJ 21/02 Foundation, Madison, WI (US) 544/177 8,003,818 B2 8/2011 Van Den Brink et al. (72) Inventors: James Anthony Dumesic, Verona, WI 8,410,326 B2 * 4/2013 Dumesic et al. ............. 585/327 (US); Dong Wang, Madison, WI (US); 2010/0312028 Al 12/2010 Olson et al. 2011/0172476 Al* 7/2011 Dumesic et al. ............. 585/324 Sikander Hussain Hakim, Madison, 2012/0035403 Al* 2/2012 Flytzani-Stephanopoulos . WI (US); David Martin Alonso, C07C 1/2078 Madison, WI (US) 585/240 (73) Assignee: Wisconsin Alumni Research OTHER PUBLICATIONS Foundation, Madison, WI (US) Levin, I.; Brandon, D. "Metastable Alumina Polymorphs: Crystal ( *) Notice: Subject to any disclaimer, the term ofthis Structures and Transition Sequences". J. Am. Ceram. Soc., 81, patent is extended or adjusted under 35 (1998). pp. 1995-2012.* U.S.C. 154(b) by 875 days. (Continued) (21) Appl. No.: 13/928,811 Primary Examiner - In Suk C Bullock (22) Filed: Jun. 27, 2013 Assistant Examiner - Aaron W Pierpont (74) Attorney, Agent, or Firm - Joseph T. Leone, Esq.; (65) Prior Publication Data DeWitt LLP US 2015/0005558 Al Jan. 1, 2015 (57) ABSTRACT (51) Int. Cl. C07C 1100 (2006.01) Described is a method to make linear alpha olefins. The C07C 11207 (2006.01) method includes the steps of contacting a feedstock having (52) U.S. Cl. a lactone and/or an unsaturated carboxylic acid with a solid CPC ........ C07C 112078 (2013.01); C07C 2521/04 acid catalyst having acidic catalytic sites including Lewis (2013.01); C07C 2521/12 (2013.01); C07C acid catalytic sites, for a time and a temperature wherein at 2523/30 (2013.01) least a fraction of the lactone and/or unsaturated carboxylic (58) Field of Classification Search acid present in the feedstock is converted into a linear alpha CPC ... C07C 1/20; C07C 2529/85; C07C 2529/40; olefin. The method may optionally take place in the presence C07C 1/22; C07C 1/2078; B0lJ 29/85; of water. The solid acid catalyst should preferably have at Cl0G 3/00 least 50% Lewis acid catalytic sites. USPC ................ 585/640, 324, 251, 242, 638, 500 See application file for complete search history. 34 Claims, 1 Drawing Sheet ,-Al,0, 100% 80% 60% 40% 20% 0% WHSV 1.83 h'' 0.37 h·' 0.18 h 1 E2Z::J Total butene yield f::,:,:,:,:,:,:,, 1-butene % in total butene US 10,207,960 B2 Page 2 (56) References Cited Mahrwald, R., vol. 1: Enolates, Organocatalysis, Biocatalysis and Natural Product Synthesis, Modern Aldo! Reactions, WILEY-VCR 2004. OTHER PUBLICATIONS Nexant Chemical Systems, Alpha Olefins(02/03-4) PERP Report, 2004. Bardin et al. ( 1998) Acidity of Keggin-Type Heteropolycompounds Nikolau, B.J. et al., Platform biochemical for a biorenewable chemical industry, The Plant Journal, 2008, 54, 536-545. Evaluated by Catalytic Probe Reactions, Sorption Microcalorimetry Shanks, B.H., Unleashing Biocatalysis/Chemical Catalysis Syner­ and Density Functional Quantum Chemical Calculations, J of gies for Efficient Biomass Conversion, ACS Chem. Biol., 2007, 2, Physical Chemistry B, 102:10817-10825. 533-535. Bond, J.Q. et al., Integrated Catalytic Conversion ofy-Valerolactone Soled, S.L. et al., Comparison of the Acidities of WOsf Al2 O3 and to Liquid Alkenes for Transportation Fuels, Science, 2010, 327, Ultrastable Faujasite Catalysts. J Cata!., 1988, 111, 286-295. 1110-1114. Van Der Klis, F. et al., Renewable linear alpha olefins by selective ethenolysis of decarboxylated unsaturated fatty acids, Eur. J Lipid Bond, J.Q. et al., y-Valerolactone Ring-Opening and Decarboxylation Sci. Technol., 2012, 114, 911-918. over SiO/Al O in the Presence of Water, Langmuir, 2010, 26, 2 3 Voge, H.H., Isomerization Equilibria among the n-Butenes, J Am. 16291-16298. Chem. Soc., 1946, 68, 550-553. Bond, J.Q. et al., Interconversion between y-valerolactone and Vogt, D., Oligomerization of Ethylene to Higher Linear a-Olefins, pentenoic acid combined with decarboxylation to form butane over Applied Homogeneous Catalysis With Organometallic Compounds silica/alumnia, J Cata!., 2011, 281, 290-299. 1996, vol. 1, pp. 245-258. Corma, A., Inorganic Solid Acids and Their Use in Acid-Catalyzed Weissermel, K., Industrial Organic Chemistry, 1997 (Book----Copy Hydrocarbon Reactions, Chem. Rev.(Washington, DC, U.S.), 1995, not provided). 95, 559-614. Roman-Leshkov, Y., et al., Activation of Carbonyl-Containing Mol­ Emeis, C.A., Determination of Integrated Molar Extinction Coef­ ecules with Solid Lewis Acids in Aqueous Media, ACS Cata!., 2011, ficients for Infrared Absorption Bands of Pyridine Adsorbed on 1, 1566-1580. Solid Acid Catalysts, J Cata!. 1993, 141, 347-354. Wang, D., et al., A highly selective route to linear alpha olefins from Gielgens, L. H. et al., Skeletal Isomerisation of 1-Butene on biomass-derived lactones and unsaturated acids, Chem. Commun., Tungsten Oxide Catalysts, J Cata!., 1995, 154, 201-207. 2013, 49, 7040-7042. Kraus, G.A. et al., A Large-Scale Synthesis of a-Olefins and a, rn -Dienes, Synthesis, 2012, 44, 3003-3005. * cited by examiner U.S. Patent Feb.19,2019 US 10,207,960 B2 100% 100% 80% 80% 60% 60% 40% 40% 20% 20% 0% 0% WHSV 21.6 h·1 1.83 h· 1 0.18 h· 1 WHSV 1.83 h·1 0.37 h· 1 0.18 h· 1 C2ZZJ Total butene yield !t:tltM 1-butene % in total butene FIG.1 FIG. 2 US 10,207,960 B2 1 2 SELECTIVE CATALYTIC PRODUCTION OF 1996, vol. 1, pp. 245-258. Short-chain LAOs (C4 -C8 ) are LINEAR ALPHA OLEFINS FROM used as co-monomers for producing high-density polyeth­ LACTONES AND UNSATURATED ylene (HDPE) and linear low-density polyethylene (LL­ CARBOXYLIC ACIDS DPE). Longer chain-length LAOs are used as precursors to 5 detergents (C12-C14), synthetic oils and plasticizers (C 6 - STATEMENT REGARDING FEDERALLY C10), and specialty chemicals such as oilfield fluids (C1c SPONSORED RESEARCH OR DEVELOPMENT C18). Id. The linearity of LAOs leads to products with desirable mechanical properties, such as increased flexibil­ This invention was made with government support under ity, and strength, and advantages such as biodegradability. DE-FCO2-07ER64494 awarded by the US Department of 1° K. Weissermel and H.-J. Arpe, Industrial Organic Chemis­ Energy and 0813570 awarded by the National Science try, 1997. The annual global demand for LAO (C4 -C20J was Foundation. The government has certain rights in the inven­ approximately 3 .4 million metric tons at the end of 2002 and tion. has been growing rapidly. Alpha Olefins(02/03-4) PERP 15 Report, Nexant Chemical Systems, 2004. CROSS-REFERENCE TO RELATED The production of LAOs is inherently challenging due to APPLICATIONS the ease of migration of the terminal double bond to internal positions. LAOs are conventionally manufactured from fos­ Not applicable. sil fuel feedstocks by two main routes, oligomerization of 20 ethylene and cracking of Fischer-Tropsch products. K. Weis­ THE NAMES OF PARTIES TO A JOINT sermel and H.-J. Arpe, Industrial Organic Chemistry, 1997. RESEARCH AGREEMENT These processes necessarily lead to a distribution of LAOs Not applicable. with different chain lengths. Moreover, LAOs with odd carbon numbers cannot be produced by direct ethylene INCORPORATION-BY-REFERENCE OF 25 oligomerization. In addition, current processes overwhelm­ MATERIAL SUBMITTED ON A COMPACT ingly rely on fossil carbon and thus are not sustainable. In DISC OR AS A TEXT FILE VIA THE OFFICE this regard, the development of a process to produce LAOs ELECTRONIC FILING SYSTEM (EFS-WEB) from renewable feedstocks has become of wide interest. For instance, a process has been demonstrated for LAO produc- Not applicable. 30 tion by decarbonylation/dehydration of fatty acids over homogenous catalysts based on Pd. G. A. Kraus and S. STATEMENT REGARDING PRIOR Riley, Synthesis, 2012, 44, 3003-3005. Another process DISCLOSURES BY THE INVENTOR OR A involves silver (II) mediated decarboxylation of fatty acids JOINT INVENTOR followed by ethenolysis over a commercial metathesis cata- 35 lyst to produce renewable LAOs. F. van der Klis, J. Le Not applicable. Notre, R. Blaauw, J. van Haveren and D.S. van-Es, Eur. J. Lipid Sci. Technol., 2012, 114, 911-918. However, these BACKGROUND OF THE INVENTION processes require using expensive homogeneous catalysts. Not only are the catalysts prohibitively expensive, because Field of the Invention 40 they are homogeneous, they are difficult to separate and recycle from the product stream. Thus there remains a Disclosed herein is a method to make linear alpha-olefins. long-felt and unmet need to produce LAOs cheaply and from renewable feedstocks. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98 45 BRIEF SUMMARY OF THE INVENTION The use of biomass feedstocks is central to satisfy the Disclosed herein is a process to convert hydroxy carbox­ long-term need for carbon-based commodity chemicals in a ylic acids, unsaturated carboxylic acids and lactones (Cn) sustainable manner. A promising strategy for converting obtained from renewable sources such as biomass to pro- biomass-derived carbohydrates to value-added chemicals is 50 duce linear alpha olefins (LAOs) (Cn_ 1 ) by selective decar­ to take advantage of synergies between the high chemo- and boxylation. The method uses inexpensive, robust heteroge­ stereo-selectivity of biocatalysis and the high efficiency of neous solid acid catalysts, and can use as a feedstock a wide chemical catalysis.
Load more

Recommended publications
  • US5523508.Pdf
    |||||I|| US005523508A United States Patent (19) 11 Patent Number: 5,523,508 Krawczyk et al. 45) Date of Patent: Jun. 4, 1996 (54) PROCESS FOR LINEAR ALPHA-OLEFIN 4,689,437 8/1987 Murray ... ... 585/526 PRODUCTION: ELMINATING WAX 4,716,138 12/1987 Murray ... ... 502/117 PRECIPITATION 4,822,915 4/1989 Murray ...................................... 568/13 4,879,428 11/1989 Harandi et al. ......................... 585/533 75) Inventors: Mark A. Krawczyk, Chicago; Richard OTHER PUBLICATIONS E. Marinangeli; R. Joe Lawson, both of Arlington Heights, all of Ill. Ullman's Encyclopedia of Industrial Chemistry, 5th Ed., V. A13, pp. 245 et. ff., VCH (1989). (month unknown). 73) Assignee: UOP, Des Plaines, Ill. Primary Examiner–Shrive Beck Assistant Examiner-Timothy H. Meeks (21) Appl. No.: 366,153 Attorney, Agent, or Firm-Thomas K. McBride; Eugene I. 22 Filed: Dec. 29, 1994 Snyder (51} int. Cl. ............................................. CO7C 2/24 57 ABSTRACT 52 U.S. Cl. ... - - 585/523; 585/315; 585/316; Linear alpha-olefin formation via oligomerization of ethyl 585/329; 585/522; 585/526; 585/527 ene using transition metal catalysis leads to a Schultz-Flory 58) Field of Search ..................................... 585/315, 316, distribution of oligomers. At modest temperatures formation 585/329, 522, 523, 526, 527 of heavy oligomers which are waxy solids only partly soluble in the LAO product mix causes reactor plugging and I56) References Cited curtailing the time of continuous runs. Recycling a portion U.S. PATENT DOCUMENTS of a lighter oligomeric fraction obviates this problem and 3,641,191 2/1972 Fernald et al.................... 260/683.150 permits runs uninterrupted by solids formation.
    [Show full text]
  • Alfa Olefins Cas N
    OECD SIDS ALFA OLEFINS FOREWORD INTRODUCTION ALFA OLEFINS CAS N°:592-41-6, 111-66-0, 872-05-9, 112-41-4, 1120-36-1 UNEP PUBLICATIONS 1 OECD SIDS ALFA OLEFINS SIDS Initial Assessment Report For 11th SIAM (Orlando, Florida, United States 1/01) Chemical Name: 1-hexene Chemical Name: 1-octene CAS No.: 592-41-6 CAS No.: 111-66-0 Chemical Name: 1-decene Chemical Name: 1-dodecene CAS No.: 872-05-9 CAS No.: 112-41-4 Chemical Name: 1-tetradecene CAS No.: 1120-36-1 Sponsor Country: United States National SIDS Contract Point in Sponsor Country: United States: Dr. Oscar Hernandez Environmental Protection Agency OPPT/RAD (7403) 401 M Street, S.W. Washington, DC 20460 Sponsor Country: Finland (for 1-decene) National SIDS Contact Point in Sponsor Country: Ms. Jaana Heiskanen Finnish Environment Agency Chemicals Division P.O. Box 140 00251 Helsinki HISTORY: SIDS Dossier and Testing Plan were reviewed at the SIDS Review Meeting or in SIDS Review Process on October 1993. The following SIDS Testing Plan was agreed: No testing ( ) Testing (x) Combined reproductive/developmental on 1-hexene, combined repeat dose/reproductive/developmental on 1-tetradecene and acute fish, daphnid and algae on 1- tetradecene. COMMENTS: The following comments were made at SIAM 6 and have been incorporated in this version of the SIAR: 2 UNEP PUBLICATIONS OECD SIDS ALFA OLEFINS 1. The use of QSAR calculations for aquatic toxicity, 2. More quantitative assessment of effects; and 3. Provide more details for each endpoint. The following comments were made at SIAM 6, but were not incorporated into the SIAR for the reasons provided: 1.
    [Show full text]
  • Wide Range Linear Alpha Olefin Processes
    IHS Chemical Process Economics Program Consolidated Report CR001 Wide Range Linear Alpha Olefin Processes By Marianna Asaro July 2014 ihs.com/chemical IHS Chemical Process Economics Program Consolidated Report | CR001 IHS Chemical agrees to assign professionally qualified personnel to the preparation of the Process Economics Program’s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither IHS Chemical nor its employees will assume any liability for the special or consequential damages arising from the Client’s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold IHS Chemical, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client’s use of the reports or other deliverables produced by IHS Chemical pursuant to this agreement. For detailed marketing data and information, the reader is referred to one of the IHS Chemical programs specializing in marketing research. The IHS CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced throughout the world. In addition the IHS DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Europe, East Asia, China, India, South & Central America, the Middle East & Africa, Canada, and Mexico. July 2014 ii © 2014 IHS IHS Chemical Process Economics Program Consolidated Report | CR001 PEP Report CR001 Wide Range Linear Alpha Olefin Processes By Marianna Asaro July 2014 Abstract This report consolidates and updates the Process Economics Program’s technical and economic analyses of wide-range linear alpha olefins (LAO) manufacturing technologies since PEP first reported on the subject in the 1960s.
    [Show full text]
  • United States Patent (19) 11 3,968,133 Knifton (45) July 6, 1976
    United States Patent (19) 11 3,968,133 Knifton (45) July 6, 1976 54 CARBOXYLATION PROCESS FOR 3,723,486 3/1973 Kajimoto...................... 260/410.9 R PREPARING LINEAR FATTY ACDS OR 3,776,929 12/1973 Mrowca....................... 260/410.9 R ESTERS 3,819,669 6/1974 Knifton........................ 260/410.9 R 3,832,391 8/1974 Parshall........................ 260/410.9 R (75) Inventor: John F. Knifton, Poughouag, N.Y. Primary Examiner-Patrick P. Garvin 73 Assignee: Texaco Inc., New York, N.Y. Assistant Examiner-John F. Niebling 22) Filed: Nov. 25, 1974 Attorney, Agent, or Firm-T. H. Whaley; C. G. Ries; (21) Appl. No.: 526,867 Bernard Marlowe 52) U.S. C. ......................... 260/410.9 R; 260/413; 57 ABSTRACT 260/497 A; 260/488 K; 260/491; 260/.532; This invention concerns a process for preparing linear 260/533 A fatty (carboxylic) acids and esters from the reaction of 51 Int. Cl’............................................ C11C 3/02 olefins, alcohols (or water) and carbon monoxide. The (58) Field of Search......... 260/410.9 R, 413, 497 A, process is catalyzed by catalytic amounts of disper 260/488 K, 491, 532,533 A sions of ligand-stabilized, palladium(II) halide com plexes, in quaternary ammonium, phosphonium or ar 56 References Cited sonium salts of trihalostannate(II) or trihaloger UNITED STATES PATENTS manate(II). These empirically selected palladium cata 3,437,676 4/1969 Kutepow...................... 260/410.9 R lysts can be recycled with fresh olefin feed several 3,530, 155 9/1970 Fenton......................... 260/410.9 R times before substantial loss of catalytic activity is 3,530,168 9/1970 Biale.....
    [Show full text]
  • Process Economics Program (PEP): Wide Range Linear Alpha Olefin Processes & On-Purpose Linear Alpha Olefin Processes PEP CR001 & CR002 Prospectus
    IHS CHEMICAL Process Economics Program (PEP): Wide Range Linear Alpha Olefin Processes & On-Purpose Linear Alpha Olefin Processes PEP CR001 & CR002 Prospectus IHS CHEMICAL PROSPECTUS PEP CR001 & CR002 Contents Contents ..................................................................................................................................... 2 Introduction ................................................................................................................................ 3 Abstract ...................................................................................................................................... 5 Key Questions Addressed in the Reports .................................................................................. 6 Deliverables ............................................................................................................................... 6 Process Technologies Reviewed in CR001 & CR002 ................................................................ 6 Table of Contents ....................................................................................................................... 7 CR001 - Wide Range Linear Alpha Olefin Processes ................................................................ 7 CR002 - On-Purpose Linear Alpha Olefin Processes .............................................................. 10 Meet the Author........................................................................................................................ 15 About the IHS Chemical Process
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 6,787,576 B2 Kiss Et Al
    USOO6787576B2 (12) United States Patent (10) Patent No.: US 6,787,576 B2 Kiss et al. (45) Date of Patent: Sep. 7, 2004 (54) LINEAR ALPHAOLEFINS FROM NATURAL 5,210,060 A 5/1993 Radlowski et al. ......... 502/202 GAS-DERVED SYNTHESIS GAS OVERA 5.248,701 A 9/1993 Soled et al. ................ 518/700 NONSHIFTING COBALT CATALYST 6,166.262 A 12/2000 Connor ....................... 568/460 (75) Inventors: Gabor Kiss, Hampton, NJ (US); Rocco FOREIGN PATENT DOCUMENTS Anthony Fiato, Basking Ridge, NJ GB 21696.14 A 7/1986 ............. CO7C/1/04 (US); Frank Hershkowitz, Liberty JP 61O18433 A 1/1986 ............ B01J/21/16 Corner, NJ (US); David Chester Long, NL 7712952 A 5/1979 ............ BO1J/23/74 Ashburn, VA (US) OTHER PUBLICATIONS (73) Assignee: ExxonMobil Research and R. Madon et al., “Primary and Secondary Reaction Path Engineering Company, Annandale, NJ ways in Ruthenium-Catalyzed Hydrocarbon Synthesis”, (US) The Journal of Physical Chemistry, 1991, 95, pp. 7795-7804. (*) Notice: Subject to any disclaimer, the term of this E. Iglesia et al., “Transport-Enhanced C-Olefin Readsorp patent is extended or adjusted under 35 tion Pathways in Ru-Catalyzed Hydrocarbon Synthesis', U.S.C. 154(b) by 0 days. Journal of Catalysis, vol. 129, pp. 238-256 (1991). R. J. Madon et al., “Non-Flory Product Distributions in (21) Appl. No.: 10/330,860 Fischer-Tropsch Synthesis Catalyzed by Ruthenium, Cobalt, and Iron”, ACS Symposium Series Selectivity in (22) Filed: Dec. 27, 2002 Catalysis, Editors: M. E. Davis and S. L. Suib, New York, (65) Prior Publication Data Aug. 25–30, 1991.
    [Show full text]
  • Linear Alpha-Olefins (681.5030)
    IHS Chemical Chemical Economics Handbook Linear alpha-Olefins (681.5030) by Elvira O. Camara Greiner with Yoshio Inoguchi Sample Report from 2010 November 2010 ihs.com/chemical November 2010 LINEAR ALPHA-OLEFINS Olefins 681.5030 B Page 2 The information provided in this publication has been obtained from a variety of sources which SRI Consulting believes to be reliable. SRI Consulting makes no warranties as to the accuracy completeness or correctness of the information in this publication. Consequently SRI Consulting will not be liable for any technical inaccuracies typographical errors or omissions contained in this publication. This publication is provided without warranties of any kind either express or implied including but not limited to implied warranties of merchantability fitness for a particular purpose or non-infringement. IN NO EVENT WILL SRI CONSULTING BE LIABLE FOR ANY INCIDENTAL CONSEQUENTIAL OR INDIRECT DAMAGES (INCLUDING BUT NOT LIMITED TO DAMAGES FOR LOSS OF PROFITS BUSINESS INTERRUPTION OR THE LIKE) ARISING OUT OF THE USE OF THIS PUBLICATION EVEN IF IT WAS NOTIFIED ABOUT THE POSSIBILITY OF SUCH DAMAGES. BECAUSE SOME STATES DO NOT ALLOW THE EXCLUSION OR LIMITATION OF LIABILITY FOR CONSEQUENTIAL OR INCIDENTAL DAMAGES THE ABOVE LIMITATION MAY NOT APPLY TO YOU. IN SUCH STATES SRI CONSULTING’S LIABILITY IS LIMITED TO THE MAXIMUM EXTENT PERMITTED BY SUCH LAW. Certain statements in this publication are projections or other forward-looking statements. Any such statements contained herein are based upon SRI Consulting’s current knowledge and assumptions about future events including without limitation anticipated levels of global demand and supply expected costs trade patterns and general economic political and marketing conditions.
    [Show full text]
  • Metallocene Polyalpha Olefins (Mpaos) Process Economics Program Report 296
    ` IHS CHEMICAL Metallocene Polyalpha Olefins (mPAOs) Process Economics Program Report 296 December 2016 ihs.com PEP Report 296 Metallocene Polyalpha Olefins (mPAOs) Gajendra Kumar Principal Analyst Tony Pavone Sr. Principal Analyst Downloaded 20 December 2016 10:10 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 296 Metallocene Polyalpha Olefins (mPAOs) PEP Report 296 Metallocene Polyalpha Olefins (mPAOs) Gajendra Kumar, Principal Analyst Tony Pavone, Sr. Principal Analyst Abstract Polyalpha olefins (PAOs) represent a family of primarily decene-1 oligomers (mostly trimers) that have found wide use as a fully synthetic lubricant base oil component. PAOs provide superior lubricant properties in viscosity, viscosity index, cold cranking capability, emulsion resistance, lower pour point, lubricity, friction reduction, low volatility in use, higher flash temperature, and thermal and oxidative stability. The downside is lower solvency and biodegradation, poorer seal swell, and higher cost. The American Petroleum Institute (API) designates PAO components as Group-4 fully synthetic basestock. Periodic shortages in decene-1 LAO (linear alpha olefin) feedstock availability have forced PAO producers to occasionally blend C10 with both lighter (C8) and heavier (C12) LAO feedstocks to produce PAO with adequate physical and performance properties. The oligomerization process is not very selective, and produces a reactor product containing LAO dimers, trimers, tetramers, and pentamers, plus unreacted feedstock. While originally developed to produce fully synthetic basestock for conventional motor oil requiring 4 centistoke (cSt) viscosity, additional product grades with different viscosities have been supplemented with newer PAO components of much higher viscosity (100+ cSt) that have found widespread use as blend stock components in heavy duty gear boxes, transfer cases, and transmissions, such as those found in wind turbine generators.
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,961,775 B2 Joshi Et Al
    US008961775B2 (12) United States Patent (10) Patent No.: US 8,961,775 B2 Joshi et al. (45) Date of Patent: Feb. 24, 2015 (54) HIGH PRODUCTIVITY KOLBE REACTION (2013.01): CI0G 3/42 (2013.01): CI0G 3/44 PROCESS FORTRANSFORMATION OF (2013.01): CI0G 3/48 (2013.01); C25B 3/10 FATTY ACDS DERVED FROM PLANT OIL (2013.01): CI0G 45/58 (2013.01): CI0G 45/64 AND ANIMAL EAT (2013.01); Y02T 50/678 (2013.01); Y02E 50/13 (2013.01); C07C 2521/04 (2013.01); C07C (71) Applicant: Altranex Corporation, Scarborough 2521/08 (2013.01); C07C2523/28 (2013.01); (CA) (Continued) (72) Inventors: Chandrashekhar H. Joshi, Kingston (58) Field of Classification Search (CA); Graham Thomas Thornton USPC ............................... 585/1: 205/413, 415, 462 Gibson, Kingston (CA); Dzmitry See application file for complete search history. Malevich, Kingston (CA); Michael (56) References Cited Glenn Horner, West Roxbury, MA (US) U.S. PATENT DOCUMENTS (73) Assignee: Altranex Corporation (CA) 4,018,844 A 4, 1977 MereSZ et al. (*) Notice: Subject to any disclaimer, the term of this 7,198,710 B2 4/2007 Miller et al. patent is extended or adjusted under 35 (Continued) U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 14/331,390 B.C.L. Weedon, "Anodic Syntheses With Carboxylic Acids,” Quar (22) Filed: Jul. 15, 2014 terly Reviews of Chemical Society, 1952, vol. 6 pp. 380-398. (Continued) (65) Prior Publication Data US 2014/O323784 A1 Oct. 30, 2014 Primary Examiner — Ellen McAvoy (74) Attorney, Agent, or Firm — American Patent Agency Related U.S.
    [Show full text]
  • Selective Production of Bio-Based Linear Alpha-Olefin from Wasted
    polymers Article Selective Production of Bio-Based Linear Alpha-Olefin from Wasted Fatty Alcohol on Al2O3 for Bio-Based Chemicals Hye-Jin Lee 1,2, Il-Ho Choi 1 , Seung-Wook Kim 2 and Kyung-Ran Hwang 1,* 1 Energy Resource Upcycling Research Laboratory, Korea Institute of Energy Research, Daejeon 34129, Korea; [email protected] (H.-J.L.); [email protected] (I.-H.C.) 2 Department of Chemical and Biological Engineering, Korea University, Seoul 136701, Korea; [email protected] * Correspondence: [email protected]; Tel.: +82-42-860-3504 Abstract: The catalytic dehydration of a bio-based fatty alcohol was performed using Al2O3 prepared by solvothermal synthesis for selective production of long-chain linear-alpha-olefins (LAO). The effect of the synthesis temperature of alumina precursors on the dehydration of 1-octadecanol (C18H38O) was examined based on the textural properties and Lewis acid–base properties of the catalysts. Amorphous alumina synthesized at 325 ◦C showed the highest surface area (233.07 m2/g) and total pore volume (1.237 cm3/g) among the catalysts and the best dehydration results: 93% conversion, 62% selectivity of 1-octadecene (C18H36), and 89% LAO purity. This was attributed to the increased Al/O ratio and atomic concentration of surface O in alumina, which were important factors in the catalytic dehydration of 1-octadecanol through the synergistic catalysis of acid–base pairs. The produced bio-based LAO can be key intermediates for synthesis of oxo alcohols and poly-alpha-olefins, as alternatives to petroleum-based LAO to achieve carbon neutrality in chemical industry.
    [Show full text]
  • Light Linear Alpha Olefin Market Study
    IHS CHEMICAL Light Linear Alpha Olefin Market Study Special Report Prospectus IHS CHEMICAL Contents Contents ..................................................................................................................................... 2 Introduction ................................................................................................................................ 3 Study Scope ............................................................................................................................... 5 Key Questions Addressed in the Study ...................................................................................... 7 Deliverables ............................................................................................................................... 8 Proposed Table of Contents ...................................................................................................... 9 Methodology ............................................................................................................................ 11 Study Team .............................................................................................................................. 15 Qualifications............................................................................................................................ 18 About IHS Chemical ................................................................................................................. 21 About IHS ................................................................................................................................
    [Show full text]
  • Light Linear Alpha Olefin Market Study
    Light Linear Alpha Olefin Market Study Chemical Strategic Report Prospectus Light Linear Alpha Olefin Market Study Light Linear Alpha Ole n Market Study Light Linear Alpha Ole n Market Study Contents Introduction The linear alpha olefin (“LAO”) business is complex, serving a broad range of industries and Introduction ............................................................................................. 3 applications therein from commodity plastics to small volume fine and performance chemicals. Study Scope ............................................................................................. 5 A simplified map of the LAO value chain is given below: Key Questions Addressed in the Study ............................................... 7 Deliverables .............................................................................................. 8 Alpha Olefins Supply Chain Proposed Table of Contents ................................................................. 9 Full Range Ethylene Polybutene-1 Processes Butene-1 Methodology .......................................................................................... 11 PE/PP Hexene-1 Study Team ............................................................................................ 15 Comnomer Dimerization Plasticizer Alcohols Qualifications ......................................................................................... 18 Octene-1 Polyolefin Elastomers Trimerization About Chemical at IHS Markit ............................................................. 21
    [Show full text]