WO2001027053A1 - Procede de dimerisation en plusieurs etapes - Google Patents

Procede de dimerisation en plusieurs etapes Download PDF

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Publication number
WO2001027053A1
WO2001027053A1 PCT/US2000/022930 US0022930W WO0127053A1 WO 2001027053 A1 WO2001027053 A1 WO 2001027053A1 US 0022930 W US0022930 W US 0022930W WO 0127053 A1 WO0127053 A1 WO 0127053A1
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WO
WIPO (PCT)
Prior art keywords
dimerization
isobutylene
isoalkene
zone
reaction
Prior art date
Application number
PCT/US2000/022930
Other languages
English (en)
Inventor
Michael H. Herron
Ramesh M. Rameswaran
Alan P. Woinsky
Original Assignee
Arco Chemical Technology, L.P.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arco Chemical Technology, L.P. filed Critical Arco Chemical Technology, L.P.
Priority to AU67935/00A priority Critical patent/AU6793500A/en
Publication of WO2001027053A1 publication Critical patent/WO2001027053A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08—Ion-exchange resins
    • C07C2531/10—Ion-exchange resins sulfonated

Definitions

  • the present invention relates to the dimerization of an isoalkene such as isobutene by a multistage dimerization process with intermediate product dimer separation.
  • a number of catalysts are known for this reaction including cold sulfuric acid, phosphoric acid on Kieselguhr, silica/alumina sometimes promoted with Ni, Co, Fe, Pt or Pd; activated natural clays plus activating substances such as ZnO metallic phosphates such as those of iron (III) and cerium optionally supported on carriers such as activated carbon, bauxite, activated carbon alone and with metal halides such as TiCfe heteropolyacids such as silicotungstic acid on silica gel and phosphomolybdic acid; BF 3 H 3 PO 3 ; dihydroxyfluroboric acid HF and fluorides or oxyfluorides of S, Se, N, P, Mo, Te, W, V and Si boiling below 300°C; BF 3 dimethyl ether complexes; BF 3 hydrocarbon complexes; BF 3 SO 2 ; and AICI 3 with catalysts such as dimethyl ether, HC1 , and nitromethane.
  • An especially preferred catalyst is a sulfonic acid-type ion exchange resin such as Amberlyst A-35.
  • a sulfonic acid-type ion exchange resin such as Amberlyst A-35.
  • U.S. Patent 4,447,668 describes isobutylene dimerization using A-35 with methyl t-butyl ether as solvent.
  • Isobutylene feed which illustratively is derived from tertiary butanol by dehydration or more preferably from a refinery fluid catalytic cracking C stream or olefin stream cracking plant derived C stream or C stream from dehydrogenation is fed via line 1 to dimerization zone 2 wherein isobutylene is dimerized. Also fed to zone 2 via line 3 is a tertiary butanol recycle stream, the tertiary butanol serving as a selectivity enhancing modifier during dimerization in especially preferred practice.
  • the isobutylene containing feed is contacted with a solid dimerization catalyst, preferably a sulfonic acid resin catalyst such as Amberlyst A-15 of Rohm & Haas at dimerization conditions whereby exceedingly high selectivity to dimer is achieved.
  • a solid dimerization catalyst preferably a sulfonic acid resin catalyst such as Amberlyst A-15 of Rohm & Haas at dimerization conditions whereby exceedingly high selectivity to dimer is achieved.
  • Reaction conditions including temperature, pressure, flow rate (space velocity) and the like are regulated so as to provide a maximum isobutylene conversion in zone 2 of 85%, preferably a maximum conversion of 60%. Usually conversion in the range 40 to 85% is suitable.
  • Packed column reactors with external cooling of a pump around stream can be used; also, packed tubes with an external cooling agent are also suitable.
  • reaction mixture is removed via line 4 from reactor 2 with a portion recycled via line 5 through heat exchanger 6 back to zone 2 via line 7.
  • the net reaction product mixture passes via line 8 to distillation column
  • reaction mixture is distilled to separate a heavy fraction comprised of diisobutylene product from lighter components of the reaction mixture including unreacted isobutylene.
  • lighter fraction passes via line
  • reaction zone 11 wherein the mixture is contacted at dimerization conditions with solid dimerization catalyst, preferably the same catalyst employed in reaction zone 2.
  • solid dimerization catalyst preferably the same catalyst employed in reaction zone 2.
  • conversion of isobutylene in the feed through line 10 preferably is 80% or more, and the reaction product mixture is removed via line 12 and passed to distillation zone 13. Reaction mixture recycle and cooling to control the exotherm in reactor 11 are also provided, these are not shown.
  • Product diisobutylene is removed from zone 13 via line 14 and is suitably combined with the similar product stream which is removed from zone 9 via line 15 and the combined stream is sent to such further treatment as might be appropriate such as hydrogenation to isooctane (not shown).
  • distillation zone 13 is illustrated as a single zone, it will be understood that a plurality of columns can be used which collectibily are represented by zone 13. Overhead from zone 13 representing unreacted C components of the feed is removed via line 16 for use in reactions such as alkylation or for fuel.
  • a tertiary butanol containing stream is removed from zone 13 via line 3 and is recycled to zone 2 with a purge being removed via line 17.
  • a particular feature of the process is that an azeotrope of tertiary butyl alcohol and diisobutylene having a composition by weight of about 60% tertiary butyl alcohol and 40% diisobutylene is removed from zone 13 via line 3 and recycled.
  • Improved overall selectivities are achieved at high overall isobutylene conversion by practice of the invention as compared to systems which call for high isobutylene conversion in a single step. It is essential not only that partial isobutylene conversion be achieved in the first reaction but that product diisobutylene formed in the first reaction be separated prior to subsequent isobutylene reaction in order that the advantages of the invention be realized. Of course, more than a series of two reaction zones can be employed with dimer separation between zones.
  • the dimerization reaction in the various reaction zones is carried out in accordance with known procedures such as those described in U.S. 5,877,372.
  • tertiary butyl alcohol by means of the Oxirane process is well known and widely practiced on an industrial scale. See, for example, U.S. 3,351 ,635.
  • dehydration of tertiary butanol to form isobutylene is well known as is the dehydrogentaiton of various C fractions. See, for example, U.S. Patents 5,625,109, 3,510,538, 4,165,343, and 4,155,945.
  • tertiary butanol in the dimerization of isobutylene in accordance with the present invention, can be employed as a selectivity enhancing modifier and this results in a substantial improvement in reaction selectivity to the dimer as compared to operation without this modifier.
  • Methyl tertiary butylene can similarly be used.
  • isoalkane such as isooctane or the like hydrocarbon can be employed as a diluent to further enhance reaction selectivity by reducing isobutylene feed concentration, and to aid in removal of the reaction exotherm although this is neither necessary nor preferred.
  • oligomerization catalysts and conditions can be employed in the several oligomerization steps. Suitable conditions include temperatures broadly in the range 0 to 200°C, preferably 10 to 120°C, and the use of pressures sufficient to maintain the liquid phase, illustratively above 250 psig, e.g. 50-500 psig.
  • Known dimerization catalysts can be used including those described in prior art such as U.S. 3,760,026.
  • the use of sulfonic acid type ion exchange resins such as Amberlyst A-15, Dowex 50 and the like is especially preferred.
  • a C 4 feed stream passes at the rate of 1000 Ibs/hr via line 1 to reactor 2.
  • the feed stream composition by volume is 40% isobutylene, 50% n-butenes, and 10% others.
  • Reactor 2 is a packed column reactor packed with Amberlyst A-35 catalyst.
  • the net reaction product mixture comprised by weight of 11% unreacted isobutylene, 46% n-butenes, 5% tertiary butyl alcohol, 29% diisobutylene, and 10% others passes via line 8 to distillation column 9.
  • An overhead stream is removed at 45°C and 70 psig and passes at the rate of 805 Ibs/hr via line 10 to reactor 11.
  • the composition by weight of this overhead stream is about 15% isobutylene, 63% n-butenes, 6% tertiary butyl alcohol, 4% isooctene, and 12% others.
  • a bottoms stream is removed via line 15 from distillation zone 9 at the rate of 280 Ibs/hr and comprises by weight 96% diisobutylene and 4% others, i.e trimer, crosspolymers and the like.
  • Reactor 11 is a packed column reactor containing A-35 catalyst also.
  • the isobutylene is dimerized at 100°C and 350 psig, feed liquid hourly space velocity is 2 hr "1 and isobutylene conversion therein is 80%.
  • the reaction mixture stream comprised by weight of 62% n-butenes, 3% isobutylene, 6% tertiary butyl alcohol, 16% diisobutylene and 13% others passes at the rate of 805 Ibs/hr to distillation column 13 wherein the reaction mixture is distilled.
  • An overhead stream is removed at 45°C and 70 psig via line 16 at the rate of 624 Ibs/hr.
  • This stream has the following composition by weight: 4% isobutylene, 80% n-C hydrocarbons, and 16% others and preferably passes to an alkylation zone (not shown). In this example, tertiary butyl alcohol is removed as sidedraw.
  • a sidestream azeotropic mixture comprised of tertiary butyl alcohol and diisobutylene is removed via line 3 and recycled to reactor 2 as above described.
  • a bottoms diisobutylene stream is removed at 185°C and 75 psig via line 14 at the rate of 181 Ibs/hr.
  • This stream comprises by weight 96% diisobutylene and 4% others, mainly higher polymer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de dimérisation d'un isoalcène (1) selon lequel l'isoalcène est soumis à une dimérisation dans une première zone de réaction (2) jusqu'à atteindre une conversion inférieure ou égale à environ 85 %, le dimère obtenu (8) est séparé dans une zone de séparation (9), et l'isoalcène n'ayant pas encore réagi (10) est soumis à une dimérisation supplémentaire dans au moins une zone de réaction suivante (11).
PCT/US2000/022930 1999-10-08 2000-08-21 Procede de dimerisation en plusieurs etapes WO2001027053A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU67935/00A AU6793500A (en) 1999-10-08 2000-08-21 Multistage dimerization process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41585799A 1999-10-08 1999-10-08
US09/415,857 1999-10-08

Publications (1)

Publication Number Publication Date
WO2001027053A1 true WO2001027053A1 (fr) 2001-04-19

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PCT/US2000/022930 WO2001027053A1 (fr) 1999-10-08 2000-08-21 Procede de dimerisation en plusieurs etapes

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AU (1) AU6793500A (fr)
WO (1) WO2001027053A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010118A1 (fr) * 2001-07-26 2003-02-06 Fortum Oyj Constituants de carburant et procedes de fabrication selective de ceux-ci
WO2003033442A1 (fr) * 2001-10-15 2003-04-24 Catalytic Distillation Technologies Recuperation d'un alcool butylique tertiare
JP2006176770A (ja) * 2004-12-16 2006-07-06 Uop Llc 単一分留カラムによる多段階オリゴマー化工法および装置
US7525002B2 (en) 2005-02-28 2009-04-28 Exxonmobil Research And Engineering Company Gasoline production by olefin polymerization with aromatics alkylation
US8395006B2 (en) 2009-03-13 2013-03-12 Exxonmobil Research And Engineering Company Process for making high octane gasoline with reduced benzene content by benzene alkylation at high benzene conversion
CN107973680A (zh) * 2017-11-23 2018-05-01 丹东明珠特种树脂有限公司 异丁烯叠合催化剂装填构造

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100220A (en) * 1977-06-27 1978-07-11 Petro-Tex Chemical Corporation Dimerization of isobutene
US4544791A (en) * 1983-06-22 1985-10-01 Institut Francais Du Petrole Process for producing premium gasoline by polymerizing C4 cuts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100220A (en) * 1977-06-27 1978-07-11 Petro-Tex Chemical Corporation Dimerization of isobutene
US4544791A (en) * 1983-06-22 1985-10-01 Institut Francais Du Petrole Process for producing premium gasoline by polymerizing C4 cuts

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010118A1 (fr) * 2001-07-26 2003-02-06 Fortum Oyj Constituants de carburant et procedes de fabrication selective de ceux-ci
US6897347B2 (en) 2001-07-26 2005-05-24 Fortum Oyj Fuel components and their selective manufacturing methods
US7304196B2 (en) 2001-07-26 2007-12-04 Neste Oil Oyj Fuel components and their selective manufacturing methods
WO2003033442A1 (fr) * 2001-10-15 2003-04-24 Catalytic Distillation Technologies Recuperation d'un alcool butylique tertiare
JP2006176770A (ja) * 2004-12-16 2006-07-06 Uop Llc 単一分留カラムによる多段階オリゴマー化工法および装置
US7803978B2 (en) 2004-12-16 2010-09-28 Uop Llc Process and apparatus for oligomerization in multiple stages with single fractionation column
US8052945B2 (en) 2004-12-16 2011-11-08 Uop Llc Apparatus for oligomerization in multiple stages with single fractionation column
US7525002B2 (en) 2005-02-28 2009-04-28 Exxonmobil Research And Engineering Company Gasoline production by olefin polymerization with aromatics alkylation
US8395006B2 (en) 2009-03-13 2013-03-12 Exxonmobil Research And Engineering Company Process for making high octane gasoline with reduced benzene content by benzene alkylation at high benzene conversion
CN107973680A (zh) * 2017-11-23 2018-05-01 丹东明珠特种树脂有限公司 异丁烯叠合催化剂装填构造

Also Published As

Publication number Publication date
AU6793500A (en) 2001-04-23

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