Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C9/00—Aliphatic saturated hydrocarbons
  • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
  • C07C9/16—Branched-chain hydrocarbons
  • C07C9/21—2, 2, 4-Trimethylpentane
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7007—Zeolite Beta
• • 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
  • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/36—Steaming
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency

Definitions

• the present invention relates to selective processes for making a reaction product comprising trimethylpentene(s) from a C4 olefinic feedstock. It also
• Isobutene oligomers are useful intermediates for the preparation of various products of commercial interest, such as isoparaffins, higher alcohols, aldehydes or carboxylic acids having 8, 12 or 16 carbon atoms.
• products of commercial interest such as isoparaffins, higher alcohols, aldehydes or carboxylic acids having 8, 12 or 16 carbon atoms.
• highly branched trimethylpentanes that can be obtained through hydrogenation of trimethylpentenes are of particular interest as gasoline octane number enhancers.
• trimethylpentanes have high RONs (Research Octane Numbers) and MONs (Motor Octane Numbers): 2,2,4-trimethylpentane, also known as isooctane, has a RON of 100 and a MON of 100; 2,3,4- trimethylpentane has a RON of 109.27 and a MON of 95.9; 2,2,3- trimethylpentane has a RON of 109.9 and a MON of 99.9.
• DE 3,542, 171-Al discloses selective dimerisation of isobutene into 2,4,4-trirnethylpent-l-ene and -2-ene, using a bismuth and/or lead doped zeolite catalyst at 150 ° C. Selectivity for dimer over trimer formation can be as high as 88 percent.
• feedstocks are produced in oil refineries, and usually comprise isobutene, 1- butene and 2-butene; they may also comprise butadiene.
• olefins is that isobutene oligomerisation conditions produce codimers of isobutene with the other normal C4 olefins of the feedstock in addition to the
• Catalysts used in such process must not only be selective for dimers over higher oligomers, but they must also favor isobutene homodimerisation over codimerisation of isobutene with the other normal C4
• USP 4,454,367 discloses a method for converting isobutene into low polymers, i.e. a mixture of isobutene dimers, trimers and tetramers, from a C4
• olefinic mixture comprising isobutene and n-butenes.
• the process uses as catalyst a high silica mordenite having a Si ⁇ 2/Al2 ⁇ 3 mole ratio of 50 to 200
• hydrocarbon mixture consisting of 26.2 mole % of butane, 1.3 mole % of isobutene, 7.5 mole % of 1-butene and 65 mole % of 2-butene was fed into a reactor packed with the high silica mordenite at a temperature of 80 ° C. Under these conditions isobutene conversion rates of up to 93 percent were achieved with low n-butene loss.
• USP 5,091,590 discloses a two-stage method for MTBE (methyl tertiary butyl ether) preparation from a C4 feedstock comprising isobutene, 1-butene
• the C4 feedstock is treated
• first reaction zone solid acid etherification catalyst particles
• the intermediate product is withdrawn from the first reaction zone and fractionated to recover MTBE.
• the remaining part of the intermediate product then undergoes the second stage of the process; it is contacted with medium pore solid acid catalyst particles to give a product containing MTBE, isobutene oligomer and C5+ alkylate.
• the preferred catalyst for this second stage is selected from ZSM-5, ZSM-11, ZSM-50, zeolite beta, MCM-22 and mixtures thereof. According to this document, the second stage reaction takes place at 70° to 280°C.
• the present invention provides a process for making a reaction product comprising trimethylpentene(s) which comprises contacting a C4 olefinic feedstock containing isobutene and n-butene(s) with a catalyst
• n-butene i.e. 1-butene and/or 2-butene.
• these feedstocks may also contain butadiene.
• Suitable C4 olefinic feeds include
• the present process advantageously oligomerizes isobutene without the need for prior separation of isobutene from the feed.
• Another advantage of the present process is that it is highly selective for isobutene homooligomerization versus isobutene /n-butene codimerization. Less than 10 wt %, preferably less than 5 wt% of the n-butenes present in the feedstock are oligomerised. Such selectivity is achieved with a catalyst comprising zeolite beta.
• zeolite beta is in proton form, herewith referred to as zeolite H-bet ' a.
• Zeolite H-beta is a zeolite with relatively large pores. It is available commercially or may be prepared synthetically in different Si/Al atomic ratios ranging for example from 10 to 150. Reference is made to "Synthesis of High Silica Alumino silicate Zeolites" by P. A. Jacobs and J.A. Martens (published as volume 33 in the series "Studies in Surface Science and Catalysis") for a review of the synthesis and properties of zeolite beta.
• Zeolite beta with Si/Al atomic ratios higher than 150 can be obtained by dealumination methods such as hydrothermal (steaming) and/or chemical treatment.
• dealumination methods such as hydrothermal (steaming) and/or chemical treatment.
• dealuminated zeolite H-beta may also be used in the present process.
• the zeolite beta catalyst may be used in the form of powders (including powders consisting wholly or in part of single crystals).
• the zeolite beta catalyst may instead be incorporated in shaped agglomerates, for example, tablets, extrudates or spheres, which may be obtained by combining the zeolite with a binder material that is substantially inert under the conditions employed in the oligomerization process.
• the zeolite catalyst may be present in amounts from 1 to 99% by weight, based on the combined weight of the zeolite and binder material.
• binder material there may be used any suitable material, for example silica, metal oxides, or clays, such as montmorillonite, bentonite and kaolin clays, the clays optionally being calcined or modified chemically prior to use.
• suitable matrix materials include silica- alumina, silica-berylia, silica-magnesia, silica-thoria, silica-titania, silica-alumina- magnesia, silica-alumina-thoria, silica- alumina- zirconia and silica-magnesia- zirconia.
• the process according to the present invention may be carried out in various types of reactors suited for heterogenous reactions, either fixed or fluid bed reactors.
• the process may be carried out in batch or continuous flow reactors or according to the catalytic distillation technique (also called reactive distillation) . Conversion of isobutene from the C4 olefinic feedstock can take
• the present process selectively converts isobutene present in the C4
• dimers represent at least 45 wt %, preferably 60 wt % of all oligomers formed, and trimethylpentenes represent at least 80 wt % of all dimers formed.
• Such selectivities for trimethylpentenes may be achieved at moderate temperatures, e.g. below 50°C.
• the present invention also encompasses the products obtained by contacting a C4 olefinic feedstock with a catalyst comprising zeolite
• Said products may be transformed into other products of commercial interest by one or several conversion steps, e.g. fractionation, hydrogenation, hydroformylation followed by oxidation or hydrogenation, carbonylation, etherif ⁇ cation, epoxidation or hydration.
• the present invention also encompasses the products obtained by these further transformation, e.g. alkanes, alcohols, ethers, aldehydes, epoxides or carboxylic acids.
• feedstock into a reaction product comprising at least 45 wt % trimethylpentenes can be immediately followed by hydrogenation.
• hydrocarbon compositions comprising at least 45 wt % trimethylpentanes, which are useful solvents for cleaning formulations, coating formulations, adhesive formulations and the like.
• Dimerization of isobutene from the C4 olefinic feedstock may be carried
• feedstock having the following composition, expressed in wt%: 12% isobutane, 19% n-butane, 14% 1-butene, 20.2% isobutene, 20.5% trans- 2-butene and 13.1% czs-2-butene
• feedstock having the following composition, expressed in wt%: 12% isobutane, 19% n-butane, 14% 1-butene, 20.2% isobutene, 20.5% trans- 2-butene and 13.1% czs-2-butene
• the composition of product mixture was then determined by gas chromatography (GC), using hydrogen as carrier gas.
• GC gas chromatography
• the injector liner was filled with a hydrogenation catalyst (0.03 g of 0.5% Pt on Al) so that, by in-situ hydrogenation, all the components were identified as paraffins.
• the conversion of butenes/isobutene was determined by comparing the GC analysis of the product mixture with the GC analysis of the feedstock under the same conditions.
• the feedstock contains butane and isobutane which are inert under the reaction conditions; butane and isobutane were thus used as internal standards for calculating conversion.
• the catalysts tested were:
• zeolite H-beta having Si/Al atomic ratio of 10.5, commercially available from Zeolyst International;
• zeolite beta in Na form used in this procedure was prepared synthetically according to the procedure disclosed in EP 187522;
• H- H-Beta 30 st. H-Beta described above which has been steamed at 650°C for 16 hours;
• - H-Beta 30 st. reg. H-Beta 30 st. described above, which has been regenerated after use by drying and calcinating at 550°C for 10 hours under air;
• H-Beta 30 nitric H-Beta 30 described above, which has been treated with 6N HNO3 under reflux for 2 hours, filtered and washed until washing liquids
• zeolite H-Beta having Si/Al atomic ratio of 50 commercially available from S ⁇ d Chemie;
• zeolite H-Beta having Si/Al atomic ratio of 100 commercially available from S ⁇ d Chemie;
• zeolite H-beta having Si/Al atomic ratio of 150 commercially available from Sud Chemie;
• H- H-Beta 150 st. H-beta 150 mentioned above which has been steamed at 650°C for 16 hours;
• H-Beta 150 nitric H-Beta 150 mentioned above which has been treated with 6N HNO3 under reflux for 2 hours, filtered and washed until washing liquids
• - nC4 means n-butene; - C8 represents the wt% of dimers formed;
• - C16 represents the wt% of tetramers formed
• - NC8 represents the wt% of dimers obtained in the form of octenes (octane after hydrogenation) ;
• - MC7 represents the wt% of dimers obtained in the form of methylheptenes (methylheptanes after hydrogenation)
• - DMC6 represents the wt% of dimers obtained in the form of dimethylhexenes (dimethylheptanes after hydrogenation) ;
• TMC5 represents the wt% of dimers obtained in the form of trimethylpentenes (trimethylpentanes after hydrogenation);
• 2,2,4-TMP represents the portion in wt% of TMC5 in the form of 2,2,4- trimethylpentane (after hydrogenation) ;
• 2,3,4-TMP represents the portion in wt% of TMC5 obtained in the form of 2,3,4-trimethylpentane (after hydrogenation).
• Feedstock is reacted with the catalyst for 2 hrs at 40°C * Remainder TMP are 2,2,3 and 2,3,3 trimethyl pentane

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• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• 1999
  • 1999-12-23 GB GBGB9930402.4A patent/GB9930402D0/en not_active Ceased
• 2000
  • 2000-12-20 WO PCT/US2000/034840 patent/WO2001046095A1/en not_active Ceased
  • 2000-12-20 CA CA002394030A patent/CA2394030C/en not_active Expired - Fee Related
  • 2000-12-20 KR KR1020027008135A patent/KR100635314B1/ko not_active Expired - Fee Related
  • 2000-12-20 CN CNB008175659A patent/CN1221497C/zh not_active Expired - Fee Related
  • 2000-12-20 AU AU24476/01A patent/AU782012B2/en not_active Ceased
  • 2000-12-20 BR BR0016719-3A patent/BR0016719A/pt not_active Application Discontinuation
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  • 2000-12-20 EP EP00988248A patent/EP1242342B1/en not_active Expired - Lifetime
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