WO2007091862A1 - Preparation method of light olefin trimers and production of heavy alkylates by using thereof - Google Patents

Preparation method of light olefin trimers and production of heavy alkylates by using thereof Download PDF

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Publication number
WO2007091862A1
WO2007091862A1 PCT/KR2007/000706 KR2007000706W WO2007091862A1 WO 2007091862 A1 WO2007091862 A1 WO 2007091862A1 KR 2007000706 W KR2007000706 W KR 2007000706W WO 2007091862 A1 WO2007091862 A1 WO 2007091862A1
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Prior art keywords
preparation
olefin
trimers
reaction
catalyst
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PCT/KR2007/000706
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English (en)
French (fr)
Inventor
Sung-Hwa Jhung
Jong-San Chang
Ji Woong Yoon
Tae-Jin Kim
Dae Hyun Choo
Hee-Du Lee
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Korea Research Institute Of Chemical Technology
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Publication of WO2007091862A1 publication Critical patent/WO2007091862A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H5/00—Musical or noise- producing devices for additional toy effects other than acoustical
    • 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
    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10D—STRINGED MUSICAL INSTRUMENTS; WIND MUSICAL INSTRUMENTS; ACCORDIONS OR CONCERTINAS; PERCUSSION MUSICAL INSTRUMENTS; AEOLIAN HARPS; SINGING-FLAME MUSICAL INSTRUMENTS; MUSICAL INSTRUMENTS NOT OTHERWISE PROVIDED FOR
    • G10D7/00—General design of wind musical instruments
    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/08—Non-electric sound-amplifying devices, e.g. non-electric megaphones
    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K3/00—Rattles or like noise-producing devices, e.g. door-knockers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium

Definitions

  • the present invention relates to a preparation method of olefin trimers useful as precursors for heavy alkylates or neo acids. More particularly, present invention relates to a preparation method of olefin trimers, with high throughput and purity, by tuning the pore-structure of acid catalysts and by increasing olefin conversion.
  • Alkylates have been prepared by the alkylation of olefins with paraffins in the presence of sulfuric acid or hydrofluoric acid (Catalysis Today, 49, 193, 1999); however, the method has a severe disadvantage of environmental problem and corrosion due to the usage of the liquid acids. Heavy alkylates with C or more carbons are obtained by the alkylation in low content of 5-10%, and are used as prime solvent or diesel additive to increase the cetane-number of diesel fuel. Therefore, development of a new process to produce heavy alkylate is necessary because the productivity is limited by conventional methods.
  • the present inventors have made intensive researches to overcome the shortcomings described above, and as a result, found a novel trimerization process in which a macroporous cation exchange resin is used in the reaction and the olefin conversion is higher than 60%. Moreover, a heavy alkylate is obtained by the hy- drogenation of trimers that are derived from the trimerization. [10] Accordingly, the object of this invention is to provide a process for producing olefin trimers with high trimers selectivity, high throughput and long catalyst life. Moreover, this invention is also to provide a method for producing a heavy alkylate by the hy- drogenation of the trimers thus obtained.
  • the present invention is directed to a novel process for preparing olefin trimers by oligomerization of olefins, wherein macroporous cation exchange resins are used as catalysts and the olefin conversion is higher than 60%.
  • the present invention is also directed to a process for preparing heavy alkylates by the hydrogenation of olefin trimers thus obtained.
  • Olefin trimers can be effectively prepared by using macroporous cation exchange resins, rather than gel-type cation exchange resins without internal surface area, that have high internal surface area, due to pores (>5nm) even in dried state, and maintaining the olefin conversion high, preferably higher than 60 %.
  • the present invention will be described in more detail as follows:
  • the olefins described in this invention are any olefins composed of C 2 or higher carbon, preferentially to be C 3 or C 4 unsaturated hydrocarbons, and more preferentially to be butenes (C 4 H 8 ) and isobutene is the most suitable olefin.
  • the oligomerization temperature does not have any limitation; however, the preferential temperature is from room temperature to 120 °C.
  • the reaction rate should be low when the temperature is too low, whereas, the conversion at high temperature is not high, due to the exothermal oligomerization reaction, and the resin catalyst can be degraded if the temperature is too high.
  • the reaction temperature of 50-100 °C is more suitable.
  • the oligomerization reaction can be performed both in batch mode and continuous mode, and the latter method is suitable for mass production of oligomers.
  • the continuous mode is operated well by using a fixed bed reactor, and the reactants can be flown upward or downward.
  • a solvent it is advisable to use a solvent to control the heat of reaction because the oligomerization reaction is very exothermic. Moreover, a solvent is helpful to transport reactants and products easily.
  • hydrocarbons such as C -C paraffins can be used. More preferably, isobutane, n-butane, pentanes, hexanes, octanes, nonanes or decanes can be used.
  • Cyclohexane can also be utilized as a solvent.
  • the reactant/ solvent ratio can be any value between 1/100 and 100/1 (wt/wt), and it is preferable to maintain the ratio between 1/10 and 10/1 because of the operation convenience and high productivity.
  • Inert gases such as nitrogen, argon, carbon dioxide and helium can be used as a diluent instead of an organic solvent. It is good to flow the reactant and the inert gas upward when diluent is used in a fixed bed reactor.
  • Any macroporous cation exchange resins can be used in the oligomerization reaction if the resin is in a hydrogen form.
  • the pore size of macropore should be larger than 5 nm even in dried form as described in Reactive and functional polymers, 35, 7, 1997.
  • the catalyst stability is low when the pore size is too large, whereas the diffusion of reactants and products are difficult or deactivation of the catalyst is too fast if the pore size is too small.
  • gel-type ion exchange resins without macropore have the drawback of low reactivity and rapid deactivation.
  • the resins to support hydrogen ion can be any composition, and the resins composed of styrene and divinylbenzene copolymers are suitable. As the content of di- vinylbenzene increases the stability of catalyst increases due to the increased degree of crosslinkings. However, the diffusion of reactants and products will be difficult. The content of divinylbenzene should be 2-98% of the total content of divinylbenzene and styrene.
  • the cation exchange resins should have functional group of sulfonic acid (-SO H) because the acidity is high when the hydrogen ion exists in the form of sulfonic acid.
  • the cation exchange resins should have at least 2-equivalent H7kg-resin. More preferably, the hydrogen ion concentration is at least 3-equivalent H7kg-resin. The hydrogen ion concentration of 4-6 equivalent HVkg-resin is most preferable.
  • Any commercial cation exchange resins can be utilized as long as the resins are macroporous and hydrogen form.
  • Amberlyst-35, Amberlyst-DT and Diaion-PK-228 are some of the examples that can be used easily.
  • Amberlyst-35 is the most suitable catalyst because the concentration of sulfonic acid is high.
  • any synthetic cation exchange resins can be used for the reaction.
  • Cation exchange resins can be used in any state such as water-containing form, dried form, alcohol-containing form and acetone-containing form.
  • the alcohol- or acetone-containing form can be obtained by solvent exchange of water with alcohol or acetone.
  • Alcohol- or acetone-containing resin is more suitable because the catalytic performance in the earlier stage of reaction is more stable and the catalyst life is longer than any other state. This may be due to the fact that the reactants are organics similar to the alcohols or acetone incorporated in the cation resins.
  • Granular catalyst is suitable for the reaction even though no specific size and morphology are mandatory. Catalyst with size greater than 0.1 mm is more suitable, and the size of 0.2-1.0 mm is most suitable for the operation ability and low pressure drop.
  • Olefin conversion does not have any limitation as long as the conversion is higher than 60%. More preferably, the conversion should be higher than 90% because the selectivity of olefin trimers increases with increasing olefin conversion. If the conversion is too low the formation of impurities such as olefin dimers cannot be avoided, whereas olefin tetramers can be increased slightly when the olefin conversion is too high.
  • the productivity is low and the concentration of high molecular weight impurity is high when the flow rate or space velocity of reactant is too low.
  • the olefin conversion and trimers selectivity are low if the space velocity is too high.
  • the suitable space velocity based on the olefin WHSV (weight hourly space velocity), is 2-100 h "1 , and more preferably the velocity is 10-50 h "1 .
  • the trimers that obtained from the olefin oligomerization can be utilized directly for the production of chemicals such as neo-acid or can be converted to heavy alkylate by hydrogenation.
  • Heavy alkylates containing C or higher carbons are obtained by hy- drogenation of the olefin trimers that are prepared by this invention.
  • the hydrogenation is described only briefly because hydrogenation is conducted relatively easily in the presence of a precious metal or nickel as described in 'Fine chemicals through heterogeneous catalysis, Wiley- VCH, 2001, pp. 351-426'.
  • the hydrogenation for heavy alkylate can be performed with any conventional reactors such as a fixed bed reactor and a continuous stirred reactor.
  • Hydrogenation catalyst can be selected from any supported catalysts such as Pd/C, Pd/alumina, Pd/silica, Pd/silica-alumina, Pt/C, Pt/alumina, Pt/silica, Pt/silica-alumina, Ru/C, Ru/alumina, Ru/silica, Ru/ silica-alumina, Ni/C, Ni/alumina, Ni/silica, Ni/silica-alumina.
  • the mixed catalysts containing two or more of above mentioned catalysts can be applicable.
  • supported mixed catalyst that containing two or more metals from Pd, Pt, Ru, Ni can be used for the hydrogenation.
  • Fig. 1 represents the change of conversion and selectivities with reaction time in the isobutene oligomerization, obtained in Example 1.
  • Fig. 2 represents the dependence of trimers selectivity on the isobutene conversion, obtained in Example 5.
  • the oligomerization reaction of isobutene was carried out at 70 °C by using a fixed bed reactor containing 2 g of dried Amberlyst-35 (size: 0.2 1.0mm, average diameter: 0.5 mm) and by flowing n-butane and isobutene (1:1 wt ratio) upward.
  • the flow rates of hydrocarbons were controlled by mass flow controllers and the isobutene flow rate was adjusted for the isobutene WHSV (weight hourly space velocity) to be 10 h "1 .
  • the reaction temperature was maintained constant by using a liquid circulator. Circulated water at fixed temperature absorbs extra heat generated from the oligomerization reaction.
  • the isobutene conversion was calculated by the analysis of gas-phase effluent by using a GC.
  • the isobutene conversion was cross-checked by measuring the total flow rates of n-butane and isobutene with mass flow meters.
  • the liquid product, after trapping using a cold trap, was analyzed by a GC for the composition of dimers, trimers and tetramers.
  • the isobutene conversion and trimers selectivity were 99.4% and 75.5 wt%, respectively, through the reaction of 70 h.
  • the dimers selectivity and tetramers selectivity were maintained low of 9.4 wt% and 15.1 wt %, respectively.
  • Table 1 Detailed reaction conditions and reaction results are summarized in Table 1.
  • the oligomerization reaction was carried out as Example 1, except that water- containing catalyst was used instead of dried catalyst. Water-containing Amberlyst-35 was used as-received from the maker. The catalyst was 2 g based on the dried catalyst, and the isobutene WHSV was 80 h "1 instead of 10 h "1 . Even though 2 h of reaction time was needed for the steady state reaction, the isobutene conversion and trimers selectivity were satisfactory after 1O h of reaction. Detailed reaction conditions and reaction results are summarized in Table 1.
  • the oligomerization reaction was carried out as Example 3 except that process parameters such as temperature, space velocity and catalyst amount were changed to reach the isobutene conversion of 40%- 100%.
  • the trimers selectivity increased with the isobutene conversion as shown in Fig. 2. It can be known that isobutene conversion should be higher than 60% for the trimers selectivity higher than 50%.
  • the present process for preparing olefin trimers is performed by use of macroporous cation exchange resins in hydrogen form and maintaining the isobutene conversion higher than 60% because the trimers selectivity increases with increasing isobutene conversion.
  • the olefin trimers thus obtained can be used for preparing neo-acid or can be hydrogenated to heavy alkylate that is used for prime solvent or diesel additive.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Acoustics & Sound (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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PCT/KR2007/000706 2006-02-09 2007-02-09 Preparation method of light olefin trimers and production of heavy alkylates by using thereof WO2007091862A1 (en)

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KR1020060012317A KR100784118B1 (ko) 2006-02-09 2006-02-09 올레핀의 삼량체 제조방법 및 그를 이용한고비점알킬레이트 제조 방법
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009079213A2 (en) 2007-12-03 2009-06-25 Gevo, Inc. Renewable compositions
US8193402B2 (en) 2007-12-03 2012-06-05 Gevo, Inc. Renewable compositions
US8373012B2 (en) 2010-05-07 2013-02-12 Gevo, Inc. Renewable jet fuel blendstock from isobutanol
US8450543B2 (en) 2010-01-08 2013-05-28 Gevo, Inc. Integrated methods of preparing renewable chemicals
US8742187B2 (en) 2011-04-19 2014-06-03 Gevo, Inc. Variations on prins-like chemistry to produce 2,5-dimethylhexadiene from isobutanol
CN113636903A (zh) * 2021-08-12 2021-11-12 万华化学集团股份有限公司 一种异丁烯齐聚制备三异丁烯的方法
EP4001248A1 (en) * 2020-11-12 2022-05-25 Neste Oyj Olefin trimerization

Citations (5)

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US4377393A (en) * 1979-11-03 1983-03-22 Ec Erdolchemie Gmbh Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture
JP2003160526A (ja) * 2001-11-27 2003-06-03 Manac Inc ヒドロキノンの二量体及び三量体の製造方法
US6703356B1 (en) * 2000-03-23 2004-03-09 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluids
US6800702B2 (en) * 2000-07-11 2004-10-05 Bp Chemicals Limited Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group
US20050182284A1 (en) * 2002-03-29 2005-08-18 Stanat Jon E. Oligomerization of olefins

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377393A (en) * 1979-11-03 1983-03-22 Ec Erdolchemie Gmbh Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture
US6703356B1 (en) * 2000-03-23 2004-03-09 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluids
US6800702B2 (en) * 2000-07-11 2004-10-05 Bp Chemicals Limited Olefin trimerisation using a catalyst comprising a source of chromium, molybdenum or tungsten and a ligand containing at least one phosphorous, arsenic or antimony atom bound to at least one (hetero)hydrocarbyl group
JP2003160526A (ja) * 2001-11-27 2003-06-03 Manac Inc ヒドロキノンの二量体及び三量体の製造方法
US20050182284A1 (en) * 2002-03-29 2005-08-18 Stanat Jon E. Oligomerization of olefins

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2225351A4 (en) * 2007-12-03 2016-11-09 Gevo Inc RENEWABLE COMPOSITIONS
US8193402B2 (en) 2007-12-03 2012-06-05 Gevo, Inc. Renewable compositions
US8378160B2 (en) 2007-12-03 2013-02-19 Gevo, Inc. Renewable compositions
US8487149B2 (en) 2007-12-03 2013-07-16 Gevo, Inc. Renewable compositions
WO2009079213A2 (en) 2007-12-03 2009-06-25 Gevo, Inc. Renewable compositions
US8450543B2 (en) 2010-01-08 2013-05-28 Gevo, Inc. Integrated methods of preparing renewable chemicals
US8373012B2 (en) 2010-05-07 2013-02-12 Gevo, Inc. Renewable jet fuel blendstock from isobutanol
US8975461B2 (en) 2010-05-07 2015-03-10 Gevo, Inc. Renewable jet fuel blendstock from isobutanol
US8742187B2 (en) 2011-04-19 2014-06-03 Gevo, Inc. Variations on prins-like chemistry to produce 2,5-dimethylhexadiene from isobutanol
EP4001248A1 (en) * 2020-11-12 2022-05-25 Neste Oyj Olefin trimerization
US11535577B2 (en) 2020-11-12 2022-12-27 Neste Oyj Olefin trimerization
CN113636903A (zh) * 2021-08-12 2021-11-12 万华化学集团股份有限公司 一种异丁烯齐聚制备三异丁烯的方法
CN113636903B (zh) * 2021-08-12 2023-03-03 万华化学集团股份有限公司 一种异丁烯齐聚制备三异丁烯的方法

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