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WO2007105875A1 - Procédé de préparation de trimères d'oléfine légers et production d'alkylats lourds à partir de ces derniers - Google Patents

Procédé de préparation de trimères d'oléfine légers et production d'alkylats lourds à partir de ces derniers Download PDF

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WO2007105875A1
WO2007105875A1 PCT/KR2007/001159 KR2007001159W WO2007105875A1 WO 2007105875 A1 WO2007105875 A1 WO 2007105875A1 KR 2007001159 W KR2007001159 W KR 2007001159W WO 2007105875 A1 WO2007105875 A1 WO 2007105875A1
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preparation
zeolites
olefin
catalyst
acid
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PCT/KR2007/001159
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Sung-Hwa Jhung
Jong-San Chang
Ji Woong Yoon
Young-Kyu Hwang
Ji-Sun Lee
Ji Hye Lee
Hee- Du Lee
Tae-Jin Kim
Seong Jun Lee
Dae Hyun Choo
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Korea Research Institute Of Chemical Technology
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Priority claimed from KR1020060022782A external-priority patent/KR100718014B1/ko
Priority claimed from KR1020060038895A external-priority patent/KR100757031B1/ko
Priority claimed from KR1020060086303A external-priority patent/KR100786613B1/ko
Application filed by Korea Research Institute Of Chemical Technology filed Critical Korea Research Institute Of Chemical Technology
Publication of WO2007105875A1 publication Critical patent/WO2007105875A1/fr

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • 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
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • 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
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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
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    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron

Definitions

  • the present invention relates to a preparation method of olefin trimers useful as precursors for heavy alkylates or neo acids; and heavy alkylates by the hydrogenation of the olefin trimers thus obtained. More particularly, present invention relates to a preparation method of olefin trimers, with high trimer selectivity and catalyst stability, by using zeolite catalysts containing pore structures that are crossing each other; by using composite acid catalysts that are composed of both Bronsted and Lewis acid catalysts; by using composite acid catalysts thus described, after post- treatment such as calcination or water-washing. Moreover, present invention relates to a preparation method of heavy alkylates by the hydrogenation of the olefin trimers thus obtained.
  • the present invention provide an effective trimerization method with improved productivity for trimers, high trimers purity and increased catalyst life-time by using zeolites catalysts, especially composed of pore structures that are crossing each other.
  • the present invention provides an effective trimerization method with improved productivity for trimers, high trimers purity and increased catalyst life-time by using composite acid catalysts that are composed of both Bronsted and Lewis acid catalysts; or by using the composite acid catalysts after post-treatment such as calcination at high temperature and water-washing.
  • the oligomerization of olefins has been carried out by using acid catalysts such as supported phosphoric acid, and olefin dimers have been generally obtained for a gasoline additive after hydrogenation of the dimers (USP 6689927, 6284938) .
  • the hydrocarbons are called alkylates if the oligomers thus obtained are hydrogenated, and the alkylates have various uses depending on the number of carbons.
  • Alkylates have also 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 Cg or more carbons are obtained, in low content of 5-10%, by the alkylation, 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 .
  • Olefin trimerization has mainly been carried out by using solid acid catalysts such as a heteropoly acid (JP 2005015383), a zirconia (JP 2005015384), a molecular sieve called Al-TS-I (USP 6914165) and a sulfated titania (J. Molecular Catalysis A, 228, 333, 2005) .
  • Ionic liquids are also used for the reaction (CNP 1379005) .
  • CNP 1379005 cation exchange resins for the oligomerization. It has been claimed that a cation exchange resin can be used in a dimerization (USP 2005/0119111A1) .
  • trimers selectivity can be maintained high by using macroporous cation exchange resins in proton form and maintaining reaction conversion high.
  • an ion exchange resin called Amberlyst-15 was used in the oligomerization of isobutene (Catalysis Today, 100, 463, 2005) .
  • the conversion was less than 40% and dimers, rather than trimers, were the main products.
  • zeolite catalysts in oligomerization (Catalysis Today, 100, 463,
  • 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 zeolite that has crossing pore structures is used in the reaction; or process in which a composite catalyst having both Lewis acid and Br ⁇ nsted acids is used in the reaction; or process in which a composite catalyst, after post-treatment such as calcination and water-washing, is used in the trimerization.
  • the trimerization reactions thus performed show surprisingly increased reaction stability and trimers yield.
  • a heavy alkylate is obtained by the hydrogenation of trimers that are derived from the trimerization.
  • 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 intended also to provide a method for producing a heavy alkylate by the hydrogenation of the trimers thus obtained.
  • the present invention is directed to a novel process for preparing olefin trimers by oligomerization of olefins, wherein zeolites having crossing pore structures; or composite catalysts having both Lewis acid and Bronsted acids; or the composite catalysts that are after-treated with a process such as calcination and water-washing are used as catalysts.
  • the present invention is also directed to a process for preparing heavy alkylates by the hydrogenation of olefin trimers thus obtained.
  • the present invention provides a novel trimerization process, with remarkably high throughput, selectivity and stability, by using a zeolite catalyst having pore composed of ten oxygens (called 10 membered ring or 10 MR) and another pore crossing the 10 MR pores or by using a zeolite catalyst having pore composed of 12 MR and another 12 MR pore crossing the 12MR.
  • a zeolite catalyst having pore composed of ten oxygens called 10 membered ring or 10 MR
  • the present invention provides a novel trimerization process, with even higher throughput, selectivity and stability, by using a composite catalyst having both Lewis and Bronsted acids or by using the composite catalyst after post-treatment such as calcination and water-washing.
  • olefin trimerization with even higher throughput, selectivity and stability, can be effectively carried out, for example, by zeolite containing ⁇ extra-framework aluminum' obtained by dealumination of a zeolite; or by zeolite or aluminophosphate (AlPO) type catalysts further containing Lewis acid such as FeCl 3 , AlCl 3 , TiCl 4 , etc. via ion exchange, supporting and physical mixing; or by calcination or successive water-washing the zeolites or aluminophosphate type catalysts containing Lewis acids.
  • AlPO aluminophosphate
  • Another scope of the present invention includes the production of heavy alkylates containing Cg or higher carbon by the hydrogenation of the olefin trimers selectively obtained by the 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' .
  • Fig. 1 represents the X-ray diffraction pattern of K-SUZ- 4, obtained in Example of Synthesis.
  • Fig. 2 represents the change of conversion and selectivities with reaction time in the isobutene oligomerization, obtained in Example 1.
  • Fig. 3 represents the change of conversion and selectivities with reaction time in the isobutene oligomerization, obtained in Example 3.
  • Fig. 4 represents the change of conversion and selectivities with reaction time in the isobutene oligomerization, obtained in Comparative Example 1.
  • Fig. 5 represents the change of conversion and selectivities with reaction time in the isobutene oligomerization, obtained in Example 5.
  • Fig. 6 represents the change of conversion with reaction time in the isobutene oligomerization, obtained in Examples 8-10 and Comparative Example 4.
  • Fig. 7 represents the change of conversion with reaction time in the isobutene oligomerization, obtained in Examples 11 and Comparative Example 5.
  • 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 (CaH 8 ) and isobutene is the most suitable olefin.
  • Olefins composed of Cg or more carbons are obtained by the oligomerization, and olefins containing C 9 or more carbons are suitable, and olefins containing Ci 2 are most suitable.
  • the oligomerization temperature does not have any limitation; however, the preferential temperature is from room temperature to 120 0 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 polymeric compounds can be obtained easily if the temperature is too high.
  • the reaction temperature of 50-100 °C is more suitable.
  • the oligomerization 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 stirred reactor or a fixed bed reactor, and the reactants can be flown upward or downward for the case of a fixed bed reactor.
  • a solvent is helpful to transport reactants and products easily.
  • hydrocarbons such as C 2 -Ci 0 paraffins can be used. More preferably, isobutane, n-butane, pentanes, hexanes, heptanes, 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 zeolite that has crossing pore structures can be applied for the oligomerization, and zeolites having 10 MR or 12 MR are preferred.
  • the pore that crossing the 10 MR can be 8 MR and/or 6 MR. SUZ-4 (USP 5118483; J. Kor. Chem. Soc, 48, 623, 2004; J. Phys . Chem. B, 103, 197, 1999; J. Phys . Chem.
  • FER ferrierite
  • FER ferrierite
  • FU-9 EP B-55529, 1985
  • ISI-6 USP 4578259
  • NU-23 EP A-103981
  • Sr-D J. Chem. Soc, 2296-2305, 1964
  • ZSM-35 USP 4016245
  • monoclinic FER Am. Mineral. , 70, 619, 1985
  • zeolite which has extra-pore (composed of 12 MR and/or 10 ⁇ 6 MR) crossing the 12 MR is suitable.
  • zeolite beta (BEA, having 12 MR and crossing 12 MR, Zeolites, 8, 446, 1988) is suitable because of high activity and catalyst stability.
  • Zeolite iso-structural to BEA such as Al-rich beta (Microporous Materials, 5, 289-297, 1996), B-containing beta (Proc. 9th Int. Zeolite Conf. , pp. 425-432, 1993; J. Incl. Phenom. MoI. Recogn.
  • Any zeolite can be used as a trimerization catalyst as long as it has at least small amount of acid sites.
  • Zeolite in any form can be used because zeolite has intrinsic acidity.
  • Zeolite in proton- form is more suitable because of high acidity and high catalytic activity, and proton-exchanged zeolite with the degree of ion exchange higher than 50% is even more suitable.
  • the composite acid catalyst of the present invention means any acid catalyst composed of both Lewis acid and Br ⁇ nsted acid or any composite acid catalyst that is further treated with calcination, water-washing, etc.
  • a Br ⁇ nsted acid any one selected from proton- or ammonium- zeolites; aluminophosphate-type molecular sieves; cation exchange resins containing functional group of sulfonic acid, carboxylic acid or phosphoric acid; and phosphoric acid supported on a support can be applicable.
  • metal-incorporated AlPO molecular sieves are suitable because the AlPO-type molecular sieves have acidity when suitable metals (to have oxidation state of 2 or 4 , for example, Si, Mg, Ti, V, Cr, Mn, Fe, Co, Ni, etc.) are incorporated in the framework.
  • Any material can be a Lewis acid if it can receive an electron, and typical element for Lewis acid can be Al, Fe, B or Ga.
  • Materials that are described as MX n are well known Lewis acids.
  • M means metallic elements selected from III, IVa, IVb, V and Vl-family of the periodic table.
  • X means halogen element such as F, Cl, Br and I
  • n represents the valance of M.
  • BF 3 , BCl 3 , BBr 3 , BI 3 , SbF 5 , SbCl 5 , AlCl 3 , AlBr 3 , TiCl 4 , TiBr 4 , ZrCl 4 , PF 5 , FeCl 3 , FeBr 3 , GaCl 3 , SnBr 4 , SnCl 4 are typical Lewis acids.
  • Extraframework aluminum species in a zeolite belong to the Lewis acid of the present invention because it is known that the extraframework aluminum species, obtained by dealumination of zeolites or related materials, have the characteristics of a Lewis acid (J " . Catalysis, 9, 225, 1967) . Any Lewis acid that is generally regarded as a Lewis acid is not restricted in the present invention.
  • the composite acid catalyst, containing both Lewis and Br ⁇ nsted acids, used in the present invention is applied in the acid catalytic reaction, trimerization, after preparation by loading Lewis acid on a solid such as zeolites, aluminophosphate-type molecular sieves or cation exchange resins via physical mixing, ion exchange or supporting, etc.
  • Ion exchange can be carried out by both solid state reaction and liquid phase reaction; however, solid phase reaction is more suitable because metal ions with high oxidation states are used.
  • Solid state ion exchange can generally be carried out by calcination at high temperature after physical mixing.
  • Organic solvents are preferable in liquid phase ion exchange or supporting using a solvent in order to prevent a hydrolysis of Lewis acids.
  • organic solvent benzene, carbon tetrachloride, toluene, cyclohexane, etc. can be used, and solvent with low polarity is more preferable.
  • the supporting process is well-explained in an open literature (Chem. Rev., 103, 4307, 2003) and HCl can be removed during supporting.
  • Lewis acid can be used for the present invention without any treatment after loading on a solid support. Moreover, the loaded Lewis acid can be used as an acid catalyst after treatment such as heating and water-washing.
  • the Lewis acid can be bonded to a Br ⁇ nsted acid, or can be well dispersed or can be ion-exchanged. Lewis acid, partly blocking the pore structure of a catalyst, can be removed by water-washing.
  • the Br ⁇ nsted acid/Lewis acid ratios there is no limitation for the Br ⁇ nsted acid/Lewis acid ratios; however, the Br ⁇ nsted acid/Lewis acid ratio can preferentially be between 99:1 and 1:99 because the effect of Lewis acid does not occur if the content of Lewis acid is too low and the initiation of the reaction is difficult if the content of Br ⁇ nsted acid is too low.
  • the Lewis acid in the present invention can be the inorganic Lewis acid mentioned above and extra-framework aluminum species, obtained from dealumination, for the case of zeolites.
  • the acid catalysts containing both Lewis and Br ⁇ nsted acids are physical mixtures of Lewis and Br ⁇ nsted acids or the post-treated Lewis and Br ⁇ nsted acids by a suitable process.
  • the post-treated catalysts are effective because the Br ⁇ nsted acid and Lewis acid are near each other, and can be obtained by calcination or water-washing the Lewis acids such as FeCl 3 and AlCl 3 that are loaded on proton-type zeolites or aluminophosphate-type molecular sieves or proton- type zeolites after dealumination.
  • the composite acid catalysts are the aforementioned MX n which are loaded, by physical mixing, ion-exchange and impregnation, on zeolites or AlPO-type molecular sieves of proton- or ammonium- form, or on cation- exchange resins which have at least one form selected from sulphonic acid, carboxylic acid and phosphoric acid.
  • any one or more than one of the material selected from the materials such as BF 3 , BCl 3 , BBr 3 , BI 3 , SbF 5 , SbCl 5 , AlCl 3 , AlBr 3 , TiCl 4 , TiBr 4 , ZrCl 4 , PF 5 , FeCl 3 , FeBr 3 , SnBr 4 , SnCl 4 can be used.
  • the above mentioned molecular sieves can be anyone selected from zeolites or AlPO molecular sieves. Zeolites or AlPO molecular sieves having crossing channels are especially suitable, and for example, zeolites beta, ferrierite, SUZ-4 and Y are more suitable.
  • the zeolites having crossing pore, composite acid catalysts having both Lewis and Br ⁇ nsted acids, or the composite catalysts post-treated by calcination or water- washing can be used as the state of powder or granule by shaping.
  • the catalysts can be used as a shaped form such as pellet, sphere and extrudate. Shaped catalysts such as granule and pellet are more suitable in order to reduce the pressure drop. 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 50% because the selectivity of olefin trimers increases with increasing olefin conversion. More preferably, the conversion should be higher than 90% for practical application. If the conversion is too low the formation of impurities such as olefin dimers is high, whereas olefin tetramers or oligomers with high molecular weight can be increased slightly when the olefin conversion is too high, requiring the increase of concentration of diluent or solvent.
  • 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 0.5-100 h "1 , and more preferably the velocity is 1-50 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 Cg or higher carbons are obtained by hydrogenation of the olefin trimers that are prepared by this invention.
  • 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 and Ni/silica- alumina.
  • the mixed catalysts containing two or more of the 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.
  • the hydrogenation can be carried out in any phase such as liquid- or gas-phase and any concentration of hydrogen is affordable as long as the total amount of hydrogen is higher than the stoichiometric amount that is needed for the hydrogenation.
  • Reaction mixtures containing water (50 mL) , KOH (3.29 g) and aluminum foil (0.4g) were mixed at 60 0 C for 12 h until it become clear solution.
  • TEAOH tetra ethylammonium hydroxide, 7.93g
  • silica sol Aldrich, Ludox-HS-40, 40 wt% Si ⁇ 2, 18.2 g was added further and stirred for another 1 h.
  • Above solution was heated at 165 °C for 48 h under autogenous pressure. During the heating for synthesis, the reactant mixture was stirred at the speed of 250 rpm.
  • the oligomerization of isobutene was carried out at 70 0 C by using a fixed bed reactor containing 2 g of the H-SUZ-4
  • the isobutene conversion was re- checked by the analysis of gas-phase effluent by using a gas chromatography (GC) .
  • the liquid product after using a cold trap, was analyzed by a GC for the composition of dimers, trimers and tetramers.
  • Table 1 the isobutene conversion, trimers selectivity and dimers selectivity were 99.9%, 68.8 wt% and 11.2 wt%, respectively, after the reaction time of 20 h.
  • the conversion and trimers selectivity were very high under the reaction condition.
  • Table 1 Detailed reaction conditions and reaction results are summarized in Table 1.
  • EXAMPLE 2 The oligomerization was carried out as Example 1, except that the K-SUZ-4 catalyst that was obtained in the Example of Synthesis was used instead of H-SUZ-4 catalyst.
  • the isobutene conversion, trimers selectivity and dimers selectivity were 99.5%, 51.9 wt% and 28.4 wt%, respectively, after 20 h of reaction.
  • Detailed reaction conditions and reaction results are summarized in Table 1.
  • EXAMPLE 4 Hydrogenation Ten (10) grams of isobutene trimers, obtained in Example 1 and purified with distillation, were loaded in a continuous stirred reactor. Cyclohexane (90 g) was added as a solvent. Catalyst basket containing 0.5 g of Pd (5%) /C was mounted on the stirring shaft. The reactor temperature was maintained at 100 0 C and the reactor pressure was raised to 10 atm by using hydrogen. The hydrogenation was started by the onset of agitation, and the reactor pressure was maintained constant (10 atm) by using a back pressure regulator. After reaction for 1 h, the product was separated from cyclohexane by distillation. By the analysis using GC/mass spectrometry, it was confirmed that the conversion of olefins to paraffins was 99.5%, and a heavy alkylate was successfully obtained.
  • the oligomerization was carried out as Example 1, except that H-mordenite catalyst was used instead of H-SUZ-4 catalyst.
  • Detailed reaction conditions and reaction results are summarized in Table 1 and Fig. 4. It was confirmed that the conversion was low and the trimers selectivity was very low even though the reaction time was very short .
  • the oligomerization was carried out as Example 1, except that H-SAPO-Il catalyst was used instead of H-SUZ-4 catalyst.
  • the H-SAPO-Il catalyst having 1-dimensional pore of 10 MR rather than crossing pore system, was obtained by the method of USP 6303534.
  • the as-synthesized SAPO-Il was calcined at 550 0 C for 10 h, ion-exchanged with ammonium chloride and calcined for 10 h at 500 0 C using an electric oven.
  • the initial activity was not high, and the isobutene conversion and trimers selectivity were 12.0% and 15.2 wt%, respectively, after short reaction time of 3h.
  • Detailed reaction conditions and reaction results are summarized in Table 1. It was confirmed that the conversion was low and the trimers selectivity was very low even though the reaction time was very short.
  • the catalyst H-beta was used as a catalyst.
  • the oligomerization of isobutene was carried out at 70 0 C by using a fixed bed reactor containing 2 g of above H-beta (diameter: 0.2 - 1.0mm, pellet-type) 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 .
  • the isobutene conversion was calculated by measuring the total flow rates of n-butane and isobutene with mass flow meters.
  • the isobutene conversion was re-checked by the analysis of gas- phase effluent by using a GC.
  • the liquid product, after trapping using a cold trap, was analyzed by a GC for the composition of dimers, trimers and tetramers.
  • EXAMPLE 6 The oligomerization was carried out as Example 5, except that the isobutene WHSV was increased to 50 h "1 instead of the isobutene WHSV of 10 h "1 .
  • the isobutene conversion, trimers selectivity and dimers selectivity were 94.7%, 57.6 wt% and 30.7wt%, respectively, after 12 h of reaction even under high space velocity.
  • Detailed reaction conditions and reaction results are summarized in Table 2.
  • Catalyst basket containing 0.5 g of Pd (5%) /C was mounted on the stirring shaft. The reactor temperature was maintained at
  • the oligomerization was carried out as Example 5, except that H-mordenite catalyst was used instead of H-beta catalyst.
  • Detailed reaction conditions and reaction results are summarized in Table 2. It was confirmed that the conversion was low and the trimers selectivity was very low even though the reaction time was very short.
  • the oligomerization of isobutene was carried out at 70 0 C by using a fixed bed reactor containing 2 g of above HY (600) (diameter: 0.2 - 1.0mm, pellet-type), after pressing, and by flowing n-butane and isobutene (1:1 wt ratio) upward.
  • the HY (600) was treated with nitrogen at 300 0 C for 1Oh to remove moisture.
  • 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 hf 1 .
  • the reaction pressure was controlled to be 15 bar by using a back pressure regulator.
  • the reaction temperature was maintained constant by using a liquid circulator. Circulated water at fixed temperature absorbs extra heat generated from the oligomerization .
  • the isobutene conversion was calculated by measuring the total flow rates of n-butane and isobutene with mass flow meters. The isobutene conversion was re-checked by the analysis of gas-phase effluent by using a GC. The liquid product, after trapping using a cold trap, was analyzed by a GC for the composition of dimers, trimers and tetramers. As shown in Fig. 6, through the reaction of 6 h, the reaction was very stable over the catalyst dealuminated under the flow of steam, compared with the HY zeolite without dealumination (C. Ex. 4). Detailed reaction conditions and reaction results are summarized in Fig. 6.
  • the FeCl 3 +HY catalyst of Ex. 9 was heated to 550 0 C with the heating rate of 1 0 C /min and maintained for 6 h at 550 0 C using a furnace.
  • the prepared catalyst was stored after sealing and named as FeCl 3 ZHY.
  • the oligomerization was carried out as Example 8, except that FeCl 3 /HY catalyst was used instead of HY (600) catalyst.
  • the calcined catalyst was cooled, washed for 10 times with
  • the prepared catalyst was stored after sealing and named as Fe/USY. A fixed amount of the catalyst, after pressing, was used in the oligomerization .
  • the oligomerization was carried out as Example 8, except that Fe/USY catalyst was used instead of HY( ⁇ OO) catalyst.
  • the reaction stability was highly improved, compared with the stability over USY (C. Ex. 5, without the loading of FeCl 3 and treatment) through reaction for 20 h.
  • Detailed reaction conditions and reaction results are summarized in Table 3, and the isobutene conversion with reaction time is shown in Fig. 7.
  • the catalyst was synthesized as Example 10, except that
  • the obtained catalyst was named as beta (500) .
  • the isobutene conversion and trimers yield were 99.9% and 57.9%, respectively, after 70 h of reaction time.
  • Table 3 Detailed reaction conditions and reaction results are summarized in Table 3.
  • Oligomerization was carried out as Example 8, except that a dealuminated ferrierite catalyst was used instead of the HY zeolite.
  • the obtained catalyst was named as ferrierite (500) .
  • the isobutene conversion and trimers yield were 99.1% and 60.9%, respectively, after 70 h of reaction time.
  • Table 3 Detailed reaction conditions and reaction results are summarized in Table 3.
  • EXAMPLE 15 Hydrogenation Ten (10) grams of trimers, obtained in Example 13 and purified with distillation, were loaded in a continuous stirred reactor. Cyclohexane (90 g) was added as a solvent. Catalyst basket containing 0.5 g of Pd (5%) /C was mounted on the stirring shaft. The reactor temperature was maintained at 100 0 C and the reactor pressure was raised to 10 atm by using hydrogen. The hydrogenation was started by the onset of agitation, and the reactor pressure was maintained constant (10 atm) by using a back pressure regulator. After reaction for 1 h, the product was separated from cyclohexane by distillation. By the analysis using GC/mass spectrometry, it was confirmed that the conversion of olefins to paraffins was 99.5%, and a heavy alkylate was successfully obtained.
  • COMPARATIVE EXAMPLE 4 The oligomerization was carried out as Example 8, except that HY catalyst was used without dealumination. As shown in Fig. 6, the catalyst stability was low and the isobutene conversion after 6 h of reaction was very low. Detailed reaction conditions and reaction results are summarized in Table 3. The isobutene conversion with reaction time is shown in Fig. 6.
  • the oligomerization was carried out as Example 11, except that USY catalyst was used without loading of FeCl 3 , heat treatment and water-washing. As shown in Fig. 7, the catalyst activity was decreased quite rapidly.
  • Detailed reaction conditions and reaction results are summarized in Table 3. The isobutene conversion with reaction time is shown in Fig. 7.
  • the present process for preparing olefin trimers is performed by use of zeolites having cross linking pores.
  • olefin trimerization reaction with higher conversion, especially high stability and high yield, can be carried out by composite acid catalysts having both Bronsted acid and Lewis acids; or by composite acid catalysts that are post-treated by calcination, water-washing, etc.
  • the olefin trimers thus obtained can be used for preparing neo- acid or can be hydrogenated to heavy alkylate that is used for a prime solvent or diesel additive.

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Abstract

La présente invention concerne un procédé de préparation d'oligomères d'oléfine, et, plus particulièrement, un procédé de préparation de trimères d'oléfine à haute sélectivité. L'oligomérisation est effectuée avec un catalyseur tel qu'un zéolithe doté de pores de réticulation; un catalyseur acide composite contenant à la fois de l'acide de Brönsted et de l'acide de Lewis; ou un catalyseur composite post-traité par calcination et/ou par lavage à l'eau. La présente invention concerne un procédé de préparation d'alkylats lourds par hydrogénation des trimères oléfiniques ainsi formés.
PCT/KR2007/001159 2006-03-10 2007-03-09 Procédé de préparation de trimères d'oléfine légers et production d'alkylats lourds à partir de ces derniers WO2007105875A1 (fr)

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KR10-2006-0022782 2006-03-10
KR1020060022782A KR100718014B1 (ko) 2006-03-10 2006-03-10 제올라이트를 이용한 올레핀의 삼량체 제조방법 및 그를이용한 고비점알킬레이트 제조 방법
KR1020060038895A KR100757031B1 (ko) 2006-04-28 2006-04-28 제올라이트를 이용한 올레핀 삼량체 제조방법 및 그를이용한 고비점알킬레이트 제조 방법
KR10-2006-0038895 2006-04-28
KR10-2006-0086303 2006-09-07
KR1020060086303A KR100786613B1 (ko) 2006-09-07 2006-09-07 올레핀 삼량체 제조 방법 및 그를 이용한 고비점알킬레이트제조 방법

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9616417B2 (en) 2011-07-22 2017-04-11 Haldor Topsoe A/S Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst
CN106582858A (zh) * 2016-12-20 2017-04-26 沈阳化工研究院有限公司 一种制备α‑烯烃低聚物的催化剂及其聚合方法
CN107754852A (zh) * 2017-10-24 2018-03-06 丹东明珠特种树脂有限公司 异丁烯叠合反应的阳离子交换树脂改性催化剂及其改性方法
CN116532158A (zh) * 2023-06-30 2023-08-04 烟台大学 一种负载Cu的β分子筛催化剂及其制备方法
WO2024112843A1 (fr) * 2022-11-23 2024-05-30 Braskem S.A. Utilisation d'un catalyseur zéolithique sous forme de protons pour produire du polyisobutylène léger

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Publication number Priority date Publication date Assignee Title
WO2001027067A1 (fr) * 1999-10-07 2001-04-19 Arco Chemical Technology, L.P. Preparation d'alkylester tertiaire
US6703356B1 (en) * 2000-03-23 2004-03-09 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluids
US20050013774A1 (en) * 2001-09-28 2005-01-20 Dakka Jihad Mohammed Crystalline molecular sieves
US20050197256A1 (en) * 2002-04-30 2005-09-08 Carl Dunlop Process for reducing the toxicity of hydrocarbons

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001027067A1 (fr) * 1999-10-07 2001-04-19 Arco Chemical Technology, L.P. Preparation d'alkylester tertiaire
US6703356B1 (en) * 2000-03-23 2004-03-09 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluids
US20050013774A1 (en) * 2001-09-28 2005-01-20 Dakka Jihad Mohammed Crystalline molecular sieves
US20050197256A1 (en) * 2002-04-30 2005-09-08 Carl Dunlop Process for reducing the toxicity of hydrocarbons

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9616417B2 (en) 2011-07-22 2017-04-11 Haldor Topsoe A/S Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst
CN106582858A (zh) * 2016-12-20 2017-04-26 沈阳化工研究院有限公司 一种制备α‑烯烃低聚物的催化剂及其聚合方法
CN106582858B (zh) * 2016-12-20 2019-08-27 沈阳化工研究院有限公司 一种制备α-烯烃低聚物的催化剂及其聚合方法
CN107754852A (zh) * 2017-10-24 2018-03-06 丹东明珠特种树脂有限公司 异丁烯叠合反应的阳离子交换树脂改性催化剂及其改性方法
WO2024112843A1 (fr) * 2022-11-23 2024-05-30 Braskem S.A. Utilisation d'un catalyseur zéolithique sous forme de protons pour produire du polyisobutylène léger
CN116532158A (zh) * 2023-06-30 2023-08-04 烟台大学 一种负载Cu的β分子筛催化剂及其制备方法

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