WO2011114707A1 - Catalyst for olefin oligomerization reaction - Google Patents

Catalyst for olefin oligomerization reaction Download PDF

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WO2011114707A1
WO2011114707A1 PCT/JP2011/001499 JP2011001499W WO2011114707A1 WO 2011114707 A1 WO2011114707 A1 WO 2011114707A1 JP 2011001499 W JP2011001499 W JP 2011001499W WO 2011114707 A1 WO2011114707 A1 WO 2011114707A1
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catalyst
olefin
reaction
isobutene
butene
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PCT/JP2011/001499
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French (fr)
Japanese (ja)
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山川　文雄
金昌 古沢
雅俊 丸木
亜紀子 辰己
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出光興産株式会社
第一稀元素化学工業株式会社
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Priority to CN2011800142098A priority Critical patent/CN102791372A/en
Priority to KR1020127024021A priority patent/KR20120136363A/en
Priority to JP2012505505A priority patent/JP5746144B2/en
Publication of WO2011114707A1 publication Critical patent/WO2011114707A1/en

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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • 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
    • C07C2/10—Catalytic processes with metal oxides
    • 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
    • C07C2/24—Catalytic processes with metals
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
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    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
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    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a catalyst for olefin oligomerization reaction. More specifically, the present invention relates to a catalyst capable of selectively producing an oligomer of isobutene from a mixed C4 fraction.
  • Olefin oligomers are useful compounds that are widely used as raw materials for fuel oils such as gasoline and diesel, lubricating oils, solvents, and other chemicals.
  • isobutene oligomers are dimers such as 2,4,4-trimethyl-1-pentene or 2,4,4-trimethyl-2-pentene (commonly known as diisobutylene), which is a high octane gasoline base material. It is particularly useful as a raw material for lubricants and chemicals.
  • isobutene oligomers are particularly useful as raw materials for isoparaffin solvents and the like.
  • butene oligomers are obtained by polymerizing the remaining fraction obtained by extracting butadiene from the C4 fraction produced by naphtha decomposition (so-called spent BB fraction) or butane-butene mixed (BB) fraction as raw materials.
  • the resulting liquid polymer mixture has a molecular weight of about 100 to 2500.
  • a method for producing a butene oligomer various methods using an acid catalyst are known.
  • a homogeneous acid catalyst process there is a method in which a raw material consisting of a BB fraction is passed through a liquid slurry in which a Friedel-Craft catalyst such as anhydrous aluminum chloride is suspended (see, for example, Patent Document 1).
  • a heterogeneous solid catalyst process there is a method of contacting a solid catalyst made of dry chlorinated alumina (see, for example, Patent Document 2).
  • a method of contacting with a solid catalyst such as fluorinated alumina, alumina boron, silica alumina, solid phosphoric acid, chromium oxide, zinc oxide, zeolite, ion exchange resin, heteropolyacid, zirconia, etc. is known (for example, patent document). 3 and 4).
  • homogeneous Lewis acid catalysts such as aluminum chloride, boron trifluoride and sulfuric acid are used in homogeneous catalysts, they have industrial problems such as waste catalyst treatment and corrosion of manufacturing equipment.
  • heterogeneous solid catalysts silica alumina, phosphate diatomaceous earth, zeolite catalyst, etc. are used. Therefore, practical reaction conditions depend on the progress of side reactions such as isomerization, decomposition, and heavy product. A major problem is a decrease in economy and a significant decrease in activity due to the deposition of these products on the catalytic active sites.
  • Industrially, the standard method process and the Kosden process have been put to practical use as the aluminum chloride method, but there are problems in terms of waste catalyst treatment and equipment corrosion.
  • n-butenes since n-butenes reacted, other than the target product was produced. Since oligomers of n-butenes and oligomers produced by the reaction of isobutene and n-butenes have a different chemical structure from isobutene oligomers, various physical properties (boiling point, flash point, solubility, etc.) Etc.).
  • An object of the present invention is to provide a catalyst for oligomerization reaction that can selectively produce isobutene oligomer by selectively reacting isobutene.
  • the following catalysts for oligomerization reaction of olefins and the like are provided.
  • Olefin oligomer obtained by firing tungsten carrier (W) or molybdenum (Mo) supported on an oxide carrier obtained by combining titania (TiO 2 ) or silica (SiO 2 ) with zirconia (ZrO 2 ). Catalyst for chemical reaction.
  • a method for producing an olefin oligomer comprising a step of bringing a raw material olefin into contact with the olefin oligomerization reaction catalyst according to any one of 1 to 3 above. 5.
  • an oligomerization reaction catalyst capable of efficiently producing an isobutene oligomer from a raw olefin containing isobutene.
  • the catalyst for oligomerization reaction of an olefin of the present invention is a composite oxide support in which titania (TiO 2 ) or silica (SiO 2 ) is composited with zirconia (ZrO 2 ), tungsten (W) or molybdenum (Mo). The supported one is fired.
  • the composite oxide support, TiO 2 or SiO 2 compositional ratio ZrO 2 [TiO 2 / ZrO 2 , SiO 2 / ZrO 2 (mol)] is 1 / 9-9 / 1 is preferred. More preferably, it is 2/8 to 6/4, and further preferably 3/7 to 4/6.
  • composition ratio of TiO 2 or SiO 2 is less than 1/9, the effect of adding (compositing) TiO 2 or SiO 2 is not sufficiently exhibited.
  • the ratio is larger than 9/1, the interaction between W or Mo to be supported and ZrO 2 is lowered, and the catalytic activity is lowered.
  • the composition of ZrO 2 and TiO 2 or SiO 2 in the composite oxide support can be controlled by the raw material ratio at the time of preparing the support. For example, it can be controlled by measuring and mixing raw materials such as zirconium nitrate, zirconium oxychloride, titanium tetrachloride, titanium sulfate, sodium silicate, and silica powder in terms of oxides.
  • the amount of W or Mo supported on the composite oxide support is preferably 1 to 30 wt%, particularly 2 to 20 wt%, more preferably 10 to 15 wt% in terms of oxide (WO 3 or MoO 3 ). % Is preferred. Outside the above range, the activity may decrease and the efficiency may deteriorate.
  • the method for supporting W or Mo on the composite oxide support is not particularly limited, and methods known in the art, for example, an impregnation method, a coprecipitation method, an adsorption method and the like can be used.
  • a compound containing a W element or a Mo element may be mixed with a precursor of a composite oxide carrier, for example, a mixture of zirconium and titanium or silicon hydroxide. Even if this mixture is calcined, the catalyst of the present invention is obtained.
  • the compound containing W element or Mo element include ammonium tungstate, sodium tungstate, ammonium molybdate, sodium molybdate, and the like.
  • the composite oxide carrier carrying W or Mo is fired to obtain the reaction catalyst of the present invention.
  • the firing temperature is preferably 300 to 1000 ° C, particularly preferably 400 to 800 ° C, and more preferably 500 to 600 ° C.
  • the temperature is lower than 300 ° C, the catalyst is not acidified.
  • the temperature exceeds 1000 ° C, the specific surface area of the catalyst is reduced or the metal component is liable to sublimate.
  • the obtained catalyst may be used as a powder or may be used after molding.
  • the molding method include compression, extrusion, and tableting.
  • a binder can be used as necessary, and the binder may be organic or inorganic (alumina, silica, etc.).
  • the reaction catalyst of the present invention can reduce the bulk density of the catalyst. W) The amount used can be reduced. Therefore, the catalyst cost can be reduced.
  • the moldability of the catalyst is good, and there is a feature that it is easy to obtain industrially required molding strength.
  • the olefin oligomerization reaction catalyst of the present invention is an olefin having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, particularly preferably an aliphatic olefin such as an ⁇ -olefin, an internal olefin, or a branched olefin.
  • butenes include (1-butene, trans-2-butene, cis-2-butene, isobutene).
  • a mixed raw material containing isobutene for example, a C4 fraction (referred to as BB, Raffinate, etc.) produced as a by-product from naphtha decomposition or the like is preferable because it has a characteristic of selectively reacting a branched olefin.
  • Olefin oligomerization can be carried out by bringing the raw material olefin into contact with the above-described catalyst for olefin oligomerization reaction of the present invention.
  • the reaction type may be either a continuous flow type or a batch type.
  • One reactor may be used, but two or more reactors may be used in combination in series or in parallel.
  • the reaction temperature varies depending on the type of raw material olefin and the catalyst used, but is usually 30 to 200 ° C., preferably 40 to 150 ° C., particularly preferably 50 to 100 ° C. If it is less than 30 degreeC, reaction rate may become slow and a conversion rate may fall.
  • the reaction pressure may be any pressure that can maintain the liquid phase, and is usually atmospheric pressure to 10 MPa, preferably 1 to 7 MPa, particularly preferably 2 to 5 MPa.
  • LHSV volumetric liquid space velocity
  • the catalyst concentration in the batch system is preferably 0.01 to 10 wt%, more preferably 0.1 to 5 wt%, and particularly preferably 0.5 to 2 wt% with respect to the raw material olefin. If the amount is too small, the reaction rate decreases and the productivity decreases. If the amount is too large, the conversion rate of n-butene increases, and a large amount of catalyst is consumed, resulting in a decrease in economic efficiency.
  • a solvent may be used or no solvent may be used. When a solvent is used, saturated hydrocarbons such as n-hexane and cyclohexane are preferable. Moreover, the temperature rise by the heat of polymerization can also be suppressed by recycling a part of the reaction product to dilute the reaction substrate.
  • the olefin oligomer containing the dimer, trimer, and tetramer of raw material olefin is obtained.
  • the catalyst for oligomerization reaction of olefin of the present invention can selectively increase the isobutene oligomer. Therefore, when a mixed C4 raw material is polymerized to produce a butene oligomer, an isobutene oligomer is selectively produced and the n-butenes hardly react. Therefore, n-butenes that have not reacted can be efficiently recovered.
  • Example 1 (1) Preparation of catalyst ⁇ Molybdenum oxide-supported titania-zirconia composite oxide catalyst (10 mol% MoO 3 / TiO 2 —ZrO 2 ) Preparation 10wt% zirconium nitrate solution in terms of zirconium oxide 60.7g, 10wt% titanium chloride solution 26.2 g in terms of titanium oxide were fractionated, and these two solutions were mixed. The total amount of the obtained mixed solution was dropped into 700 g of 25% aqueous ammonia to obtain a hydroxide slurry. The hydroxide slurry was separated by filtration and washed thoroughly with ion exchange water as appropriate to obtain a hydroxide from which impurities were removed.
  • Gas phase part / GC CP4900 manufactured by Varian ⁇ Detector: TCD (4ch.) -Column Ch. 1: MS-5A (length 10m) Temperature: 100 ° C., carrier gas: Ar Ch. 2: PoraPLOT-Q (length 10m) Temperature: 80 ° C., carrier gas: He Ch. 3: Al 2 O 3 / KCl (length 10 m) Temperature: 80 ° C., carrier gas: He Ch.
  • the conversion rate and product liquid composition were calculated by the following calculation formulas.
  • the composition of the product liquid was butene trimer (C12) as the main component (61.9%), and the selectivity of isobutene dimer (DIB) in the C8 oligomer was 54.1%.
  • Example 2 A catalyst was prepared in the same manner as in Example 1 except that the catalyst in which the calcination temperature of the catalyst in Example 1 was changed to 800 ° C. was used, and an oligomerization reaction was performed. As a result, 32 hours after the start of the reaction, the isobutene conversion rate was 92.2%, and the n-butene conversion rate at that time was 2.9%.
  • the composition of the product liquid was butene trimer (C12) as the main component (55.6%), and the DIB selectivity in the C8 oligomer was 41.2%.
  • Example 3 A catalyst was prepared in the same manner as in Example 1 except that the amount of ammonium molybdate solution added was changed to 2.4 g in terms of molybdenum oxide.
  • the composition of the obtained catalyst was 2.7 wt% as MoO 3 and 29.3 wt% as TiO 2 .
  • the oligomerization reaction was carried out in the same manner as in Example 1. 8 hours after the start of the reaction, the conversion of isobutene was 93.3%, and the conversion of n-butene at that time was 3.5%.
  • the composition of the product liquid was butene trimer (C12) as the main component (40.4%), but the amount of high oligomers having 20 or more carbon atoms increased.
  • the DIB selectivity in the C8 oligomer was 49.5%.
  • Example 4 (1) Preparation of catalyst-Preparation of tungsten oxide-supported titania-zirconia composite oxide catalyst (10 mol% WO 3 / TiO 2 -ZrO 2 )
  • 5 wt% tungsten instead of ammonium molybdate solution
  • a catalyst was prepared in the same manner as in Example 1 except that 19.6 g of ammonium acid solution was added in terms of tungsten oxide.
  • the composition of the obtained catalyst was 19.6 wt% as WO 3 , 24.3 wt% as TiO 2 , and the remaining 56.1 wt% was Zr (converted to ZrO 2 ).
  • Example 5 Preparation of tungsten oxide-supported silica-zirconia composite oxide catalyst (10 mol% WO 3 / SiO 2 -ZrO 2 ) 10 wt% zirconium nitrate solution in terms of zirconium oxide 77.2 g, 25 wt% sodium silicate solution in terms of silicon dioxide 4.7 g of each was taken and these two solutions were mixed. The total amount of the obtained mixed solution was dropped into 700 g of 25% aqueous ammonia to obtain a hydroxide slurry. The hydroxide slurry was separated by filtration and washed thoroughly with ion exchange water as appropriate to obtain a hydroxide from which impurities were removed.
  • Comparative Example 1 An oligomerization reaction was carried out in the same manner as in Example 1 except that a molybdenum-supported zirconia catalyst (10 mol% MoO 3 / ZrO 2 , manufactured by Daiichi Rare Element Chemical Industries, Ltd.) was used. However, the reaction temperature was 100 ° C. 8 hours after the start of the reaction, the conversion of isobutene was 96.7%, and the n-butene conversion at that time was 8.8%. The conversion rate of isobutene was similar to the results of the TiO 2 composite catalysts of Examples 1 to 3 at a reaction temperature of 50 ° C., and it was found that the activity was dramatically improved by combining with TiO 2 . It is also clear that the TiO 2 composite catalyst has a lower n-butene conversion rate and superior isobutene selectivity.
  • a molybdenum-supported zirconia catalyst 10 mol% MoO 3 / ZrO 2 , manufactured by Daiichi Rare Element Chemical Industries
  • Comparative Example 2 An oligomerization reaction was carried out in the same manner as in Example 4 except that a tungsten-supported zirconia catalyst (10 mol% WO 3 / ZrO 2 , manufactured by Daiichi Rare Element Chemical Co., Ltd.) was used. 16 hours after the start of the reaction, the conversion of isobutene was 93.6%, and the conversion of n-butene at that time was 7.1%. Compared to the TiO 2 or SiO 2 composite catalyst of Examples 4 and 5, the isobutene conversion is similar, but the n-butene conversion is high. Therefore, it is clear that the composite catalyst of the present invention is superior in isobutene selectivity.
  • Comparative Example 3 The same procedure as in Example 1 was performed except that Mo and W were not supported on a titania-zirconia support (40 mol% TiO 2 —ZrO 2 , manufactured by Daiichi Rare Element Chemical Co., Ltd.). It was found that even when the reaction temperature was 100 ° C., the reaction did not proceed at all, and the carrier alone had no activity. That is, it was confirmed that an isobutene oligomerization catalyst having extremely high activity and high selectivity was formed by loading Mo or W on a TiO 2 —ZrO 2 carrier.
  • a titania-zirconia support 40 mol% TiO 2 —ZrO 2 , manufactured by Daiichi Rare Element Chemical Co., Ltd.
  • Comparative Example 4 As a typical solid acid catalyst, an oligomerization reaction was carried out in the same manner as in Example 1 except that an industrially used silica alumina catalyst (SiO 2 90%) was used.
  • the composition of the product liquid was a mixture having butene dimer (C8) and trimer (C12) as main components and various isomer structures.
  • the DIB selectivity in the C8 oligomer was only 12.3%. Also from this result, it was confirmed that the catalysts of the examples had extremely high isobutene selectivity.
  • the composition of the product liquid was a mixture having butene dimer (C8) and trimer (C12) as main components and various isomer structures. Also from this result, it is clear that the catalyst described in the examples has extremely high isobutene selectivity.
  • Example 6 The same catalyst as in Example 1 was used.
  • the oligomerization reaction was performed in the same manner as in Example 1 except that the reaction conditions were changed as follows.
  • -Mixed C4 raw material composition 1-butene 20%, 2-butene 18%, isobutene 48%, butane 13%, others 1% ⁇
  • Raw material flow rate: 40cc / h (LHSV 2)
  • the mixed C4 raw material used in this example is a C4 fraction obtained from an ethylene unit (naphtha cracking) (BBR (butane-butene raffinate) (Raffinate-I) after butadiene extraction).
  • BBR butane-butene raffinate
  • Raffinate-I ethylene unit after butadiene extraction
  • Example 7 The catalyst having the same catalyst composition as in Example 2 was used, and the oligomerization reaction was performed in the same manner as in Example 6. As a result, 64 hours after the start of the reaction, the conversion rate of isobutene was 88.1%, and the conversion rate of n-butene was 4.9%. The DIB selectivity in the C8 oligomer was 88.3%.
  • Comparative Example 6 The same catalyst as in Comparative Example 4 was used, and the oligomerization reaction was performed in the same manner as in Example 6. As a result, 16 hours after the start of the reaction, the isobutene conversion rate was 81.9%, and the n-butene conversion rate at that time was 17.8%. The DIB selectivity in the C8 oligomer was 41.3%. Therefore, it can be seen that the catalyst of this example has very high isobutene selectivity.
  • Table 1 below shows the results of Examples 1 to 7 and Comparative Examples 1 to 6.
  • the olefin oligomerization reaction catalyst of the present invention can be suitably used for the production of olefin oligomers, particularly isobutene oligomers.

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Abstract

A catalyst for an olefin oligomerization reaction, which is produced by supporting tungsten (W) or molybdenum (Mo) on an oxide carrier that is a complex of zirconia (ZrO2) and titania (TiO2) or silica (SiO2) and burning the supported product.

Description

オレフィンのオリゴマー化反応用触媒Olefin oligomerization catalyst
　本発明は、オレフィンのオリゴマー化反応用触媒に関する。さらに詳しくは、混合Ｃ４留分からイソブテンのオリゴマーを選択的に製造することができる触媒に関する。 The present invention relates to a catalyst for olefin oligomerization reaction. More specifically, the present invention relates to a catalyst capable of selectively producing an oligomer of isobutene from a mixed C4 fraction.
　オレフィンオリゴマーは、ガソリン、ディーゼル等の燃料油、潤滑油、溶剤、その他化学品の原料として、幅広く使用されている有用な化合物である。なかでも、イソブテンオリゴマーは、例えば、２量体である２，４，４－トリメチル－１－ペンテン又は２，４，４－トリメチル－２－ペンテン（通称、ジイソブチレン）は、高オクタン価ガソリン基材や潤滑油・化学品の原料等として特に有用である。３量体や４量体においても、イソブテンオリゴマーはイソパラフィン溶剤等の原料として特に有用である。 Olefin oligomers are useful compounds that are widely used as raw materials for fuel oils such as gasoline and diesel, lubricating oils, solvents, and other chemicals. Among them, isobutene oligomers are dimers such as 2,4,4-trimethyl-1-pentene or 2,4,4-trimethyl-2-pentene (commonly known as diisobutylene), which is a high octane gasoline base material. It is particularly useful as a raw material for lubricants and chemicals. Also in trimers and tetramers, isobutene oligomers are particularly useful as raw materials for isoparaffin solvents and the like.
　ブテンオリゴマーは、一般に、ナフサ分解で生成するＣ４留分からブタジエンを抽出した残りの留分（いわゆるスペントＢＢ留分）、又はブタン－ブテン混合（ＢＢ）留分を原料として用い、これらを重合させて得られた分子量が１００～２５００程度の液状ポリマーの混合物である。 Generally, butene oligomers are obtained by polymerizing the remaining fraction obtained by extracting butadiene from the C4 fraction produced by naphtha decomposition (so-called spent BB fraction) or butane-butene mixed (BB) fraction as raw materials. The resulting liquid polymer mixture has a molecular weight of about 100 to 2500.
　ブテンオリゴマーの製造方法としては、酸触媒を用いる様々な方法が知られている。例えば、均一系酸触媒プロセスとして、ＢＢ留分からなる原料を、無水塩化アルミニウム等のフリーデル・クラフト触媒を懸濁させた液体スラリーに通す方法がある（例えば、特許文献１参照）。また、不均一系固体触媒プロセスとして、乾燥塩素化アルミナからなる固体触媒に接触させる方法がある（例えば、特許文献２参照）。さらに、フッ素化アルミナ、アルミナホウ素、シリカアルミナ、固体リン酸、酸化クロム、酸化亜鉛、ゼオライト、イオン交換樹脂、ヘテロポリ酸、ジルコニア等の固体触媒に接触させる方法が知られている（例えば、特許文献３、４参照）。 As a method for producing a butene oligomer, various methods using an acid catalyst are known. For example, as a homogeneous acid catalyst process, there is a method in which a raw material consisting of a BB fraction is passed through a liquid slurry in which a Friedel-Craft catalyst such as anhydrous aluminum chloride is suspended (see, for example, Patent Document 1). Further, as a heterogeneous solid catalyst process, there is a method of contacting a solid catalyst made of dry chlorinated alumina (see, for example, Patent Document 2). Furthermore, a method of contacting with a solid catalyst such as fluorinated alumina, alumina boron, silica alumina, solid phosphoric acid, chromium oxide, zinc oxide, zeolite, ion exchange resin, heteropolyacid, zirconia, etc. is known (for example, patent document). 3 and 4).
　しかしながら、均一系触媒では、塩化アルミニウム、三弗化硼素、硫酸等の強ルイス酸触媒が用いられているため、廃触媒処理や製造装置の腐食等の工業的問題を有している。
　一方、不均一系固体触媒では、シリカアルミナ、燐酸珪藻土、ゼオライト触媒等が用いられているため、実用的な反応条件化では、異性化、分解、生成物の重質化といった副反応の進行による経済性の低下と、それら生成物の触媒活性点への堆積による著しい活性低下が大きな課題である。
　尚、工業的には塩化アルミ法としてスタンダード法プロセスやコスデン法プロセスが実用化されているが、廃触媒処理や装置腐食等の点で問題がある。 However, since homogeneous Lewis acid catalysts such as aluminum chloride, boron trifluoride and sulfuric acid are used in homogeneous catalysts, they have industrial problems such as waste catalyst treatment and corrosion of manufacturing equipment.
On the other hand, in the case of heterogeneous solid catalysts, silica alumina, phosphate diatomaceous earth, zeolite catalyst, etc. are used. Therefore, practical reaction conditions depend on the progress of side reactions such as isomerization, decomposition, and heavy product. A major problem is a decrease in economy and a significant decrease in activity due to the deposition of these products on the catalytic active sites.
Industrially, the standard method process and the Kosden process have been put to practical use as the aluminum chloride method, but there are problems in terms of waste catalyst treatment and equipment corrosion.
　また、触媒反応によって得られるオリゴマー組成に関して、従来の製造方法では、いずれの触媒系も、原料組成とブテン転化率が決まれば、各オリゴマーの生成割合と異性体組成はほぼ決定されるため、イソブテンのみを選択的にオリゴマー化して、イソブテンオリゴマーのみの収率を増加させることができないという問題があった。即ち、混合Ｃ４留分中のイソブテンとｎ－ブテン類は、ある特定の割合（反応速度比）でオリゴマー化されるため、ｎ－ブテン類をオリゴマー化せずにイソブテンオリゴマーのみを製造したい場合においても、ｎ－ブテン類が反応するため、目的物以外のものが生成していた。ｎ－ブテン類のオリゴマーや、イソブテンとｎ－ブテン類が反応して生成したオリゴマー類は、イソブテンオリゴマーとは化学構造が異なるため、溶剤等として用いる場合、各種物性（沸点、引火点、溶解性等）にも影響する。 In addition, regarding the oligomer composition obtained by catalytic reaction, in the conventional production method, since the formation ratio and isomer composition of each oligomer are almost determined in any catalyst system if the raw material composition and the butene conversion rate are determined, isobutene There was a problem that it was not possible to selectively oligomerize only, and increase the yield of isobutene oligomer alone. That is, since isobutene and n-butenes in the mixed C4 fraction are oligomerized at a specific ratio (reaction rate ratio), when it is desired to produce only isobutene oligomers without oligomerizing n-butenes. However, since n-butenes reacted, other than the target product was produced. Since oligomers of n-butenes and oligomers produced by the reaction of isobutene and n-butenes have a different chemical structure from isobutene oligomers, various physical properties (boiling point, flash point, solubility, etc.) Etc.).
特開昭６０－１２４６０２号公報JP 60-124602 A 特開昭５７－８２３２５号公報JP-A-57-82325 特開昭５６－４０６１８号公報JP-A-56-40618 特開２００５－１５３８４号公報JP 2005-15384 A
　本発明の目的は、イソブテンを選択的に反応させ、イソブテンオリゴマーを効率的に製造できるオリゴマー化反応用触媒を提供することである。 An object of the present invention is to provide a catalyst for oligomerization reaction that can selectively produce isobutene oligomer by selectively reacting isobutene.
　本発明によれば、以下のオレフィンのオリゴマー化反応用触媒等が提供される。
１．ジルコニア（ＺｒＯ２）に、チタニア（ＴｉＯ２）又はシリカ（ＳｉＯ２）を複合化した酸化物担体に、タングステン（Ｗ）又はモリブデン（Ｍｏ）を担持したものを焼成して得られる、オレフィンのオリゴマー化反応用触媒。
２．前記複合酸化物担体へのＷ又はＭｏの担持量が、酸化物換算（ＷＯ３又はＭｏＯ３）で１～３０ｗｔ％である１に記載のオレフィンのオリゴマー化反応用触媒。
３．前記オレフィン中の、分岐型オレフィンを選択的にオリゴマー化する１又は２に記載のオレフィンのオリゴマー化反応用触媒。
４．上記１～３のいずれかに記載のオレフィンのオリゴマー化反応用触媒に、原料オレフィンを接触させる工程を有する、オレフィンオリゴマーの製造方法。
５．前記原料オレフィンが、炭素数４～１２のオレフィン類である４に記載のオレフィンオリゴマーの製造方法。
６．前記原料オレフィンが、ナフサ分解等から副生するＣ４留分である４に記載のオレフィンオリゴマーの製造方法。
７．上記４～６のいずれかに記載のオレフィンオリゴマーの製造方法により得られ、原料オレフィンの２量体、３量体及び４量体を含むオレフィンオリゴマー。 According to the present invention, the following catalysts for oligomerization reaction of olefins and the like are provided.
1. Olefin oligomer obtained by firing tungsten carrier (W) or molybdenum (Mo) supported on an oxide carrier obtained by combining titania (TiO 2 ) or silica (SiO 2 ) with zirconia (ZrO 2 ). Catalyst for chemical reaction.
2. 2. The catalyst for olefin oligomerization reaction according to 1, wherein the amount of W or Mo supported on the composite oxide support is 1 to 30 wt% in terms of oxide (WO 3 or MoO 3 ).
3. 3. The catalyst for olefin oligomerization reaction according to 1 or 2, which selectively oligomerizes a branched olefin in the olefin.
4). A method for producing an olefin oligomer, comprising a step of bringing a raw material olefin into contact with the olefin oligomerization reaction catalyst according to any one of 1 to 3 above.
5. 5. The method for producing an olefin oligomer according to 4, wherein the raw material olefin is an olefin having 4 to 12 carbon atoms.
6). 5. The method for producing an olefin oligomer according to 4, wherein the raw material olefin is a C4 fraction by-produced from naphtha cracking or the like.
7). An olefin oligomer obtained by the method for producing an olefin oligomer according to any one of 4 to 6 above and comprising a dimer, trimer and tetramer of raw material olefins.
　本発明によれば、イソブテンを含有する原料オレフィンから、イソブテンオリゴマーを効率的に製造できるオリゴマー化反応用触媒を提供することが提供できる。 According to the present invention, it is possible to provide an oligomerization reaction catalyst capable of efficiently producing an isobutene oligomer from a raw olefin containing isobutene.
　本発明のオレフィンのオリゴマー化反応用触媒は、ジルコニア（ＺｒＯ２）に、チタニア（ＴｉＯ２）又はシリカ（ＳｉＯ２）を複合化した複合酸化物担体に、タングステン（Ｗ）又はモリブデン（Ｍｏ）を担持したものを焼成したものである。
　複合酸化物担体について、ＺｒＯ２に対するＴｉＯ２又はＳｉＯ２の組成比［ＴｉＯ２／ＺｒＯ２、ＳｉＯ２／ＺｒＯ２（ｍｏｌ）］は、１／９～９／１が好ましい。より好ましくは、２／８～６／４であり、さらに好ましくは３／７～４／６である。ＴｉＯ２又はＳｉＯ２の組成比が１／９未満では、ＴｉＯ２やＳｉＯ２の添加（複合化）効果が充分に発現しない。一方、９／１より大きいと担持させるＷ又はＭｏと、ＺｒＯ２との相互作用が低下して触媒活性が低下する。 The catalyst for oligomerization reaction of an olefin of the present invention is a composite oxide support in which titania (TiO 2 ) or silica (SiO 2 ) is composited with zirconia (ZrO 2 ), tungsten (W) or molybdenum (Mo). The supported one is fired.
The composite oxide support, TiO 2 or SiO 2 compositional ratio ZrO 2 [TiO 2 / ZrO 2 , SiO 2 / ZrO 2 (mol)] is 1 / 9-9 / 1 is preferred. More preferably, it is 2/8 to 6/4, and further preferably 3/7 to 4/6. When the composition ratio of TiO 2 or SiO 2 is less than 1/9, the effect of adding (compositing) TiO 2 or SiO 2 is not sufficiently exhibited. On the other hand, when the ratio is larger than 9/1, the interaction between W or Mo to be supported and ZrO 2 is lowered, and the catalytic activity is lowered.
　複合酸化物担体におけるＺｒＯ２及びＴｉＯ２又はＳｉＯ２の組成は、担体調製時の原料比によって制御できる。例えば、原料となる、硝酸ジルコニウム、オキシ塩化ジルコニウム、四塩化チタン、硫酸チタン、ケイ酸ナトリウム、シリカ粉末等を酸化物換算で計量し、混合することにより制御できる。 The composition of ZrO 2 and TiO 2 or SiO 2 in the composite oxide support can be controlled by the raw material ratio at the time of preparing the support. For example, it can be controlled by measuring and mixing raw materials such as zirconium nitrate, zirconium oxychloride, titanium tetrachloride, titanium sulfate, sodium silicate, and silica powder in terms of oxides.
　複合酸化物担体へのＷ又はＭｏの担持量は、酸化物（ＷＯ３又はＭｏＯ３）換算で１～３０ｗｔ％であることが好ましく、特に２～２０ｗｔ％であることが好ましく、さらに１０～１５ｗｔ％であることが好ましい。上記範囲外では、活性が低下して効率が悪くなるおそれがある。 The amount of W or Mo supported on the composite oxide support is preferably 1 to 30 wt%, particularly 2 to 20 wt%, more preferably 10 to 15 wt% in terms of oxide (WO 3 or MoO 3 ). % Is preferred. Outside the above range, the activity may decrease and the efficiency may deteriorate.
　複合酸化物担体にＷ又はＭｏの担持させる方法は、特に限定はなく、本技術分野で公知である方法、例えば、含浸法、共沈法、吸着法等を用いることができる。
　尚、複合酸化物担体の前駆体、例えば、ジルコニウム及びチタン又はケイ素の水酸化物の混合物に、Ｗ元素又はＭｏ元素を含有する化合物を混合してもよい。この混合物を焼成しても本発明の触媒が得られる。
　Ｗ元素又はＭｏ元素を含有する化合物としては、例えば、タングステン酸アンモニウム、タングステン酸ナトリウム、モリブデン酸アンモニウム、モリブデン酸ナトリウム等が使用できる。 The method for supporting W or Mo on the composite oxide support is not particularly limited, and methods known in the art, for example, an impregnation method, a coprecipitation method, an adsorption method and the like can be used.
A compound containing a W element or a Mo element may be mixed with a precursor of a composite oxide carrier, for example, a mixture of zirconium and titanium or silicon hydroxide. Even if this mixture is calcined, the catalyst of the present invention is obtained.
Examples of the compound containing W element or Mo element include ammonium tungstate, sodium tungstate, ammonium molybdate, sodium molybdate, and the like.
　Ｗ又はＭｏを担持させた複合酸化物担体を焼成し、本発明の反応用触媒とする。焼成温度は３００～１０００℃が好ましく、特に４００℃～８００℃が好ましく、さらに５００～６００℃が好ましい。３００℃よりも低いと触媒が酸性化せず、一方、１０００℃を超えると触媒の比表面積が低下したり、金属成分の昇華が起こりやすいため、活性が低下することがある。 The composite oxide carrier carrying W or Mo is fired to obtain the reaction catalyst of the present invention. The firing temperature is preferably 300 to 1000 ° C, particularly preferably 400 to 800 ° C, and more preferably 500 to 600 ° C. When the temperature is lower than 300 ° C, the catalyst is not acidified. On the other hand, when the temperature exceeds 1000 ° C, the specific surface area of the catalyst is reduced or the metal component is liable to sublimate.
　得られた触媒は粉末のままで使用してもよく、成型して使用してもよい。成型方法としては、圧縮、押し出し、打錠等の方法がある。
　必要に応じてバインダーを用いることもでき、バインダーは有機系、無機系（アルミナ、シリカ等）のいずれを用いてもよい。
　本発明の反応用触媒は、ＴｉＯ２又はＳｉＯ２を添加しないＺｒＯ２にＭｏ又はＷを担持させた触媒と比較して、触媒の嵩密度を軽くすることができ、体積当りの金属（Ｍｏ，Ｗ）使用量を減らすことができる。従って、触媒コストの低減が可能となる。また、触媒の成型性もよく、工業的に必要な成型強度が得やすいという特徴もある。 The obtained catalyst may be used as a powder or may be used after molding. Examples of the molding method include compression, extrusion, and tableting.
A binder can be used as necessary, and the binder may be organic or inorganic (alumina, silica, etc.).
Compared with a catalyst in which Mo or W is supported on ZrO 2 to which TiO 2 or SiO 2 is not added, the reaction catalyst of the present invention can reduce the bulk density of the catalyst. W) The amount used can be reduced. Therefore, the catalyst cost can be reduced. In addition, the moldability of the catalyst is good, and there is a feature that it is easy to obtain industrially required molding strength.
　本発明のオレフィンのオリゴマー化反応用触媒は、炭素数４～１２、好ましくは炭素数４～８、特に好ましくは炭素数４のオレフィン類（α－オレフィン、内部オレフィン、分岐オレフィン等の脂肪族オレフィン）のオリゴマー化に好適に使用できる。ブテン類としては、（１－ブテン、ｔｒａｎｓ－２－ブテン、ｃｉｓ－２－ブテン、イソブテン）等がある。特に、分岐型オレフィンを選択的に反応させる特性があるため、イソブテンを含む混合原料、例えば、ナフサ分解等から副生するＣ４（ＢＢ，Ｒａｆｆｉｎａｔｅ等と呼ばれる）留分が好ましい。 The olefin oligomerization reaction catalyst of the present invention is an olefin having 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, particularly preferably an aliphatic olefin such as an α-olefin, an internal olefin, or a branched olefin. ) Can be suitably used for oligomerization. Examples of butenes include (1-butene, trans-2-butene, cis-2-butene, isobutene). In particular, a mixed raw material containing isobutene, for example, a C4 fraction (referred to as BB, Raffinate, etc.) produced as a by-product from naphtha decomposition or the like is preferable because it has a characteristic of selectively reacting a branched olefin.
　オレフィンのオリゴマー化は、上述した本発明のオレフィンのオリゴマー化反応用触媒に、原料オレフィンを接触させることにより実施できる。
　反応型式は連続流通式でも回分式でもどちらでもよい。反応器は一つでもよいが、二つ以上を直列又は並列に組み合わせて使うこともできる。
　反応温度は、原料オレフィンの種類や用いる触媒によって異なるが、通常、３０～２００℃であり、好ましくは４０～１５０℃、特に好ましくは５０～１００℃である。３０℃未満では、反応速度が遅くなり、転化率が低下することがある。２００℃超では、ｎ－ブテンのオリゴマー化が進行し、ｎ－ブテンの転化率が上がってしまうことがある。
　反応圧力は、液相を維持できる圧力であればよく、通常、大気圧～１０ＭＰａであり、好ましくは１～７ＭＰａ、特に好ましくは２～５ＭＰａである。 Olefin oligomerization can be carried out by bringing the raw material olefin into contact with the above-described catalyst for olefin oligomerization reaction of the present invention.
The reaction type may be either a continuous flow type or a batch type. One reactor may be used, but two or more reactors may be used in combination in series or in parallel.
The reaction temperature varies depending on the type of raw material olefin and the catalyst used, but is usually 30 to 200 ° C., preferably 40 to 150 ° C., particularly preferably 50 to 100 ° C. If it is less than 30 degreeC, reaction rate may become slow and a conversion rate may fall. If it exceeds 200 ° C., the oligomerization of n-butene proceeds and the conversion of n-butene may increase.
The reaction pressure may be any pressure that can maintain the liquid phase, and is usually atmospheric pressure to 10 MPa, preferably 1 to 7 MPa, particularly preferably 2 to 5 MPa.
　反応時間（連続流通式の場合は液滞留時間）は、２分～１０時間が好ましい（触媒に対する原料供給量は、体積基準の液空間速度（ＬＨＳＶ）で０．１～３０）。特に、好ましくは３分～５時間（ＬＨＳＶ＝０．２～２０）である。さらに好ましくは４分～１時間（ＬＨＳＶ＝１～１５）である。反応時間が短すぎるとイソブテン転化率が低下し、オリゴマー生成量が低下することがある。反応時間が長すぎると、ｎ－ブテンの転化率が上がってしまうことがある。上記反応時間は、触媒量当たり原料が接触する時間を示す。
　回分式の場合の触媒濃度は、原料オレフィンに対して０．０１～１０ｗｔ％が好ましく、０．１～５ｗｔ％がより好ましく、０．５～２ｗｔ％が特に好ましい。少なすぎると、反応速度が低下し、生産性が低下する。多すぎると、ｎ－ブテンの転化率が上がったり、触媒を多量に消費するため経済性が低下する。
　反応には溶媒を使用してもよく、無溶媒でもよい。溶媒を用いる場合は、ｎ－ヘキサン、シクロヘキサン等の飽和炭化水素が好ましい。また、反応生成物の一部をリサイクルして反応基質を希釈することで、重合熱による温度上昇を抑制することもできる。 The reaction time (liquid retention time in the case of a continuous flow system) is preferably 2 minutes to 10 hours (the amount of raw material supplied to the catalyst is 0.1 to 30 in terms of volumetric liquid space velocity (LHSV)). In particular, it is preferably 3 minutes to 5 hours (LHSV = 0.2 to 20). More preferably, it is 4 minutes to 1 hour (LHSV = 1 to 15). If the reaction time is too short, the isobutene conversion rate may decrease and the amount of oligomer formation may decrease. If the reaction time is too long, the conversion of n-butene may increase. The said reaction time shows the time when a raw material contacts per catalyst amount.
The catalyst concentration in the batch system is preferably 0.01 to 10 wt%, more preferably 0.1 to 5 wt%, and particularly preferably 0.5 to 2 wt% with respect to the raw material olefin. If the amount is too small, the reaction rate decreases and the productivity decreases. If the amount is too large, the conversion rate of n-butene increases, and a large amount of catalyst is consumed, resulting in a decrease in economic efficiency.
In the reaction, a solvent may be used or no solvent may be used. When a solvent is used, saturated hydrocarbons such as n-hexane and cyclohexane are preferable. Moreover, the temperature rise by the heat of polymerization can also be suppressed by recycling a part of the reaction product to dilute the reaction substrate.
　上記の反応により、原料オレフィンの２量体、３量体及び４量体を含むオレフィンオリゴマーが得られる。
　本発明のオレフィンのオリゴマー化反応用触媒は、特に、イソブテンオリゴマーを選択的に増加させることができる。従って、混合Ｃ４原料を重合させてブテンオリゴマーを製造すると、イソブテンオリゴマーが選択的に生成し、ｎ－ブテン類はほとんど反応しない。そのため、反応しなかったｎ－ブテン類を効率よく回収できる。 By said reaction, the olefin oligomer containing the dimer, trimer, and tetramer of raw material olefin is obtained.
In particular, the catalyst for oligomerization reaction of olefin of the present invention can selectively increase the isobutene oligomer. Therefore, when a mixed C4 raw material is polymerized to produce a butene oligomer, an isobutene oligomer is selectively produced and the n-butenes hardly react. Therefore, n-butenes that have not reacted can be efficiently recovered.
実施例１
（１）触媒の調製
・酸化モリブデン担持チタニア－ジルコニア複合酸化物触媒（１０ｍｏｌ％ＭｏＯ３／ＴｉＯ２－ＺｒＯ２）の調製
　１０ｗｔ％硝酸ジルコニウム溶液を酸化ジルコニウム換算で６０．７ｇ、１０ｗｔ％塩化チタン溶液を酸化チタン換算で２６．２ｇ、それぞれ分取し、これら２つの溶液を混合した。得られた混合溶液を２５％アンモニア水７００ｇに全量滴下し、水酸化物スラリーを得た。水酸化物スラリーをろ別し、適宜イオン交換水で十分に水洗し、不純物を除去した水酸化物を得た。
　得られた水酸化物に５ｗｔ％のモリブデン酸アンモニウム溶液を酸化モリブデン換算で１３．１ｇ添加し、混練した後、１５０℃で恒量になるまで乾燥した。
　その後、６００℃で焼成し、触媒であるモリブデン担持チタニア－ジルコニア複合酸化物を得た。
　この触媒の組成を蛍光Ｘ線分析（ＸＲＦ）で分析した。各金属成分の含有率は、Ｍｏが１３．１ｗｔ％（ＭｏＯ３換算）、Ｔｉが２６．２ｗｔ％（ＴｉＯ２換算）であり、残りの６０．７ｗｔ％がＺｒ（ＺｒＯ２換算）であった。 Example 1
(1) Preparation of catalyst ・ Molybdenum oxide-supported titania-zirconia composite oxide catalyst (10 mol% MoO 3 / TiO 2 —ZrO 2 ) Preparation 10wt% zirconium nitrate solution in terms of zirconium oxide 60.7g, 10wt% titanium chloride solution 26.2 g in terms of titanium oxide were fractionated, and these two solutions were mixed. The total amount of the obtained mixed solution was dropped into 700 g of 25% aqueous ammonia to obtain a hydroxide slurry. The hydroxide slurry was separated by filtration and washed thoroughly with ion exchange water as appropriate to obtain a hydroxide from which impurities were removed.
13.1 g of 5 wt% ammonium molybdate solution was added to the obtained hydroxide in terms of molybdenum oxide, kneaded, and then dried at 150 ° C. until a constant weight was obtained.
Thereafter, it was calcined at 600 ° C. to obtain a molybdenum-supporting titania-zirconia composite oxide as a catalyst.
The composition of this catalyst was analyzed by X-ray fluorescence analysis (XRF). As for the content of each metal component, Mo was 13.1 wt% (MoO 3 equivalent), Ti was 26.2 wt% (TiO 2 equivalent), and the remaining 60.7 wt% was Zr (ZrO 2 equivalent). .
（２）オリゴマー化反応
　固定床高圧流通反応装置を用いて、上記で調製した触媒の反応成績を調べた。ステンレス製反応管（内径１０ｍｍ、長さ１００ｃｍ）に触媒を２０ｃｃ（１６ｇ）充填し、Ｎ２流通下２５０℃に加熱して前処理した。その後、３ＭＰａ加圧下で、混合Ｃ４原料（１－ブテン１３ｖｏｌ％、２－ブテン２６ｖｏｌ％、イソブテン１２ｖｏｌ％、ブタン４８ｖｏｌ％、その他１ｖｏｌ％）を８０ｃｃ／ｈ（液）の流量で供給した（ＬＨＳＶ＝４）。その後、触媒層内温が５０℃になるよう、反応管ヒーターを調節して反応させた。得られた反応生成物（気相及び液相）の組成を、ガスクロマトグラフを用いて分析した。
　尚、上記混合Ｃ４原料はＦＣＣ（流動接触分解）装置から得られるＣ４留分（ＦＣＣ－ＢＢ）である。 (2) Oligomerization reaction Using a fixed bed high-pressure flow reactor, the reaction results of the catalyst prepared above were examined. A stainless steel reaction tube (inner diameter 10 mm, length 100 cm) was filled with 20 cc (16 g) of catalyst, and pretreated by heating to 250 ° C. under N 2 flow. Thereafter, mixed C4 raw material (1-butene 13 vol%, 2-butene 26 vol%, isobutene 12 vol%, butane 48 vol%, other 1 vol%) was supplied at a flow rate of 80 cc / h (liquid) under a pressure of 3 MPa (LHSV = 4). Thereafter, the reaction was performed by adjusting the reaction tube heater so that the internal temperature of the catalyst layer was 50 ° C. The composition of the obtained reaction product (gas phase and liquid phase) was analyzed using a gas chromatograph.
The mixed C4 raw material is a C4 fraction (FCC-BB) obtained from an FCC (fluid catalytic cracking) apparatus.
　分析には２台のガスクロマトグラフ（ＧＣ）を用いた。「気相部」は主にＣ４異性体の分析に、「液相部」は主にＣ４オリゴマー（Ｃ８～Ｃ２０＋）の分析に用いた。
１．気相部
・ＧＣ：Ｖａｒｉａｎ社製　ＣＰ４９００
・検出器：ＴＣＤ（４ｃｈ．）
・カラム
　Ｃｈ．１：ＭＳ－５Ａ（長さ１０ｍ）
　　　　　　温度：１００℃、キャリアガス：Ａｒ
　Ｃｈ．２：ＰｏｒａＰＬＯＴ－Ｑ（長さ１０ｍ）
　　　　　　温度：８０℃、キャリアガス：Ｈｅ
　Ｃｈ．３：Ａｌ２Ｏ３／ＫＣｌ（長さ１０ｍ）
　　　　　　温度：８０℃、キャリアガス：Ｈｅ
　Ｃｈ．４：ＣＰ－Ｓｉｌｌ　５ＣＢ（長さ８ｍ）
　　　　　　温度：１２０℃、キャリアガス：Ｈｅ
２．液相部
・ＧＣ：Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製　６８５０ＧＣ
・カラム：ＨＰ－１（３０ｍ，０．２５ｍｍ，０．２５μｍ）
　　　　　キャリアガス：Ｈｅ（１．５ｃｃ／ｍｉｎ）
　　　　　注入口温度：２８０℃：Ｓｐｌｉｔ：１／２０
・オーブン：５０℃で５分間保持し、１０℃／ｍｉｎで昇温し、３００℃で１０分間保持した。
・検出器：ＦＩＤ，３００℃ Two gas chromatographs (GC) were used for the analysis. The “gas phase part” was mainly used for analysis of C4 isomers, and the “liquid phase part” was mainly used for analysis of C4 oligomers (C8 to C20 +).
1. Gas phase part / GC: CP4900 manufactured by Varian
・ Detector: TCD (4ch.)
-Column Ch. 1: MS-5A (length 10m)
Temperature: 100 ° C., carrier gas: Ar
Ch. 2: PoraPLOT-Q (length 10m)
Temperature: 80 ° C., carrier gas: He
Ch. 3: Al 2 O 3 / KCl (length 10 m)
Temperature: 80 ° C., carrier gas: He
Ch. 4: CP-Sill 5CB (length 8m)
Temperature: 120 ° C., carrier gas: He
2. Liquid phase part / GC: 6850GC manufactured by Agilent Technologies
Column: HP-1 (30m, 0.25mm, 0.25μm)
Carrier gas: He (1.5 cc / min)
Inlet temperature: 280 ° C .: Split: 1/20
Oven: held at 50 ° C. for 5 minutes, heated at 10 ° C./min, and held at 300 ° C. for 10 minutes.
-Detector: FID, 300 ° C
　転化率、生成液組成は以下の計算式にて算出した。
Figure JPOXMLDOC01-appb-M000001
 The conversion rate and product liquid composition were calculated by the following calculation formulas.
Figure JPOXMLDOC01-appb-M000001
　反応開始から４９時間後、イソブテン転化率は９５．０％で、その時のｎ－ブテン転化率はわずか１．９％しかなく、イソブテンが極めて高選択的にオリゴマー化された。生成液の組成はブテン３量体（Ｃ１２）が主成分であり（６１．９％）、Ｃ８オリゴマー中のイソブテン２量体（ＤＩＢ）の選択率は５４．１％であった。 49 hours after the start of the reaction, the conversion of isobutene was 95.0%, the conversion of n-butene was only 1.9%, and isobutene was oligomerized very highly selectively. The composition of the product liquid was butene trimer (C12) as the main component (61.9%), and the selectivity of isobutene dimer (DIB) in the C8 oligomer was 54.1%.
実施例２
　実施例１の触媒の焼成温度を８００℃に変えた触媒を用いた以外は、実施例１と同様にして触媒を調製し、オリゴマー化反応を実施した。
　その結果、反応開始から３２時間後、イソブテン転化率は９２．２％で、その時のｎ－ブテン転化率は２．９％であった。生成液の組成はブテン３量体（Ｃ１２）が主成分であり（５５．６％）、Ｃ８オリゴマー中のＤＩＢ選択率は４１．２％であった。 Example 2
A catalyst was prepared in the same manner as in Example 1 except that the catalyst in which the calcination temperature of the catalyst in Example 1 was changed to 800 ° C. was used, and an oligomerization reaction was performed.
As a result, 32 hours after the start of the reaction, the isobutene conversion rate was 92.2%, and the n-butene conversion rate at that time was 2.9%. The composition of the product liquid was butene trimer (C12) as the main component (55.6%), and the DIB selectivity in the C8 oligomer was 41.2%.
実施例３
　モリブデン酸アンモニウム溶液の添加量を酸化モリブデン換算で２．４ｇに変更した以外は、実施例１と同様にして触媒を調製した。得られた触媒の組成は、ＭｏＯ３として２．７ｗｔ％、ＴｉＯ２として２９．３ｗｔ％であった。
　また、実施例１と同様にしてオリゴマー化反応を実施した。反応開始から８時間後、イソブテン転化率は９３．３％で、その時のｎ－ブテン転化率は３．５％であった。生成液の組成はブテン３量体（Ｃ１２）が主成分であったが（４０．４％）、炭素数２０以上の高オリゴマーの生成量が増大した。Ｃ８オリゴマー中のＤＩＢ選択率は４９．５％であった。 Example 3
A catalyst was prepared in the same manner as in Example 1 except that the amount of ammonium molybdate solution added was changed to 2.4 g in terms of molybdenum oxide. The composition of the obtained catalyst was 2.7 wt% as MoO 3 and 29.3 wt% as TiO 2 .
Further, the oligomerization reaction was carried out in the same manner as in Example 1. 8 hours after the start of the reaction, the conversion of isobutene was 93.3%, and the conversion of n-butene at that time was 3.5%. The composition of the product liquid was butene trimer (C12) as the main component (40.4%), but the amount of high oligomers having 20 or more carbon atoms increased. The DIB selectivity in the C8 oligomer was 49.5%.
実施例４
（１）触媒の調製
・酸化タングステン担持チタニア－ジルコニア複合酸化物触媒（１０ｍｏｌ％ＷＯ３／ＴｉＯ２－ＺｒＯ２）の調製
　実施例１の触媒調製において、モリブデン酸アンモニウム溶液の代わりに５ｗｔ％のタングステン酸アンモニウム溶液を酸化タングステン換算で１９．６ｇ添加した他は、実施例１と同様にして触媒を調製した。得られた触媒の組成は、ＷＯ３として１９．６ｗｔ％、ＴｉＯ２として２４．３ｗｔ％であり、残りの５６．１ｗｔ％がＺｒ（ＺｒＯ２換算）であった。 Example 4
(1) Preparation of catalyst-Preparation of tungsten oxide-supported titania-zirconia composite oxide catalyst (10 mol% WO 3 / TiO 2 -ZrO 2 ) In the catalyst preparation of Example 1, 5 wt% tungsten instead of ammonium molybdate solution A catalyst was prepared in the same manner as in Example 1 except that 19.6 g of ammonium acid solution was added in terms of tungsten oxide. The composition of the obtained catalyst was 19.6 wt% as WO 3 , 24.3 wt% as TiO 2 , and the remaining 56.1 wt% was Zr (converted to ZrO 2 ).
（２）オリゴマー化反応
　反応条件は、触媒充填量を５ｃｃとしてＬＨＳＶ＝１６、反応温度を６０℃に変えた以外は、実施例１と同様にした。
　反応開始から４４時間後、イソブテン転化率は９３．７％で、その時のｎ－ブテン転化率は４．２％であった。生成液の組成はブテン３量体（Ｃ１２）が主成分であった（５８．５％）。 (2) Oligomerization reaction The reaction conditions were the same as in Example 1 except that the catalyst loading was 5 cc, LHSV = 16, and the reaction temperature was changed to 60 ° C.
44 hours after the start of the reaction, the conversion of isobutene was 93.7%, and the conversion of n-butene at that time was 4.2%. The composition of the product liquid was butene trimer (C12) as a main component (58.5%).
実施例５
・酸化タングステン担持シリカ－ジルコニア複合酸化物触媒（１０ｍｏｌ％ＷＯ３／ＳｉＯ２－ＺｒＯ２）の調製
　１０ｗｔ％硝酸ジルコニウム溶液を酸化ジルコニウム換算で７７．２ｇ、２５ｗｔ％ケイ酸ナトリウム溶液を二酸化ケイ素換算で４．７ｇ、それぞれ分取し、これら２つの溶液を混合した。得られた混合溶液を２５％アンモニア水７００ｇに全量滴下し、水酸化物スラリーを得た。水酸化物スラリーをろ別し、適宜イオン交換水で十分に水洗し、不純物を除去した水酸化物を得た。
　得られた水酸化物に５ｗｔ％のタングステン酸アンモニウム溶液を酸化タングステン換算で１８．１ｇ添加し、混練した後、１５０℃で恒量になるまで乾燥した。
　その後、６００℃で焼成し、触媒であるタングステン担持シリカ－ジルコニア複合酸化物を得た。
　得られた触媒の組成は、ＷＯ３として１８．１ｗｔ％、ＳｉＯ２として４．７ｗｔ％であった。
（２）オリゴマー化反応
　実施例４と同様にしてオリゴマー化反応を行った。
　反応開始から４８時間後、イソブテン転化率は９４．７％で、その時のｎ－ブテン転化率は５．３％であった。生成液の組成はブテン３量体（Ｃ１２）が主成分であった（５７．９％）。 Example 5
Preparation of tungsten oxide-supported silica-zirconia composite oxide catalyst (10 mol% WO 3 / SiO 2 -ZrO 2 ) 10 wt% zirconium nitrate solution in terms of zirconium oxide 77.2 g, 25 wt% sodium silicate solution in terms of silicon dioxide 4.7 g of each was taken and these two solutions were mixed. The total amount of the obtained mixed solution was dropped into 700 g of 25% aqueous ammonia to obtain a hydroxide slurry. The hydroxide slurry was separated by filtration and washed thoroughly with ion exchange water as appropriate to obtain a hydroxide from which impurities were removed.
18.1 g of a 5 wt% ammonium tungstate solution was added to the obtained hydroxide in terms of tungsten oxide, kneaded, and dried at 150 ° C. until a constant weight was obtained.
Thereafter, firing was performed at 600 ° C. to obtain a tungsten-supported silica-zirconia composite oxide as a catalyst.
The composition of the obtained catalyst was 18.1 wt% as WO 3 and 4.7 wt% as SiO 2 .
(2) Oligomerization reaction An oligomerization reaction was carried out in the same manner as in Example 4.
48 hours after the start of the reaction, the conversion of isobutene was 94.7%, and the conversion of n-butene at that time was 5.3%. The composition of the product liquid was butene trimer (C12) as a main component (57.9%).
比較例１
　モリブデン担持ジルコニア触媒（１０ｍｏｌ％ＭｏＯ３／ＺｒＯ２、第一稀元素化学工業株式会社製）を使用した以外は、実施例１と同様にオリゴマー化反応を実施した。但し、反応温度は１００℃とした。
　反応開始から８時間後、イソブテン転化率は９６．７％で、その時のｎ－ブテン転化率は８．８％であった。
　イソブテン転化率は、実施例１～３のＴｉＯ２複合化触媒の反応温度５０℃での結果と同程度であり、ＴｉＯ２と複合化させることにより活性が飛躍的に向上することが分かった。また、ＴｉＯ２複合化触媒の方がｎ－ブテン転化率が低く、イソブテン選択性が優れていることが明らかである。 Comparative Example 1
An oligomerization reaction was carried out in the same manner as in Example 1 except that a molybdenum-supported zirconia catalyst (10 mol% MoO 3 / ZrO 2 , manufactured by Daiichi Rare Element Chemical Industries, Ltd.) was used. However, the reaction temperature was 100 ° C.
8 hours after the start of the reaction, the conversion of isobutene was 96.7%, and the n-butene conversion at that time was 8.8%.
The conversion rate of isobutene was similar to the results of the TiO 2 composite catalysts of Examples 1 to 3 at a reaction temperature of 50 ° C., and it was found that the activity was dramatically improved by combining with TiO 2 . It is also clear that the TiO 2 composite catalyst has a lower n-butene conversion rate and superior isobutene selectivity.
比較例２
　タングステン担持ジルコニア触媒（１０ｍｏｌ％ＷＯ３／ＺｒＯ２、第一稀元素化学工業株式会社製）を使用した以外は、実施例４と同様にオリゴマー化反応を実施した。
　反応開始から１６時間後、イソブテン転化率は９３．６％で、その時のｎ－ブテン転化率は７．１％であった。実施例４及び５のＴｉＯ２又はＳｉＯ２複合化触媒と比較して、イソブテン転化率は同程度であるが、ｎ－ブテン転化率が高い。従って、本発明の複合化触媒の方がイソブテン選択性に優れていることが明らかである。 Comparative Example 2
An oligomerization reaction was carried out in the same manner as in Example 4 except that a tungsten-supported zirconia catalyst (10 mol% WO 3 / ZrO 2 , manufactured by Daiichi Rare Element Chemical Co., Ltd.) was used.
16 hours after the start of the reaction, the conversion of isobutene was 93.6%, and the conversion of n-butene at that time was 7.1%. Compared to the TiO 2 or SiO 2 composite catalyst of Examples 4 and 5, the isobutene conversion is similar, but the n-butene conversion is high. Therefore, it is clear that the composite catalyst of the present invention is superior in isobutene selectivity.
比較例３
　チタニア－ジルコニア担体（４０ｍｏｌ％ＴｉＯ２－ＺｒＯ２、第一稀元素化学工業株式会社製）にＭｏやＷを担持させずに用いた以外は、実施例１と同様に実施した。
　反応温度が１００℃であっても反応は全く進行せず、担体のみでは活性を有していないことが分かった。即ち、ＴｉＯ２－ＺｒＯ２担体にＭｏ又はＷを担持することにより、極めて高活性・高選択性を有するイソブテンのオリゴマー化触媒が形成されることが確認できた。 Comparative Example 3
The same procedure as in Example 1 was performed except that Mo and W were not supported on a titania-zirconia support (40 mol% TiO 2 —ZrO 2 , manufactured by Daiichi Rare Element Chemical Co., Ltd.).
It was found that even when the reaction temperature was 100 ° C., the reaction did not proceed at all, and the carrier alone had no activity. That is, it was confirmed that an isobutene oligomerization catalyst having extremely high activity and high selectivity was formed by loading Mo or W on a TiO 2 —ZrO 2 carrier.
比較例４
　代表的な固体酸触媒として、工業的に使用されているシリカアルミナ触媒（ＳｉＯ２　９０％）を使用した以外は、実施例１と同様にオリゴマー化反応を実施した。
　触媒充填量は実施例１～３、比較例１のＭｏ系触媒の実験に合わせて２０ｃｃ（ＬＨＳＶ＝４）とし、反応温度は８０℃で実施した。
　反応開始から２０時間後、イソブテン転化率は９８．０％で、その時のｎ－ブテン転化率は２６．０％であった。生成液の組成はブテン２量体（Ｃ８）及び３量体（Ｃ１２）が主成分で、多種多様な異性体構造を有する混合物となっていた。Ｃ８オリゴマー中のＤＩＢ選択率は１２．３％しかなかった。この結果からも、実施例の触媒が、極めて高いイソブテン選択性を有していることが確認できた。 Comparative Example 4
As a typical solid acid catalyst, an oligomerization reaction was carried out in the same manner as in Example 1 except that an industrially used silica alumina catalyst (SiO 2 90%) was used.
The catalyst charge was 20 cc (LHSV = 4) in accordance with the experiments of the Mo-based catalyst of Examples 1 to 3 and Comparative Example 1, and the reaction temperature was 80 ° C.
20 hours after the start of the reaction, the conversion of isobutene was 98.0%, and the n-butene conversion at that time was 26.0%. The composition of the product liquid was a mixture having butene dimer (C8) and trimer (C12) as main components and various isomer structures. The DIB selectivity in the C8 oligomer was only 12.3%. Also from this result, it was confirmed that the catalysts of the examples had extremely high isobutene selectivity.
比較例５
　比較例４と同じ触媒を用い、触媒充填量を実施例４及び５、比較例２のＷ系触媒の実験に合わせて５ｃｃ（ＬＨＳＶ＝１６）とし、反応温度は８０℃でオリゴマー化反応を実施した。
　反応開始から１６時間後、イソブテン転化率は８１．５％で、その時のｎ－ブテン転化率は１１．８％であった。生成液の組成はブテン２量体（Ｃ８）及び３量体（Ｃ１２）が主成分で、多種多様な異性体構造を有する混合物となっていた。この結果からも、実施例に記載した触媒が、極めて高いイソブテン選択性を有していることが明らかである。 Comparative Example 5
The same catalyst as in Comparative Example 4 was used, the catalyst filling amount was 5 cc (LHSV = 16) in accordance with the experiments of the W-based catalyst of Examples 4 and 5 and Comparative Example 2, and the oligomerization reaction was carried out at a reaction temperature of 80 ° C. did.
16 hours after the start of the reaction, the isobutene conversion rate was 81.5%, and the n-butene conversion rate at that time was 11.8%. The composition of the product liquid was a mixture having butene dimer (C8) and trimer (C12) as main components and various isomer structures. Also from this result, it is clear that the catalyst described in the examples has extremely high isobutene selectivity.
実施例６
　触媒は実施例１と同じものを用いた。
　以下のように反応条件を変更した他は、実施例１と同様にしてオリゴマー化反応を行った。
・反応管内径：１４ｍｍ
・反応圧力：２ＭＰａ
・混合Ｃ４原料組成：１－ブテン２０％、２－ブテン１８％、イソブテン４８％、ブタン１３％、他１％
・原料流量：４０ｃｃ／ｈ（ＬＨＳＶ＝２）
　尚、本実施例で用いた混合Ｃ４原料は、エチレン装置（ナフサ分解）から得られるＣ４留分（ブタジエン抽出後のＢＢＲ（ブタン－ブテンラフィネート）（Ｒａｆｆｉｎａｔｅ－Ｉ））である。
　その結果、反応開始から１１２時間後、イソブテン転化率は８７．３％で、その時のｎ－ブテン転化率は３．０％であった。また、Ｃ８オリゴマー中のＤＩＢ選択率は９２．０％であった。 Example 6
The same catalyst as in Example 1 was used.
The oligomerization reaction was performed in the same manner as in Example 1 except that the reaction conditions were changed as follows.
-Reaction tube inner diameter: 14 mm
・ Reaction pressure: 2 MPa
-Mixed C4 raw material composition: 1-butene 20%, 2-butene 18%, isobutene 48%, butane 13%, others 1%
・ Raw material flow rate: 40cc / h (LHSV = 2)
The mixed C4 raw material used in this example is a C4 fraction obtained from an ethylene unit (naphtha cracking) (BBR (butane-butene raffinate) (Raffinate-I) after butadiene extraction).
As a result, 112 hours after the start of the reaction, the isobutene conversion was 87.3%, and the n-butene conversion at that time was 3.0%. The DIB selectivity in the C8 oligomer was 92.0%.
実施例７
　触媒は実施例２と同じ触媒組成のものを用い、実施例６と同様にしてオリゴマー化反応を行った。
　その結果、反応開始から６４時間後、イソブテン転化率は８８．１％で、その時のｎ－ブテン転化率は４．９％であった。また、Ｃ８オリゴマー中のＤＩＢ選択率は８８．３％であった。 Example 7
The catalyst having the same catalyst composition as in Example 2 was used, and the oligomerization reaction was performed in the same manner as in Example 6.
As a result, 64 hours after the start of the reaction, the conversion rate of isobutene was 88.1%, and the conversion rate of n-butene was 4.9%. The DIB selectivity in the C8 oligomer was 88.3%.
比較例６
　触媒は比較例４と同じものを用い、実施例６と同様にしてオリゴマー化反応を行った。
　その結果、反応開始から１６時間後、イソブテン転化率は８１．９％で、その時のｎ－ブテン転化率は１７．８％であった。また、Ｃ８オリゴマー中のＤＩＢ選択率は４１．３％であった。
　従って、本実施例の触媒はイソブテン選択性が極めて高いことが分かる。 Comparative Example 6
The same catalyst as in Comparative Example 4 was used, and the oligomerization reaction was performed in the same manner as in Example 6.
As a result, 16 hours after the start of the reaction, the isobutene conversion rate was 81.9%, and the n-butene conversion rate at that time was 17.8%. The DIB selectivity in the C8 oligomer was 41.3%.
Therefore, it can be seen that the catalyst of this example has very high isobutene selectivity.
　以下表１に、実施例１～７及び比較例１～６の結果を示す。
Figure JPOXMLDOC01-appb-T000001
 Table 1 below shows the results of Examples 1 to 7 and Comparative Examples 1 to 6.
Figure JPOXMLDOC01-appb-T000001
　本発明のオレフィンのオリゴマー化反応用触媒は、オレフィンオリゴマー、特に、イソブテンオリゴマーの製造に好適に使用できる。 The olefin oligomerization reaction catalyst of the present invention can be suitably used for the production of olefin oligomers, particularly isobutene oligomers.
　上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
　この明細書に記載の文献の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will recognize that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The entire contents of the documents described in this specification are incorporated herein.

Claims (7)

  1. 　ジルコニア（ＺｒＯ２）に、チタニア（ＴｉＯ２）又はシリカ（ＳｉＯ２）を複合化した酸化物担体に、タングステン（Ｗ）又はモリブデン（Ｍｏ）を担持したものを焼成して得られる、オレフィンのオリゴマー化反応用触媒。 Olefin oligomer obtained by firing tungsten carrier (W) or molybdenum (Mo) supported on an oxide carrier obtained by combining titania (TiO 2 ) or silica (SiO 2 ) with zirconia (ZrO 2 ). Catalyst for chemical reaction.
  2. 　前記複合酸化物担体へのＷ又はＭｏの担持量が、酸化物換算（ＷＯ３又はＭｏＯ３）で１～３０ｗｔ％である請求項１に記載のオレフィンのオリゴマー化反応用触媒。 The catalyst for olefin oligomerization reaction according to claim 1, wherein the amount of W or Mo supported on the composite oxide support is 1 to 30 wt% in terms of oxide (WO 3 or MoO 3 ).
  3. 　前記オレフィン中の、分岐型オレフィンを選択的にオリゴマー化する請求項１又は２に記載のオレフィンのオリゴマー化反応用触媒。 The olefin oligomerization reaction catalyst according to claim 1 or 2, wherein a branched olefin in the olefin is selectively oligomerized.
  4. 　請求項１～３のいずれかに記載のオレフィンのオリゴマー化反応用触媒に、原料オレフィンを接触させる工程を有する、オレフィンオリゴマーの製造方法。 A method for producing an olefin oligomer, comprising a step of bringing a raw material olefin into contact with the olefin oligomerization reaction catalyst according to any one of claims 1 to 3.
  5. 　前記原料オレフィンが、炭素数４～１２のオレフィン類である請求項４に記載のオレフィンオリゴマーの製造方法。 The method for producing an olefin oligomer according to claim 4, wherein the raw material olefin is an olefin having 4 to 12 carbon atoms.
  6. 　前記原料オレフィンが、ナフサ分解等から副生するＣ４留分である請求項４に記載のオレフィンオリゴマーの製造方法。 The method for producing an olefin oligomer according to claim 4, wherein the raw material olefin is a C4 fraction by-produced from naphtha cracking or the like.
  7. 　請求項４～６のいずれかに記載のオレフィンオリゴマーの製造方法により得られ、原料オレフィンの２量体、３量体及び４量体を含むオレフィンオリゴマー。 An olefin oligomer obtained by the method for producing an olefin oligomer according to any one of claims 4 to 6 and comprising a dimer, a trimer and a tetramer of raw material olefins.
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