WO2015093378A1 - 成形体及びその製造方法、α-オレフィン二量化用触媒、並びにα-オレフィン二量体の製造方法 - Google Patents
成形体及びその製造方法、α-オレフィン二量化用触媒、並びにα-オレフィン二量体の製造方法 Download PDFInfo
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- WO2015093378A1 WO2015093378A1 PCT/JP2014/082757 JP2014082757W WO2015093378A1 WO 2015093378 A1 WO2015093378 A1 WO 2015093378A1 JP 2014082757 W JP2014082757 W JP 2014082757W WO 2015093378 A1 WO2015093378 A1 WO 2015093378A1
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- molded body
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- compound
- olefin
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- 239000003054 catalyst Substances 0.000 title claims description 84
- 238000006471 dimerization reaction Methods 0.000 title claims description 80
- 239000004711 α-olefin Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- 239000000539 dimer Substances 0.000 title claims description 10
- -1 carbonate compound Chemical class 0.000 claims abstract description 61
- 239000011148 porous material Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 38
- 229910052708 sodium Inorganic materials 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 38
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 34
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 24
- 239000002994 raw material Substances 0.000 description 24
- 238000000465 moulding Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000005979 thermal decomposition reaction Methods 0.000 description 15
- 238000011068 loading method Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000004438 BET method Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000007906 compression Methods 0.000 description 10
- 230000006835 compression Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005259 measurement Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 6
- 239000011736 potassium bicarbonate Substances 0.000 description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 6
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229960003975 potassium Drugs 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C11/113—Methylpentenes
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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
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- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
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Definitions
- the present invention relates to a molded article useful as a catalyst carrier, a production method thereof, an ⁇ -olefin dimerization catalyst produced using the molded article, and a production method of an ⁇ -olefin dimer using the catalyst.
- An ⁇ -olefin dimer represented by 4-methyl-1-pentene (including a codimer, the same applies hereinafter) is used as a monomer for polyolefin production.
- Many basic catalysts have been conventionally proposed as a catalyst for producing a corresponding dimer by ⁇ -olefin dimerization reaction (including co-dimerization reaction, the same applies hereinafter).
- a catalyst obtained by supporting an alkali metal on a carrier containing an anhydrous potassium compound as a main component is often used.
- the carrier may be molded into pellets, etc., since water is used for molding, potassium hydrogen carbonate dissolves and the mold can be filled smoothly. It was not possible, and it was estimated that the physical properties of the molded body were non-uniform.
- the problem to be solved by the present invention is that the ⁇ -olefin dimerization reaction is difficult to disintegrate, the reaction can be continued stably over a long period of time, the reaction activity is high, and the reaction selectivity is high.
- -To provide a high-strength and porous shaped article used as a carrier for an olefin dimerization catalyst, and a method for producing the same.
- the problem to be solved by the present invention is to provide an ⁇ -olefin dimerization catalyst using the molded article, and a method for producing an ⁇ -olefin dimer using the catalyst.
- the present inventors have used at least one of sodium carbonate and potassium carbonate, and have a specific pore volume and crushing strength as a catalyst support. It has been found that the above problems can be solved.
- a hydrogen carbonate compound to the raw material of the molded body used for the catalyst carrier, molding the raw material and heat-treating it at a specific temperature, the above-mentioned specific molded body can be obtained, and the above problems can be solved.
- the headline and the present invention were completed.
- Na least one carbonate compound selected from 2 CO 3 and K 2 CO 3 comprises (A1), pore volume pore diameter is in the range of 0.05 .mu.m ⁇ 10 [mu] m is 0.10 mL / g ⁇ A molded body having a crushing strength of 1.8 kgf to 10.0 kgf and 0.30 mL / g.
- the molded product of the present invention has high strength and porosity.
- the ⁇ -olefin dimerization catalyst using the molded body as a carrier for the ⁇ -olefin dimerization catalyst has higher reaction activity, higher reaction selectivity than the known catalysts, and is less likely to collapse during the reaction. The catalyst life can be significantly improved.
- a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively, unless otherwise specified.
- the molded body of the present invention contains at least one carbonic acid compound (A1) selected from Na 2 CO 3 and K 2 CO 3, and has a pore volume in the range of 0.05 ⁇ m to 10 ⁇ m and a pore volume of 0.001. It is 10 mL / g to 0.30 mL / g, and the crushing strength is 1.8 kgf to 10.0 kgf.
- A1 carbonic acid compound selected from Na 2 CO 3 and K 2 CO 3
- the pore volume is 0.10 mL / g or more, the amount of alkali metal supported can be increased, and when the pore volume is 0.30 mL / g or less, the strength of the molded body is increased. be able to. Moreover, when the crushing strength is 1.8 kgf or more, the catalyst life can be improved, and when the crushing strength is 10.0 kgf or less, a decrease in pore volume can be suppressed.
- the pore volume having a pore diameter in the above range can be generally measured by a mercury intrusion method using a mercury porosimeter.
- the pore volume is preferably 0.14 mL / g to 0.28 mL / g, more preferably 0.15 mL / g to 0.25 mL / g.
- the pore volume can be adjusted by the blending ratio of the hydrogen carbonate compound (A) in the mixture as the raw material of the molded body.
- the pore volume can be adjusted by adjusting the density of the tableting product to be described later.
- the crushing strength indicates the strength of the molded body in the radial direction. There is a direction corresponding to the radial direction in any of the noodle shape, columnar shape, convex shape, ring shape, and spherical shape, which will be described later, but in the case of a molded body having no shape corresponding to the radial direction, the weakest direction
- the strength is the crushing strength.
- the crushing strength is generally known as a physical property representing the pressure-resistant strength of the granulated product, and usually presses one molded body such as a pellet or a tablet in the body direction, and measures the force when crushing. Is. JIS Z8841 “Granulated material-Strength test method” defines the test method.
- the crushing strength is preferably 1.8 kgf to 8.5 kgf, more preferably 2.2 kgf to 8.5 kgf, and still more preferably 4.6 kgf to 8.4 kgf.
- the molded body of the present invention has Na n Y or K n Y (wherein Y is SO 4 , SiO 3 , F, Cl, or Br, and n is an integer of 1 or 2 determined by the valence of Y) It may further contain at least one compound (B1) represented by: Moreover, the molded object of this invention may further contain the graphite (C).
- the carbonic acid compound (A1) is selected from sodium carbonate (Na 2 CO 3 ) and potassium carbonate (K 2 CO 3 ), and may be either one kind or two kinds. In the case of two types, the mixing ratio is not particularly limited.
- the content of the carbonic acid compound (A1) is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
- Y in the formula represented by Na n Y or K n Y is SO 4 , SiO 3 , F, Cl, or Br, and n is an integer of 1 or 2 determined by the valence of Y. That is, the compound (B1) is sodium or potassium sulfate, sulfite, fluoride, chloride, or bromide. As the compound (B1), it may be any one of the compounds represented by Na n Y or K n Y, may be two or more. When there are two or more, the mixing ratio is not particularly limited.
- the content is preferably more than 0% by mass and 30% by mass or less, more preferably more than 0% by mass and 20% by mass or less, and more than 0% by mass. More preferably, it is 10 mass% or less.
- the graphite (C) that may be contained in the compact corresponds to the graphite (C) described later in the section “Molding the mixture”.
- the graphite (C) added to the mixture as the raw material of the compact may be oxidized depending on the heat treatment temperature and atmosphere, but any amount of the graphite (C) added to the raw material is contained in the compact. It may remain.
- the content is preferably more than 0% by mass and 10% by mass or less, and more preferably more than 0% by mass and 5% by mass or less.
- the method for producing a molded article of the present invention comprises 10 to 100 parts by mass of at least one hydrogen carbonate compound (A) represented by AHCO 3 and at least one compound (B) represented by B n X. After forming a mixture comprising 0 parts by mass to 90 parts by mass (a total of 100 parts by mass of (A) and (B)), the mixture was heat-treated at a temperature of 100 ° C. to 500 ° C. 97% by mass or more of A) is pyrolyzed.
- A hydrogen carbonate compound represented by AHCO 3
- B n X B n X
- a in the formula represented by AHCO 3 is Na or K. That is, the hydrogen carbonate compound (A) is at least one compound selected from sodium hydrogen carbonate and potassium hydrogen carbonate.
- the bicarbonate compound (A), may be any one of the compounds represented by AHCO 3, may be two or more. When there are two or more, the mixing ratio is not particularly limited.
- the hydrogen carbonate compound (A) is a compound that is thermally decomposed in this step.
- potassium hydrogen carbonate in which A in the formula is K is preferably used.
- B n X (B) is Na or K
- X is CO 3 , SO 4 , SiO 3 , F, Cl, or Br
- n is 1 or 2 determined by the valence of X It is an integer of 2. That is, compound (B) is sodium or potassium carbonate, sulfate, sulfite, fluoride, chloride, or bromide.
- the compound (B) may be any one of the compounds represented by B n X, may be two or more. When there are two or more, the mixing ratio is not particularly limited.
- potassium carbonate in which B in the formula is K, X is CO 3 and n is 2 is preferably used.
- the mixture used as the raw material of the molded article of the present invention comprises the hydrogen carbonate compound (A) and the compound (B).
- the hydrogen carbonate compound (A) is 10 parts by mass to 100 parts by mass, preferably 30 parts by mass to 100 parts by mass, based on 100 parts by mass of the total of the hydrogen carbonate compound (A) and the compound (B). More preferred is from 100 parts by mass.
- the compound (B) is 0 to 90 parts by mass, preferably 0 to 70 parts by mass, per 100 parts by mass in total of the hydrogen carbonate compound (A) and the compound (B). More preferably, it is from 60 parts by mass to 60 parts by mass.
- the case where a compound (B) is 0 mass part ie, the case where a compound (B) is not contained in a mixture is included.
- a compound corresponding to the carbonate compound (A1) is present in the molded body, and the ⁇ -olefin dimerization catalyst described later is present. This is because it can be suitably used as a carrier.
- the compound in which X in the formula represented by B n X is SO 4 , SiO 3 , F, Cl, or Br per 100 parts by mass of the total amount of the hydrogen carbonate compound (A) and the compound (B), It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.
- the mixture as the raw material of the molded body of the present invention provides a molded body having the pore volume of 0.10 mL / g to 0.30 mL / g and the crushing strength of 1.8 kgf to 10.0 kgf.
- other compounds other than the hydrogen carbonate compound (A) and the compound (B) may be included. Examples of such other compounds include ammonium bicarbonate. When the mixture contains ammonium hydrogen carbonate, the pore volume of the molded body can be increased.
- the mixture comprising the hydrogen carbonate compound (A) and the compound (B) preferably has a median diameter (d50) in a volume statistic of 5 ⁇ m to 600 ⁇ m, more preferably 20 ⁇ m to 500 ⁇ m. 50 ⁇ m to 450 ⁇ m is more preferable, and 50 ⁇ m to 300 ⁇ m is particularly preferable.
- the mixture containing the hydrogen carbonate compound (A) and the compound (B) preferably has a content of particles having a particle diameter of 40 ⁇ m or less of 3% by mass to 30% by mass.
- a content of particles having a particle diameter of 40 ⁇ m or less is within the above range.
- higher molded body strength can be obtained.
- the content of particles having a particle diameter of 40 ⁇ m or less is within the above range, the fluidity of the molded body raw material is ensured, and when the mixture is molded, it is difficult to cause blocking due to clogging in the middle and the like can be uniformly filled. .
- the molding method of the mixture is not particularly limited, and methods such as extrusion molding, compression molding and granulation molding are employed. Since the hydrogen carbonate compound (A) is dissolved in water, it is preferable not to add water to the mixture (that is, the mixture does not contain water).
- a molding raw material having a viscosity capable of maintaining the shape by adding a liquid to the above mixture is molded through a mold. Since the hydrogen carbonate compound (A) dissolves in water, it is preferable to use a solvent (such as an organic solvent) in which the hydrogen carbonate compound (A) does not dissolve when performing extrusion molding.
- a solvent such as an organic solvent
- the above mixture is filled in a die serving as a mold, and compressed and molded with a scissors.
- compression molding is preferable, and tableting molding is particularly preferable because of the properties of the mixture as a raw material of the molded body.
- tableting is performed, if a raw material that satisfies the characteristics of the mixture described above is used, the raw material is uniformly filled in the mortar, so that there is a tendency to obtain a molded body with small variations in density.
- graphite (C) When tableting is performed, graphite (C) is added to the mixture containing the hydrogen carbonate compound (A) and the compound (B) as necessary for the purpose of smoothing the movement of the mortar and the punch. be able to.
- graphite (C) There is no restriction
- the median diameter (d50) in the volume statistics is in the range of 5 ⁇ m to 500 ⁇ m, and the specific surface area measured by the BET method is in a wide range of 0.1 m 2 / g to 300 m 2 / g. Is.
- Graphite (C) may be natural graphite or artificial graphite.
- the amount of graphite (C) added to the mixture as a raw material of the molded body can be arbitrarily set as long as tableting can be performed, but 0.3 to 10 parts by mass per 100 parts by mass of the mixture Preferably, the amount is 0.5 to 5 parts by mass. If the added amount of graphite is within this range, there is hardly a problem that the added amount is too large and the strength of the molded body is lowered. In addition, since the amount added is too small, the friction with the mortar and pestle increases, the movement of the apparatus becomes poor, and there is almost no problem that the density of the molded body is not stable. Therefore, it becomes possible to mold well.
- the tableting density is preferably 1.6 g / mL to 2.3 g / mL, more preferably 1.8 g / mL to 2.2 g / mL.
- the tableting density can be adjusted by controlling the compressive strength.
- the size and shape of the molded body There is no particular limitation on the size and shape of the molded body. Various types are selected depending on conditions such as a molding apparatus, and can take any of a noodle shape, a cylindrical shape, a convex shape, a ring shape, and a spherical shape. In the case of tableting, a cylindrical shape, a convex shape, and a ring shape are preferable, and a cylindrical shape is more preferable from the viewpoint of ease of molding and strength.
- a commercially available tableting machine can be used, which may be a rotary type or a press type, and an apparatus with an optimal scale can be selected as appropriate according to the production amount.
- the molded body When the molded body is formed into a columnar shape, it is usually molded to have a diameter of 2 mm to 5 mm and a height of 2 mm to 6 mm. If the size of the molded body is within this range, the molded body is too small, the number of tableting increases, and the problem of lowering productivity and increasing costs is reduced. In addition, when the molded body is too large and is used as a catalyst carrier, the diffusion of raw materials and products in the reaction system is slowed down, and the problem of reducing the reaction activity and selectivity is reduced.
- the temperature of the heat treatment step is 100 ° C. to 500 ° C., preferably 150 ° C. to 450 ° C., more preferably 180 ° C. to 400 ° C.
- the said temperature can be arbitrarily determined by the kind of the hydrogen carbonate compound (A) to be used.
- the decomposition start temperatures of sodium hydrogen carbonate and potassium hydrogen carbonate corresponding to the hydrogen carbonate compound (A) are 270 ° C. and 100 ° C., respectively.
- By heat treatment 97 mass% or more, preferably 98 mass% or more, more preferably 99 mass% or more of the hydrogen carbonate compound (A) is thermally decomposed.
- the thermal decomposition rate is adjusted by the temperature of the heat treatment step and the heat treatment time.
- the thermal decomposition rate can be obtained by lengthening the heat treatment time.
- the thermal decomposition rate of the hydrogen carbonate compound (A) is in the above range, a molded article having a sufficient pore volume and preferable as a carrier for the ⁇ -olefin dimerization catalyst can be obtained.
- the gas generated by the thermal decomposition can be forcibly discharged.
- a method for forcibly discharging the generated gas include introducing air, a reducing gas, or an inert gas. Of these, the use of air is particularly desirable for operation.
- the structure of the heat treatment apparatus is not particularly limited, and a general heating furnace, electric furnace, belt furnace, hot air circulation furnace, or the like can be used.
- the hydrogen carbonate compound (A) is thermally decomposed and pores are formed in the portion where the generated gas is removed.
- a porous molded body has been obtained by reducing the compressive strength at the time of molding and ensuring a space formed between the particles, but in that case, the strength of the molded body tends to be weakened.
- the strength of the molded body tends to be weakened.
- the present invention since a method of obtaining a porous molded body by thermally decomposing the hydrogen carbonate compound (A) present inside after molding the molded body is taken, the strength is sacrificed as in the prior art. There is no need to mold it.
- the compression strength in order to obtain a high strength, the compression strength can be optimized and molded, and then many pores can be formed. Therefore, a high-strength and porous molded body can be formed.
- the molded body obtained by such a method has almost no decrease in strength compared to the molded body before the heat treatment step, despite the presence of a large number of pores inside the molded body. Compared with the molded body produced by the technique, a molded body having a large pore volume and high strength can be obtained.
- the molded product produced by the production method of the present invention is excellent in strength and shape uniformity, it is suitable as a catalyst carrier, particularly as a carrier for an ⁇ -olefin dimerization catalyst.
- the ⁇ -olefin dimerization catalyst of the present invention is obtained by supporting an alkali metal (D) on the molded article of the present invention.
- the alkali metal (D) is preferably sodium, potassium, or a mixture of sodium and potassium.
- the alkali metal (D) is a zero-valent metal that is not ionized and may contain components other than the alkali metal as long as the alkali metal purity is 90% or more.
- components other than alkali metals include Group 1 elements of the periodic table such as lithium and potassium, various oxides or hydroxides, and metal elements other than Group 1 elements of the periodic table.
- the temperature during the supporting treatment is usually in the range of 150 ° C to 400 ° C. From the viewpoint of obtaining a catalyst having excellent catalytic activity, catalyst life, and selectivity to an ⁇ -olefin dimerization product, the temperature during the supporting treatment is preferably in the range of 200 ° C to 350 ° C, preferably 200 ° C to 300 ° C. A range is more preferred.
- the atmosphere during the supporting treatment may be a reducing atmosphere or an inert atmosphere as long as it is not moisture and an oxidizing atmosphere. In consideration of safety and economy, it is preferable to perform the treatment in a nitrogen atmosphere.
- the support is vibrated, rotated, or stirred in order to uniformly support the alkali metal (D) during the supporting treatment. It is known that the supported alkali metal (D) undergoes an exchange reaction with the alkali metal in the carrier by contacting the carrier with heating.
- the content (support rate) of the alkali metal (D) in the ⁇ -olefin dimerization catalyst is usually 0.5% by mass to 100% by mass when the total amount of the alkali metal (D) and the carrier is 100% by mass. It is in the range of 10% by mass, preferably in the range of 1% by mass to 6% by mass.
- the molded body of the present invention is characterized by having a higher molded body strength and a larger pore volume than the molded body produced by the prior art. By having such a large pore volume, it becomes possible to carry more alkali metal (D). Since there is a correlation between the alkali metal (D) loading and the catalyst activity, the ⁇ -olefin dimerization catalyst of the present invention can be reacted with higher activity. In general, the higher the activity, the greater the load on the carrier and the tendency for the catalyst carrier to collapse, but the molded article of the present invention has a very high strength. This is particularly preferable because problems are unlikely to occur.
- the method for producing an ⁇ -olefin dimer according to the present invention is one in which an ⁇ -olefin dimerization reaction is performed in the presence of the ⁇ -olefin dimerization catalyst of the present invention.
- ⁇ -olefins include lower ⁇ -olefins such as ethylene, propylene, 1-butene, isobutylene and 1-pentene.
- dimerization reactions the production of 4-methyl-1-pentene by dimerization of propylene, and the production of 3-methyl-1-pentene by co-dimerization of 1-butene and ethylene, It is preferable to use an olefin dimerization catalyst.
- the reaction temperature in the dimerization reaction of ⁇ -olefin using the ⁇ -olefin dimerization catalyst of the present invention is usually 0 ° C. to 300 ° C., preferably 50 ° C. to 200 ° C.
- the reaction pressure is usually from normal pressure to 19.6 MPa (200 kg / cm 2 -G), preferably from 1.96 MPa to 14.7 MPa (20 kg / cm 2 -G to 150 kg / cm 2 -G). is there.
- the state of the ⁇ -olefin in the reactor varies depending on the reaction conditions and the type of ⁇ -olefin, but can generally be in a liquid phase state, a gas phase state, or a supercritical state.
- the reaction can be carried out in a fixed bed system or a fluidized bed system, but it is preferably carried out in a fixed bed system.
- alpha-olefin liquid hourly space velocity typically 0.1hr -1 ⁇ 10hr -1, preferably in the range of 0.5hr -1 ⁇ 5hr -1.
- Unreacted ⁇ -olefin and product are separated from the mixture after completion of the reaction according to a conventional method, and the unreacted ⁇ -olefin is recycled in the reaction.
- Example 1 Manufacture of molded products] 70 parts by mass of KHCO 3 (purity 99%, catalog number 43300-1201), which is a hydrogen carbonate compound (A), and K 2 CO 3 (purity 99%, purity 99%, measured by the BET method) 30 parts by mass of a specific surface area of 1.3 m 2 / g and a bulk density of 0.46 g / mL) were mixed to obtain 100 parts by mass of a mixed powder.
- the median diameter (d50) of the mixture powder was 120 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 7.5% by mass.
- FIG. 1 shows the measurement results of the pore distribution when the pore volume was measured for the heat-treated product (molded product (1)) and the product before heat treatment.
- the loading rate at this time was 3.5 mass%.
- Example 2 Preparation of ⁇ -olefin dimerization catalyst
- 94 parts by mass of the molded body (1) obtained in Example 1 was dried in a nitrogen stream at 300 ° C. for 2 hours, 6 parts by mass of sodium was added under a nitrogen atmosphere and 3.5 hours at 280 ° C.
- an ⁇ -olefin dimerization catalyst (2) was prepared.
- the loading rate at this time was 6.0% by mass.
- Example 3 [Manufacture of molded products]
- KHCO 3 manufactured by Junsei Chemical, purity 99% or more, catalog number 43300-1201
- the median diameter (d50) of KHCO 3 was 150 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 3.0% by mass.
- the loading rate at this time was 3.5 mass%.
- Example 4 Manufacture of molded products
- a mixture powder of 100 parts by mass was obtained in the same manner as in Example 1 except that the amount of KHCO 3 used was 50 parts by mass and the amount of K 2 CO 3 used was 50 parts by mass.
- the median diameter (d50) of the mixture powder was 100 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 13.0% by mass.
- a heat-treated molded product (molded product (3)) was prepared in the same manner as in Example 1 except that the compression strength was controlled so that the tablet molded product density was 1.9 g / mL as a tablet raw material. Obtained.
- the thermal decomposition rate of KHCO 3 was 100% by mass.
- the pore volume of the obtained heat-treated molded body was 0.21 mL / g, and the crushing strength in the radial direction was 4.6 kgf.
- the loading rate at this time was 3.5 mass%.
- Example 5 Manufacture of molded products
- 100 parts by mass of a mixture powder was obtained in the same manner as in Example 1 except that K 2 CO 3 that passed through a 212 ⁇ m sieve was used.
- the median diameter (d50) of the mixture powder was 100 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 23.0% by mass.
- a heat-treated molded product (molded product (4)) was obtained in the same manner as in Example 1 except that the compression strength was controlled so that the tablet compacted product density was 2.0 g / mL as a tablet raw material.
- the thermal decomposition rate of KHCO 3 was 100% by mass.
- the pore volume of the obtained heat-treated molded body was 0.20 mL / g, and the crushing strength in the radial direction was 8.4 kgf.
- the loading rate at this time was 3.5 mass%.
- Example 6 Manufacture of molded products
- 100 parts by mass of a mixture powder was obtained in the same manner as in Example 4 except that K 2 CO 3 that passed through a 212 ⁇ m sieve was used.
- the median diameter (d50) of the mixture powder was 90 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 26.5% by mass.
- a heat-treated molded article (molded article (5)) was obtained in the same manner as in Example 1 except that the compression strength was controlled so that the density of the tableted molded article was 1.9 g / mL as a tablet raw material.
- the thermal decomposition rate of KHCO 3 was 100% by mass.
- the pore volume of the obtained heat-treated molded body was 0.20 mL / g, and the crushing strength in the radial direction was 7.8 kgf.
- the loading rate at this time was 3.5 mass%.
- Example 7 [Manufacture of molded products] 13 parts by mass of powder (median diameter (d50) 15 ⁇ m) obtained by pulverizing hydrogen carbonate compound (A) KHCO 3 (manufactured by Junsei Chemical, purity 99%, catalog number 43300-1201) with a mortar, (B) 87 parts by mass of K 2 CO 3 (purity 99%, specific surface area measured by the BET method is 1.2 m 2 / g, bulk density 0.94 g / mL), and a mixture of 100 parts by mass A powder was obtained.
- the median diameter (d50) of the mixture powder was 260 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 14.6% by mass.
- the loading rate at this time was 3.5 mass%.
- Example 8 Manufacture of molded products
- a mixture powder of 100 parts by mass was obtained in the same manner as in Example 1 except that the amount of KHCO 3 used was 80 parts by mass and the amount of K 2 CO 3 used was 20 parts by mass.
- the median diameter (d50) of the mixture powder was 120 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 5.0% by mass.
- a heat-treated molded product (molded product (7)) was obtained in the same manner as in Example 1 except that the compression strength was controlled so that the tablet compacted product density was 2.0 g / mL as a tablet raw material.
- the pore volume of the obtained heat-treated molded product was 0.24 mL / g.
- the crushing strength in the radial direction was 5.2 kgf
- the crushing strength in the longitudinal direction was 22.5 kgf.
- K 2 CO 3 manufactured by Asahi Glass, purity 99%
- the median diameter (d50) of K 2 CO 3 was 110 ⁇ m, and the content of particles having a particle diameter of 40 ⁇ m or less was 4.0% by mass.
- the added sodium was fixed inside the carrying container and the outer surface of the molded body, and there were some that were difficult to discharge from the container. From this, it was judged that the added sodium was not fully supported on the molded body.
- the loading rate at this time is considered to be less than 3.5% by mass.
- the loading rate at this time was 1.0 mass%.
- Tables 1 to 3 show the physical properties of the molded products obtained in Examples 1 to 8 and Comparative Examples 1 to 3, the results of sodium loading, and the results of the dimerization reaction of propylene. According to the present invention, it can be seen that a molded body having a large pore volume and a high crushing strength can be obtained. Since the strength of the molded body is high, powdering of the catalyst in the subsequent alkali metal supporting step and ⁇ -olefin dimerization reaction step is suppressed, and a long-life catalyst can be prepared. Moreover, since the pore volume of the molded body is large, the entire amount is supported on the molded body even if the amount of sodium supported is increased. Therefore, it can be seen that a catalyst having a high reaction activity (in this case, propylene conversion) can be obtained.
- a catalyst having a high reaction activity in this case, propylene conversion
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Abstract
Description
また、米国特許第5081094号明細書に開示されている炭酸水素カリウムを含む担体を用いた触媒は、紛体状であるため工業生産に適さないものであった。米国特許第5081094号明細書には、担体をペレット状等に成形してもよいことの開示があるものの、成形に水を用いるため炭酸水素カリウムが溶解し、成形金型への充填がスムーズにできず、成形体の物性が不均一となることが推定された。
[1] Na2CO3及びK2CO3から選ばれる少なくとも1種の炭酸化合物(A1)を含み、細孔直径が0.05μm~10μmの範囲にある細孔容積が0.10mL/g~0.30mL/gであり、かつ、圧壊強度が1.8kgf~10.0kgfである、成形体。
[2] 上記炭酸化合物(A1)の含有率が70質量%以上である、上記[1]に記載の成形体。
[3] NanY又はKnY(式中のYはSO4、SiO3、F、Cl、又はBrであり、nはYの価数によって決定される1又は2の整数である。)で表される少なくとも1種の化合物(B1)を更に含む、上記[1]又は[2]に記載の成形体。
[4] 上記細孔容積が0.14mL/g~0.28mL/gであり、かつ、上記圧壊強度が2.2kgf~8.5kgfである、上記[1]~[3]のいずれか1項に記載の成形体。
[5] 上記炭酸化合物(A1)がK2CO3である、上記[1]~[4]のいずれか1項に記載の成形体。
[6] グラファイト(C)を更に含む、上記[1]~[5]のいずれか1項に記載の成形体。
[7] 上記[1]~[6]のいずれか1項に記載の成形体にアルカリ金属(D)を担持して得られる、α-オレフィン二量化用触媒。
[8] 上記[7]に記載のα-オレフィン二量化用触媒の存在下でα-オレフィンの二量化反応を行う、α-オレフィン二量体の製造方法。
[9] AHCO3(式中のAはNa又はKである。)で表される少なくとも1種の炭酸水素化合物(A)10質量部~100質量部と、
BnX(式中のBはNa又はKであり、XはCO3、SO4、SiO3、F、Cl、又はBrであり、nはXの価数によって決定される1又は2の整数である。)で表される少なくとも1種の化合物(B)0質量部~90質量部と、
を含んでなる混合物((A)と(B)との合計100質量部)を成形した後、100℃~500℃の温度で熱処理し、上記炭酸水素化合物(A)の97質量%以上を熱分解する、上記[1]に記載の成形体の製造方法。
[10] 上記混合物が水を含有しない、上記[9]に記載の成形体の製造方法。
[11] 上記混合物の成形を打錠成形で行う、上記[9]又は[10]に記載の成形体の製造方法。
[12] 上記混合物の体積統計値でのメジアン径(d50)が5μm~600μmの範囲にある、上記[9]~[11]のいずれか1項に記載の成形体の製造方法。
[13] 上記混合物中、粒子径40μm以下の粒子の含有率が3質量%~30質量%である、上記[9]~[12]のいずれか1項に記載の成形体の製造方法。
なお、本明細書において「~」を用いて示された数値範囲は、特に断らない限り、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
また、本明細書における圧壊強度の単位[kgf]は、1kfg=9.8Nの関係式により[N]に変換可能である。
本発明の成形体は、Na2CO3及びK2CO3から選ばれる少なくとも1種の炭酸化合物(A1)を含み、細孔直径が0.05μm~10μmの範囲にある細孔容積が0.10mL/g~0.30mL/gであり、かつ、圧壊強度が1.8kgf~10.0kgfである。
また、上記圧壊強度が1.8kgf以上であることにより、触媒寿命を改善することができ、上記圧壊強度が10.0kgf以下であることにより、細孔容積の減少を抑えることができる。
圧壊強度は好ましくは1.8kgf~8.5kgfであり、より好ましくは2.2kgf~8.5kgfであり、更に好ましくは4.6kgf~8.4kgfである。
また、本発明の成形体は、グラファイト(C)を更に含んでいてもよい。
炭酸化合物(A1)は、炭酸ナトリウム(Na2CO3)及び炭酸カリウム(K2CO3)から選ばれ、いずれか1種のみであってもよく、2種であってもよい。2種である場合、その混合割合は特に限定されない。炭酸化合物(A1)としてはK2CO3が好ましい。
炭酸化合物(A1)の含有率は、70質量%以上であることが好ましく、80質量%以上であることがより好ましく、90質量%以上であることが更に好ましい。
NanY又はKnYで表される式中のYはSO4、SiO3、F、Cl、又はBrであり、nはYの価数によって決定される1又は2の整数である。すなわち、化合物(B1)は、ナトリウム又はカリウムの、硫酸塩、亜硫酸塩、フッ化物、塩化物、又は臭化物である。化合物(B1)としては、NanY又はKnYで表される化合物のいずれか1種であってもよく、2種以上であってもよい。2種以上である場合、その混合割合は特に限定されない。
成形体中に化合物(B1)が含まれる場合、その含有率は0質量%超30質量%以下であることが好ましく、0質量%超20質量%以下であることがより好ましく、0質量%超10質量%以下であることが更に好ましい。
成形体に含まれてもよいグラファイト(C)としては、「混合物の成形」の項で後述するグラファイト(C)に相当する。成形体の原料となる混合物に添加されたグラファイト(C)は、熱処理温度及び雰囲気によっては酸化することもありうるが、原料に添加されたグラファイト(C)のうち任意の量が成形体中に残存していてよい。
成形体中にグラファイト(C)が含まれる場合、その含有率は0質量%超10質量%以下であることが好ましく、0質量%超5質量%以下であることがより好ましい。
本発明の成形体の製造方法は、AHCO3で表される少なくとも1種の炭酸水素化合物(A)10質量部~100質量部と、BnXで表される少なくとも1種の化合物(B)0質量部~90質量部と、を含んでなる混合物((A)と(B)との合計100質量部)を成形した後、100℃~500℃の温度で熱処理し、上記炭酸水素化合物(A)の97質量%以上を熱分解するものである。
AHCO3で表される式中のAはNa又はKである。すなわち、炭酸水素化合物(A)は、炭酸水素ナトリウム及び炭酸水素カリウムから選ばれる少なくとも1種の化合物である。炭酸水素化合物(A)としては、AHCO3で表される化合物のいずれか1種であってもよく、2種以上であってもよい。2種以上である場合、その混合割合は特に限定されない。
BnXで表される式中のBはNa又はKであり、XはCO3、SO4、SiO3、F、Cl、又はBrであり、nはXの価数によって決定される1又は2の整数である。すなわち、化合物(B)は、ナトリウム又はカリウムの、炭酸塩、硫酸塩、亜硫酸塩、フッ化物、塩化物、又は臭化物である。化合物(B)としては、BnXで表される化合物のいずれか1種であってもよく、2種以上であってもよい。2種以上である場合、その混合割合は特に限定されない。
本発明の成形体の原料となる混合物は、上記炭酸水素化合物(A)と上記化合物(B)とを含んでなる。炭酸水素化合物(A)と化合物(B)との合計100質量部当たり、炭酸水素化合物(A)は10質量部~100質量部であり、30質量部~100質量部であることが好ましく、40質量部~100質量部であることがより好ましい。また、炭酸水素化合物(A)と化合物(B)との合計100質量部当たり、化合物(B)は0質量部~90質量部であり、0質量部~70質量部であることが好ましく、0質量部~60質量部であることがより好ましい。
上記炭酸水素化合物(A)と上記化合物(B)とを含んでなる混合物は、体積統計値でのメジアン径(d50)が5μm~600μmであることが好ましく、20μm~500μmであることがより好ましく、50μm~450μmであることが更に好ましく、50μm~300μmであることが特に好ましい。
一般的に、小粒径の粒子は打錠成形時に粒子の動きが悪いために排除されることが望ましいことが知られているが、粒子径40μm以下の粒子の含有率を上記範囲内とすることにより、より高い成形体強度を得ることができる。また、粒子径40μm以下の粒子の含有率が上記範囲内であれば、成形体原料の流動性が確保され、混合物を成形する際、途中に詰まるなどしてブロッキングを起こしにくく、均一に充填できる。なお、炭酸水素化合物(A)の粒径分布と化合物(B)の粒径分布とに違いがあっても、混合後に全体として粒子径40μm以下の粒子の含有率が上記範囲内となっていればよい。
本発明において、混合物の成形法としては特に限定されず、押出成形、圧縮成形、造粒成形等の方法が採用される。上記炭酸水素化合物(A)は水に溶解するため、混合物には水を添加しないこと(すなわち、混合物が水を含有しないこと)が好ましい。
打錠成形体密度は、好ましくは1.6g/mL~2.3g/mLであり、より好ましくは1.8g/mL~2.2g/mLである。打錠成形体密度は、圧縮強度を制御することにより調整できる。
上記成形法により得られた成形体は、熱処理工程を経て最終的に本発明の成形体となる。
熱処理により、炭酸水素化合物(A)の97質量%以上、好ましくは98質量%以上、より好ましくは99質量%以上が熱分解される。
熱分解率は、熱処理工程の温度及び熱処理時間により調整される。熱処理温度が比較的低い場合は、熱処理時間を長くすることにより上記の熱分解率を得ることができる。炭酸水素化合物(A)の熱分解率が上記範囲にあることによって、十分な細孔容積を持ち、α-オレフィン二量化用触媒の担体として好ましい成形体を得ることができる。
本発明のα-オレフィン二量化用触媒は、本発明の成形体にアルカリ金属(D)を担持して得られるものである。
本発明のα-オレフィン二量体の製造方法は、本発明のα-オレフィン二量化用触媒の存在下でα-オレフィンの二量化反応を行うものである。
反応器内のα-オレフィンの状況は当該反応条件及びα-オレフィンの種類によって異なるが、一般的に液相状態、気相状態、超臨界状態が取りうる。これらの中でも、気相状態又は超臨界状態で反応を実施することが好ましい。また、反応は固定床方式で行うこともできるし、流動床方式で行うこともできるが、固定床方式で行うことが好ましい。固定床方式で反応を行う場合に、α-オレフィンの液空間速度(LHSV)は通常0.1hr-1~10hr-1、好ましくは0.5hr-1~5hr-1の範囲である。反応終了後の混合物から定法に従って未反応のα-オレフィン及び生成物が分離され、未反応のα-オレフィンは反応に循環再利用される。
窒素を流通させたグローブボックス中、20μm~850μmの網ふるいの上部に30gの粉体を入れ、手動でふるいにかけた。ふるい分けした後の各ふるい上での粉体の質量を測定することにより、メジアン径(d50)を算出した。
窒素を流通させたグローブボックス中、40μmの網ふるいの上部に30gの粉体を入れ、手動でふるいにかけた。ふるいをパスした粉体質量を測定し、最初に入れた30gで割ることにより、粒子径40μm以下の粒子の含有率を算出した。
得られた成形体を示差熱天秤(Rigaku製 8120)で400℃まで昇温して重量減少量を測定し、成形時の炭酸水素化合物(A)の含有量と重量減少量との関係から、熱分解率を計算した。なお、化学量論的に、2モルの炭酸水素化合物(A)から、1モルの水と1モルのCO2とが発生する。熱分解率が100質量%の場合は、それ以上の熱分解が起こらないため、示差熱天秤での重量減少は認められない。
水銀ポロシメーター(マイクロメトリクス社製、Auto PoreIV)を用いて水銀圧入法によって、細孔直径が0.05μm~10μmの範囲にある細孔容積を測定した。
デジタル硬度計(藤原製作所製、KHT-40N)を用い、JIS Z8841「造粒物-強度試験法」に記載の方法に従って、成形体の半径方向(円柱状成形体の胴方向)の圧壊強度を測定した。実施例8については成形体の縦方向(円柱状成形体の軸線方向)の圧壊強度も測定した。
圧壊強度の測定原理は、静止している試料台の上に、被測定対象である円柱状成形体を載置し、可動式の加圧面を上部から一定速度で下降させ、円柱状成形体に押し付けて破壊するときの強度を測定するものである。
α-オレフィン(プロピレン)の二量化反応終了後、反応器内よりα-オレフィン二量化用触媒を取り出し、目視にて触媒の粉化の有無を確認した。
〔成形体の製造〕
炭酸水素化合物(A)であるKHCO3(純正化学製、純度99%、カタログ番号43300-1201)70質量部と、化合物(B)であるK2CO3(純度99%、BET法で測定した比表面積1.3m2/g、嵩密度0.46g/mL)30質量部とを混合し、100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は120μmであり、粒子径40μm以下の粒子の含有率は7.5質量%であった。
上記成形体(1)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(1)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(1)4gを単管型反応器(直径18mm)に充填し、反応器内温度140℃、反応圧力9.8MPa、プロピレン流量4g/hで触媒層に連続的にプロピレンを供給し、プロピレンの二量化反応による4-メチル-1-ペンテン(以下、4MP-1と略す)の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表1に示す。
〔α-オレフィン二量化用触媒の調製〕
実施例1において得られた成形体(1)94質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム6質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(2)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(2)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表1に示す。
〔成形体の製造〕
炭酸水素化合物(A)としてKHCO3(純正化学製、純度99%以上、カタログ番号43300-1201)を用いた。KHCO3のメジアン径(d50)は150μmであり、粒子径40μm以下の粒子の含有率は3.0質量%であった。
上記成形体(2)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(3)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(3)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表1に示す。
〔成形体の製造〕
KHCO3の使用量を50質量部とし、K2CO3の使用量を50質量部とした以外は実施例1と同様にして100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は100μmであり、粒子径40μm以下の粒子の含有率は13.0質量%であった。
上記成形体(3)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(4)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(4)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表1に示す。
〔成形体の製造〕
乳鉢で軽く押し潰して粉砕した後、212μmのふるいを通過したK2CO3を使用した以外は実施例1と同様にして100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は100μmであり、粒子径40μm以下の粒子の含有率は23.0質量%であった。
上記成形体(4)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(5)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(5)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表2に示す。
〔成形体の製造〕
乳鉢で軽く押し潰して粉砕した後、212μmのふるいを通過したK2CO3を使用した以外は実施例4と同様にして100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は90μmであり、粒子径40μm以下の粒子の含有率は26.5質量%であった。
上記成形体(5)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(6)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(6)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表2に示す。
〔成形体の製造〕
炭酸水素化合物(A)であるKHCO3(純正化学製、純度99%、カタログ番号43300-1201)を乳鉢で粉砕して得られた粉体(メジアン径(d50)15μm)13質量部と、化合物(B)であるK2CO3(純度99%、BET法で測定した比表面積が1.2m2/g、嵩密度0.94g/mL)87質量部とを混合し、100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は260μmであり、粒子径40μm以下の粒子の含有率は14.6質量%であった。
上記成形体(6)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(7)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(7)4gを単管型反応器(直径18mm)に充填し、反応器内温度140℃、反応圧力9.8MPa、プロピレン流量4g/hで触媒層に連続的にプロピレンを供給し、プロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表2に示す。
〔成形体の製造〕
KHCO3の使用量を80質量部とし、K2CO3の使用量を20質量部とした以外は実施例1と同様にして100質量部の混合物粉体を得た。混合物粉体のメジアン径(d50)は120μmであり、粒子径40μm以下の粒子の含有率は5.0質量%であった。
〔成形体の製造〕
化合物(B)としてK2CO3(旭硝子製、純度99%)を用いた。K2CO3のメジアン径(d50)は110μmであり、粒子径40μm以下の粒子の含有率は4.0質量%であった。
上記成形体(C1)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(C1)を調製した。
〔α-オレフィン二量化用触媒の調製方法〕
比較例1において得られた成形体(C1)99質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム1質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(C2)を調製した。
上記調製方法により得られたα-オレフィン二量化用触媒(C2)4gを用いて実施例1と同様の方法によりプロピレンの二量化反応による4MP-1の合成反応を行った。流通反応を180時間実施したときのプロピレン転化率及び4MP-1選択率を表3に示す。
〔成形体の製造〕
打錠成形体密度が1.55g/mLとなるように圧縮強度を制御して打錠成形した以外は、比較例1と同様にして熱処理成形体(成形体(C2))を得た。得られた熱処理成形体の細孔容積は0.21mL/gであった。また、半径方向の圧壊強度は1.1kgfであった。
上記成形体(C2)96.5質量部を窒素気流中、300℃で2時間乾燥させた後、窒素雰囲気気流下、ナトリウム3.5質量部を添加し、280℃で3.5時間撹拌してα-オレフィン二量化用触媒(C3)の調製を試みた。しかし、担持中に成形体(C2)が粉化したため、触媒としての回収が不可能になった。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (13)
- Na2CO3及びK2CO3から選ばれる少なくとも1種の炭酸化合物(A1)を含み、細孔直径が0.05μm~10μmの範囲にある細孔容積が0.10mL/g~0.30mL/gであり、かつ、圧壊強度が1.8kgf~10.0kgfである、成形体。
- 前記炭酸化合物(A1)の含有率が70質量%以上である、請求項1に記載の成形体。
- NanY又はKnY(式中のYはSO4、SiO3、F、Cl、又はBrであり、nはYの価数によって決定される1又は2の整数である。)で表される少なくとも1種の化合物(B1)を更に含む、請求項1又は請求項2に記載の成形体。
- 前記細孔容積が0.14mL/g~0.28mL/gであり、かつ、前記圧壊強度が2.2kgf~8.5kgfである、請求項1~請求項3のいずれか1項に記載の成形体。
- 前記炭酸化合物(A1)がK2CO3である、請求項1~請求項4のいずれか1項に記載の成形体。
- グラファイト(C)を更に含む、請求項1~請求項5のいずれか1項に記載の成形体。
- 請求項1~請求項6のいずれか1項に記載の成形体にアルカリ金属(D)を担持して得られる、α-オレフィン二量化用触媒。
- 請求項7に記載のα-オレフィン二量化用触媒の存在下でα-オレフィンの二量化反応を行う、α-オレフィン二量体の製造方法。
- AHCO3(式中のAはNa又はKである。)で表される少なくとも1種の炭酸水素化合物(A)10質量部~100質量部と、
BnX(式中のBはNa又はKであり、XはCO3、SO4、SiO3、F、Cl、又はBrであり、nはXの価数によって決定される1又は2の整数である。)で表される少なくとも1種の化合物(B)0質量部~90質量部と、
を含んでなる混合物((A)と(B)との合計100質量部)を成形した後、100℃~500℃の温度で熱処理し、前記炭酸水素化合物(A)の97質量%以上を熱分解する、請求項1に記載の成形体の製造方法。 - 前記混合物が水を含有しない、請求項9に記載の成形体の製造方法。
- 前記混合物の成形を打錠成形で行う、請求項9又は請求項10に記載の成形体の製造方法。
- 前記混合物の体積統計値でのメジアン径(d50)が5μm~600μmの範囲にある、請求項9~請求項11のいずれか1項に記載の成形体の製造方法。
- 前記混合物中、粒子径40μm以下の粒子の含有率が3質量%~30質量%である、請求項9~請求項12のいずれか1項に記載の成形体の製造方法。
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---|---|---|---|---|
WO2018117247A1 (ja) | 2016-12-22 | 2018-06-28 | 三井化学株式会社 | 多孔質成形体の製造方法、α-オレフィン二量化用触媒の製造方法、α-オレフィン二量体の製造方法、多孔質成形体、及びα-オレフィン二量化用触媒 |
WO2019189636A1 (ja) | 2018-03-29 | 2019-10-03 | 三井化学株式会社 | 多孔質成形体及びその製造方法、α-オレフィン二量化用触媒及びその製造方法、並びに、α-オレフィン二量体の製造方法 |
WO2023190652A1 (ja) * | 2022-03-30 | 2023-10-05 | 三井化学株式会社 | オレフィン二量体の製造方法、オレフィン二量化触媒 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58114737A (ja) | 1981-12-28 | 1983-07-08 | Mitsui Petrochem Ind Ltd | α−オレフイン二量化用触媒 |
JPS6238240A (ja) * | 1985-06-24 | 1987-02-19 | フイリツプス ペトロリユ−ム コンパニ− | 触媒支持体の製造方法 |
JPH0342043A (ja) | 1989-07-07 | 1991-02-22 | Mitsui Petrochem Ind Ltd | α―オレフインの二量化触媒 |
US5081094A (en) | 1990-08-10 | 1992-01-14 | Phillips Petroleum Company | Alkali metal bicarbonate/alkali metal carbonate support, catalyst system, and olefin dimerization processes therewith |
JPH07222927A (ja) | 1993-11-19 | 1995-08-22 | Ube Ind Ltd | 低級α−オレフィンの二量化触媒 |
JPH0834749A (ja) * | 1994-05-19 | 1996-02-06 | Mitsui Petrochem Ind Ltd | 重合用オレフィンの精製法およびポリオレフィンの製造法 |
JPH08109144A (ja) * | 1994-10-07 | 1996-04-30 | Ube Ind Ltd | 1−ペンテンの製法 |
JP2006326418A (ja) | 2005-05-24 | 2006-12-07 | Mitsui Chemicals Inc | α−オレフィン二量化用触媒およびα−オレフィン二量体の製造方法。 |
JP2008149275A (ja) | 2006-12-19 | 2008-07-03 | Mitsui Chemicals Inc | α−オレフィン二量化用触媒およびα−オレフィン二量体の製造方法。 |
JP2012062987A (ja) * | 2010-09-17 | 2012-03-29 | Fuji Electric Co Ltd | 真空断熱材及びその製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3972721A (en) * | 1974-03-01 | 1976-08-03 | Ppg Industries, Inc. | Thermally stable and crush resistant microporous glass catalyst supports and methods of making |
CA1198409A (en) | 1981-12-28 | 1985-12-24 | Keiji Kawamoto | Catalyst composition suitable for the dimerization or codimerization of alpha-olefins |
US5474963A (en) * | 1993-04-09 | 1995-12-12 | Ube Industries, Ltd. | Catalyst for dimerizing α-olefin monomer |
JPH0922927A (ja) | 1995-07-05 | 1997-01-21 | Tokyo Electron Ltd | 位置決め装置および検査装置 |
EP0908436A4 (en) * | 1996-04-10 | 2001-01-10 | Kyowa Yuka Kk | METHOD FOR DIMERIZING LOW OLEFINS |
CN1060408C (zh) | 1997-09-10 | 2001-01-10 | 中国石油化工总公司 | 高效脱氯剂及其制备方法 |
CN102380340B (zh) * | 2010-09-06 | 2013-06-19 | 中国石油化工股份有限公司 | 一种脱硫剂及其制备方法 |
-
2014
- 2014-12-10 KR KR1020167015747A patent/KR101847319B1/ko active IP Right Grant
- 2014-12-10 JP JP2015553503A patent/JP6014277B2/ja active Active
- 2014-12-10 WO PCT/JP2014/082757 patent/WO2015093378A1/ja active Application Filing
- 2014-12-10 EP EP14871087.4A patent/EP3075448B1/en active Active
- 2014-12-10 US US15/103,216 patent/US10500570B2/en active Active
- 2014-12-10 CN CN201480068134.5A patent/CN105813738B/zh active Active
-
2016
- 2016-06-24 ZA ZA2016/04291A patent/ZA201604291B/en unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58114737A (ja) | 1981-12-28 | 1983-07-08 | Mitsui Petrochem Ind Ltd | α−オレフイン二量化用触媒 |
JPS6238240A (ja) * | 1985-06-24 | 1987-02-19 | フイリツプス ペトロリユ−ム コンパニ− | 触媒支持体の製造方法 |
JPH0342043A (ja) | 1989-07-07 | 1991-02-22 | Mitsui Petrochem Ind Ltd | α―オレフインの二量化触媒 |
US5081094A (en) | 1990-08-10 | 1992-01-14 | Phillips Petroleum Company | Alkali metal bicarbonate/alkali metal carbonate support, catalyst system, and olefin dimerization processes therewith |
JPH07222927A (ja) | 1993-11-19 | 1995-08-22 | Ube Ind Ltd | 低級α−オレフィンの二量化触媒 |
JPH0834749A (ja) * | 1994-05-19 | 1996-02-06 | Mitsui Petrochem Ind Ltd | 重合用オレフィンの精製法およびポリオレフィンの製造法 |
JPH08109144A (ja) * | 1994-10-07 | 1996-04-30 | Ube Ind Ltd | 1−ペンテンの製法 |
JP2006326418A (ja) | 2005-05-24 | 2006-12-07 | Mitsui Chemicals Inc | α−オレフィン二量化用触媒およびα−オレフィン二量体の製造方法。 |
JP2008149275A (ja) | 2006-12-19 | 2008-07-03 | Mitsui Chemicals Inc | α−オレフィン二量化用触媒およびα−オレフィン二量体の製造方法。 |
JP2012062987A (ja) * | 2010-09-17 | 2012-03-29 | Fuji Electric Co Ltd | 真空断熱材及びその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3075448A4 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018117247A1 (ja) | 2016-12-22 | 2018-06-28 | 三井化学株式会社 | 多孔質成形体の製造方法、α-オレフィン二量化用触媒の製造方法、α-オレフィン二量体の製造方法、多孔質成形体、及びα-オレフィン二量化用触媒 |
JPWO2018117247A1 (ja) * | 2016-12-22 | 2019-10-31 | 三井化学株式会社 | 多孔質成形体の製造方法、α−オレフィン二量化用触媒の製造方法、α−オレフィン二量体の製造方法、多孔質成形体、及びα−オレフィン二量化用触媒 |
US11247194B2 (en) | 2016-12-22 | 2022-02-15 | Mitsui Chemicals, Inc. | Method for producing porous molded body, method for producing catalyst for α-olefin dimerization, method for producing α-olefin dimer, porous molded body, and catalyst for α-olefin dimerization |
US11772072B2 (en) | 2016-12-22 | 2023-10-03 | Mitsui Chemicals, Inc. | Method for producing porous molded body, method for producing catalyst for α-olefin dimerization, method for producing α-olefin dimer, porous molded body, and catalyst for α-olefin dimerization |
WO2019189636A1 (ja) | 2018-03-29 | 2019-10-03 | 三井化学株式会社 | 多孔質成形体及びその製造方法、α-オレフィン二量化用触媒及びその製造方法、並びに、α-オレフィン二量体の製造方法 |
KR20200126401A (ko) | 2018-03-29 | 2020-11-06 | 미쓰이 가가쿠 가부시키가이샤 | 다공질 성형체 및 그의 제조 방법, α-올레핀 이량화용 촉매 및 그의 제조 방법, 및 α-올레핀 이량체의 제조 방법 |
JPWO2019189636A1 (ja) * | 2018-03-29 | 2020-12-03 | 三井化学株式会社 | 多孔質成形体及びその製造方法、α−オレフィン二量化用触媒及びその製造方法、並びに、α−オレフィン二量体の製造方法 |
JP6999799B2 (ja) | 2018-03-29 | 2022-02-04 | 三井化学株式会社 | 多孔質成形体及びその製造方法、α-オレフィン二量化用触媒及びその製造方法、並びに、α-オレフィン二量体の製造方法 |
KR20220144414A (ko) | 2018-03-29 | 2022-10-26 | 미쓰이 가가쿠 가부시키가이샤 | 다공질 성형체 및 그의 제조 방법, α-올레핀 이량화용 촉매 및 그의 제조 방법, 및 α-올레핀 이량체의 제조 방법 |
US11759768B2 (en) | 2018-03-29 | 2023-09-19 | Mitsui Chemicals, Inc. | Porous formed body and production method thereof, α-olefin dimerization catalyst and production method thereof, and method of producing α-olefin dimer |
WO2023190652A1 (ja) * | 2022-03-30 | 2023-10-05 | 三井化学株式会社 | オレフィン二量体の製造方法、オレフィン二量化触媒 |
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