JP4551109B2 - 触媒の製造方法 - Google Patents
触媒の製造方法 Download PDFInfo
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- JP4551109B2 JP4551109B2 JP2004118478A JP2004118478A JP4551109B2 JP 4551109 B2 JP4551109 B2 JP 4551109B2 JP 2004118478 A JP2004118478 A JP 2004118478A JP 2004118478 A JP2004118478 A JP 2004118478A JP 4551109 B2 JP4551109 B2 JP 4551109B2
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- 239000003054 catalyst Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229910000510 noble metal Inorganic materials 0.000 claims description 70
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 150000002736 metal compounds Chemical class 0.000 claims description 29
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000010931 gold Substances 0.000 claims description 16
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 150000007514 bases Chemical class 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 12
- 239000002344 surface layer Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 238000006722 reduction reaction Methods 0.000 description 28
- 230000009467 reduction Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- 239000002923 metal particle Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 102000002322 Egg Proteins Human genes 0.000 description 5
- 108010000912 Egg Proteins Proteins 0.000 description 5
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 210000003278 egg shell Anatomy 0.000 description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- -1 for example Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- 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
- B01J21/08—Silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- B01J37/16—Reducing
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
そこで、本発明の主たる目的は、気相還元法によらず、設備、ランニングコスト等の点において有利な液相還元法を採用して、エッグシェル型であって、かつ、気相還元法で得られる触媒と同等以上の大きな貴金属表面積を有し、触媒活性が高く、酢酸ビニルを高い空時収量にて得られる酢酸ビニル合成用触媒を提供することにある。
下記各工程:
(a) 水溶性貴金属化合物水溶液を担体に含浸させる工程、
(b) 前記含浸後の担体と塩基性化合物水溶液とを接触させて、前記貴金属化合物を非水溶性貴金属化合物に転化させる工程、
(c) 前記非水溶性貴金属化合物を還元して、担体表面層に貴金属が担持された貴金属担持担体を生成させる工程、および
(d) 前記貴金属担持担体に、アルカリ金属および/またはアルカリ土類金属化合物を担持させる工程
を含む、
貴金属とアルカリ金属および/またはアルカリ土類金属化合物とが担持されている触媒の製造方法であって、
上記水溶性貴金属化合物水溶液および上記塩基性化合物水溶液の少なくとも一方が、酸化して両性酸化物を与える元素を含むことを特徴とする触媒の製造方法を提供する。
本発明は、更に該製造方法により得られる触媒、および該触媒の存在下における酢酸ビニルの製造方法をも提供する。
[(a)工程]
本発明に用いる担体としては、不活性な担体であれば特に制限なく用いることが可能であり、例えば、アルミナ、シリカ、活性炭等が挙げられ、特に、シリカが好ましい。
次いで、上記含浸後の担体を塩基性化合物水溶液と接触させる。具体的には、例えば、上記含浸後の担体を塩基性化合物水溶液中に浸漬する、上記含浸後の担体に塩基性化合物水溶液を滴下乃至流下させる等の手段が挙げられる。
該工程において、塩基性化合物との反応により、上記水溶性貴金属化合物を非水溶性貴金属化合物に転化させる。この際、貴金属化合物の担体表面層への引き出しが同時に生じて、担体表面層へ非水溶性貴金属化合物を担持させることができる。
また、上記(b)工程において、上記塩基性化合物水溶液に上記元素の化合物を混合させてもよい。更に、上記(a)工程および(b)工程の双方において、前記のとおりにして、上記元素の化合物を混合して使用しても差し支えない。
上記(a)および(b)工程に引き続いて、従来の液相還元法による酢酸ビニル合成用触媒の製造方法と同様にして、ヒドラジン、ホウ素化水素ナトリウム、アルコール、ギ酸等の還元剤を用いて、上記非水溶性貴金属化合物を還元して、貴金属単体、例えば、パラジウムおよび金を形成させ、次に純水にて洗浄を行い、乾燥させて貴金属担持担体を得る。
本発明触媒に担持される主活性成分である個々の貴金属の担持量は、本発明触媒質量に対して、各々、通常、0.1〜10.0質量%、好ましくは0.1〜3.0質量%の範囲とすることが好ましい。例えば、パラジウムおよび金の組み合わせである場合、パラジウムおよび金の担持量は、本発明触媒質量に対して、各々、通常、0.1〜10.0質量%、好ましくは0.1〜3.0質量%の範囲とすることが好ましい。
貴金属粒子の表面積は、担体表面層に担持された貴金属粒子に、一酸化炭素を化学吸着させて、その一酸化炭素の吸着量から貴金属表面積を算出することにより測定することができる。
酢酸ビニルの合成に対する触媒活性の評価基準である空時収量(STY:Space Time Yield)は、反応容器に触媒を充填し、エチレン、酸素および酢酸を供給して反応させ、酢酸ビニルを合成し、得られた酢酸ビニルの単位時間当たり、および単位触媒体積当たりの質量(g/L-cat/hr)として求められる。
なお、必要に応じて、更に窒素、二酸化炭素、水蒸気等を追加して反応性を評価することも可能である。
シリカ担体(ズードケミー社製:KA-160)1L当たり、3.5gの金属Pdおよび1.5gの金属Auが担持されるように、Na2[PdCl4]水溶液およびH[AuCl4]水溶液を秤量して混合し、予め調べておいたシリカ担体の飽和吸水量となるように純水で希釈した。該希釈液を前記シリカ担体1Lに吸水させて、前記Pd化合物およびAu化合物を担体に担持させた。
この触媒を反応器に充填し、反応温度(触媒温度)140℃および反応圧力0.78MPaの条件下で、エチレン:酸素:酢酸(容量比)=83:7:10の混合ガスを供給して酢酸ビニルの合成を行った。酢酸ビニルの空時収量は、398(g/L-cat/hr)であった。
上記比較例1と同じにして、シリカ担体にPd化合物およびAu化合物を担体に担持させ、Na2[SiO3]・9H2O水溶液に、Pd化合物およびAu化合物担持シリカ担体を加えて浸漬させた。
その後、浸漬処理後のPd化合物およびAu化合物担持シリカ担体を取り出し、純水を用いて洗浄した。硝酸銀溶液の滴下により洗浄液が白濁しなくなるまで洗浄を行なった後、乾燥させた。
次に、上記比較例1と同じにして、酢酸カリウムを担持させて、触媒を得た。
この触媒を用いて、上記比較例1と同じにして、酢酸ビニルの合成を行ったところ、酢酸ビニルの空時収量は、591(g/L-cat/hr)であった。
上記比較例1に記載のNa2[PdCl4]水溶液およびH[AuCl4]水溶液を秤量して混合する際に、更に、0.6gのZnCl2を該混合溶液に添加したこと以外は、比較例1と同じにして、触媒を得た。
この触媒を用いて、上記比較例1と同じにして、酢酸ビニルの合成を行ったところ、酢酸ビニルの空時収量は、623(g/L-cat/hr)であった。
上記比較例1に記載の、33.7gのNa2[SiO3]・9H2Oを純水に溶解し、液量が430mLになるように調整することに代えて、29.0gのAlCl3・6H2Oと24.0gのNaOHとを純水に溶解し、液量が430mLになるように調整すること以外は、比較例1と同じにして、触媒を得た。
この触媒を用いて、上記比較例1と同じにして、酢酸ビニルの合成を行ったところ、酢酸ビニルの空時収量は、440(g/L-cat/hr)であった。
上記比較例1、比較例2、実施例1および実施例2で得られた触媒について、その空時収量および貴金属(Pd)表面積を、表1にまとめて示す。
Claims (4)
- 下記各工程:
(a) 水溶性貴金属化合物水溶液を担体に含浸させる工程、
(b) 前記含浸後の担体と塩基性化合物水溶液とを接触させて、前記貴金属化合物を非水溶性貴金属化合物に転化させる工程、
(c) 前記非水溶性貴金属化合物を液相還元して、担体表面層に貴金属が担持された貴金属担持担体を生成させる工程、および
(d) 前記貴金属担持担体に、アルカリ金属および/またはアルカリ土類金属化合物を担持させる工程
を含む、貴金属とアルカリ金属および/またはアルカリ土類金属化合物とが担持されている触媒の製造方法であって、上記貴金属がパラジウムおよび金の組み合わせであること、上記アルカリ金属および/またはアルカリ土類金属化合物が酢酸カリウムであること、及び上記水溶性貴金属化合物水溶液および上記塩基性化合物水溶液の少なくとも一方が、ZnまたはAlを含むことを特徴とする触媒の製造方法。 - 前記ZnまたはAlを水溶性の無機化合物として含む、請求項1に記載の製造方法。
- 請求項1又は2に記載の製造方法により得られる酢酸ビニル合成用触媒。
- 請求項3に記載の触媒の存在下で、エチレン、酢酸および酸素を気相中で反応させることを特徴とする酢酸ビニルの製造方法。
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EP05008062A EP1588763A3 (en) | 2004-04-14 | 2005-04-13 | Production process for catalyst for producing vinyl acetate |
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JP4963922B2 (ja) * | 2006-10-04 | 2012-06-27 | 昭和電工株式会社 | 酢酸アルケニル製造用触媒の製造方法 |
WO2016198561A1 (en) * | 2015-06-12 | 2016-12-15 | Evonik Degussa Gmbh | Electroless deposition of au-pd bimetallic catalysts for alkenyl acetate production |
WO2017002576A1 (ja) * | 2015-06-29 | 2017-01-05 | 昭和電工株式会社 | 酢酸アリルの製造方法 |
CN104959136B (zh) * | 2015-06-30 | 2017-08-01 | 大连理工大学 | 一种用于树脂加氢蛋壳型催化剂的制备方法 |
CN106582872B (zh) * | 2015-10-19 | 2019-09-06 | 中国石油化工股份有限公司 | 合成乙烯法醋酸乙烯所用的催化剂 |
CN110302799B (zh) * | 2018-03-20 | 2022-03-22 | 碳能科技(北京)有限公司 | 电化学还原二氧化碳为一氧化碳的催化剂及其制备方法 |
CN117567273A (zh) * | 2018-07-27 | 2024-02-20 | 株式会社可乐丽 | 1,3-双酰氧基-2-亚甲基丙烷的制造方法 |
CN113908830B (zh) * | 2021-09-23 | 2023-03-28 | 西安交通大学 | 一种负载型贵金属催化剂及制备方法和应用 |
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