JP6611399B2 - 触媒の製造方法 - Google Patents
触媒の製造方法 Download PDFInfo
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- JP6611399B2 JP6611399B2 JP2018539956A JP2018539956A JP6611399B2 JP 6611399 B2 JP6611399 B2 JP 6611399B2 JP 2018539956 A JP2018539956 A JP 2018539956A JP 2018539956 A JP2018539956 A JP 2018539956A JP 6611399 B2 JP6611399 B2 JP 6611399B2
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- 239000003054 catalyst Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 239000000463 material Substances 0.000 claims description 35
- 239000003446 ligand Substances 0.000 claims description 32
- 238000000465 moulding Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 20
- 238000000859 sublimation Methods 0.000 claims description 19
- 230000008022 sublimation Effects 0.000 claims description 19
- 150000001299 aldehydes Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 12
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- 230000000996 additive effect Effects 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Description
本出願は、2016年11月16日付韓国特許出願第10−2016−0152616号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示されたすべての内容は、本明細書の一部として含まれる。
リガンド昇華率(重量%)=昇華したリガンド量(kg)/昇華前のリガンド量(kg)*100
Mo12PaAbBcCdDeEfOg
前記化学式1において、
Aは、W、V、Nb及びCrで構成された群より選ばれる1種以上の元素であり、Bは、As、B、Sb、Ce、Pd及びTeで構成された群より選ばれる1種以上の元素であり、Cは、Si、Al、Zr、Rh、Cu、Ti、Ag及びSnで構成された群より選ばれる1種以上の元素であり、Dは、Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr及びBaで構成された群より選ばれる1種以上の元素であり、Eは、Fe、Co及びNiで構成された群より選ばれる1種以上の元素であり、
a、b、c、d、e、f及びgは、各元素の原子比率を示し、aは0.5〜2、bは0.01〜10、cは0〜15、dは0.01〜20、eは0.01〜20、fは0.01〜15であり、gは各原子の酸化状態によって決定される値である。
リガンド昇華率(重量%)=昇華したリガンド量(kg)/昇華前のリガンド量(kg)*100
Mo12PaAbBcCdDeEfOg
前記化学式1において、
Aは、W、V、Nb及びCrで構成された群より選ばれる1種以上の元素であり、Bは、As、B、Sb、Ce、Pd及びTeで構成された群より選ばれる1種以上の元素であり、Cは、Si、Al、Zr、Rh、Cu、Ti、Ag及びSnで構成された群より選ばれる1種以上の元素であり、Dは、Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr及びBaで構成された群より選ばれる1種以上の元素であり、Eは、Fe、Co及びNiで構成された群より選ばれる1種以上の元素であり、
a、b、c、d、e、f及びgは、各元素の原子比率を示し、aは0.5〜2、bは0.01〜10、cは0〜15、dは0.01〜20、eは0.01〜20、fは0.01〜15であり、gは各原子の酸化状態によって決定される値である。
[数1]
リガンド昇華率(重量%)=昇華したリガンド量(kg)/昇華前のリガンド量(kg)*100
前記昇華前リガンドの量は、金属前駆体を溶解した反応液に含まれたリガンドの含有量を意味する。
超純水3000mLにパラモリブデン酸アンモニウム((NH4)6Mo7O24・4H2O)500g、パラタングステン酸アンモニウム((NH4)10W12O41・5H2O)0.62g、メタバナジン酸アンモニウム(NH4VO3)5.52g及び硝酸セシウム(CsNO3)46.0gを溶解して第1反応液を製造した。
P1.2Mo12W0.01V0.2Cu0.2Fe0.3Sb0.1Cs1.0
リガンド昇華率(重量%)=昇華したリガンド量(kg)/昇華前のリガンド量(kg)*100
(比較例1:触媒の製造)
超純水3000mLにパラモリブデン酸アンモニウム((NH4)6Mo7O24・4H2O)500g、パラタングステン酸アンモニウム((NH4)10W12O41・5H2O)0.62g、メタバナジン酸アンモニウム(NH4VO3)5.52g及び硝酸セシウム(CsNO3)46.0gを溶解して第1反応液を製造した。
P1.2Mo12W0.01V0.2Cu0.2Fe0.3Sb0.1Cs1.0
高圧反応器に超純水3000mL、三酸化モリブデン(MoO3)500g、85重量%リン酸水溶液42.15g、五酸化バナジウム(V2O5)14.45gを添加し、130℃で5時間攪拌して第1反応液を製造した。
P1.5Mo11V0.5Cu0.2Fe0.2Cs1.25
(Moの原子比率を12に換算すれば、P1.64Mo12V0.55Cu0.22Fe0.22Cs1.36である)
高圧反応器に超純水3000mL、三酸化モリブデン(MoO3)500g、85重量%リン酸水溶液42.15g、五酸化バナジウム(V2O5)14.45gを添加し、130℃で5時間攪拌して第1反応液を製造した。
P1.5Mo11V0.5Cu0.2Fe0.2Cs1.25
(Moの原子比率を12に換算すればP1.64Mo12V0.55Cu0.22Fe0.22Cs1.36である)
前記実施例及び比較例により製造した各触媒を固定層に充電したステンレス反応器を用いてメタクロレイン(methacrolein)を酸化反応させてメタクリル酸(methacrylic acid)を製造した。
メタクロレイン転換率(mol%)=[反応したメタクロレインのモル数/供給されたメタクロレインのモル数]X100
[数3]
メタクロレイン選択度(mol%)=[生成されたメタクリル酸のモル数/反応したメタクロレインのモル数]X100
[数4]
収率(mol%)=[生成されたメタクリル酸のモル数/供給されたメタクロレインのモル数]X100
Claims (9)
- 下記化学式1で表される触媒の製造方法であって、
前記触媒は、不飽和アルデヒドから不飽和カルボン酸を製造する際に用いられる不飽和カルボン酸製造用触媒であり、
金属前駆体を混合攪拌してスラリーを製造する段階と、
前記スラリーを110℃〜130℃で乾燥、粉砕及び混練した後に第1加圧成形する段階と、
第1加圧成形した材料を110℃〜130℃で乾燥して粉砕した後に第2加圧成形する段階と、
第2加圧成形した材料を300℃〜500℃で焼成する段階とを含み、
前記金属前駆体は、金属及びリガンドを含み、リガンドはNH 3 、NH 2 、NO X (ここでxは1〜3の整数)、Cl、F、N、OH、SO x (ここでxは3または4)、O、CO、COO、SCN、CN、NCS、ONO、C n H m O x (ここで、nは1〜20の整数、mは1〜40の整数、xは1〜10の整数)及び炭素数1〜20のアルコキシドで構成された群より選ばれる1種以上であり、
下記数式1で計算されるリガンド昇華率が0重量%以上である触媒の製造方法:
[数1]
リガンド昇華率(重量%)=昇華したリガンド量(kg)/昇華前のリガンド量(kg)*100
[化1]
Mo12PaAbBcCdDeEfOg
前記化学式1において、
Aは、W、V、Nb及びCrで構成された群より選ばれる1種以上の元素であり、Bは、As、B、Sb、Ce、Pd及びTeで構成された群より選ばれる1種以上の元素であり、Cは、Si、Al、Zr、Rh、Cu、Ti、Ag及びSnで構成された群より選ばれる1種以上の元素であり、Dは、Na、K、Li、Rb、Cs、Ta、Ca、Mg、Sr及びBaで構成された群より選ばれる1種以上の元素であり、Eは、Fe、Co及びNiで構成された群より選ばれる1種以上の元素であり、
a、b、c、d、e、f及びgは、各元素の原子比率を示し、aは0.5〜2、bは0.01〜10、cは0〜15、dは0.01〜20、eは0.01〜20、fは0.01〜15であり、gは各原子の酸化状態によって決定される値である。 - 前記金属前駆体は、パラモリブデン酸アンモニウム((NH 4 ) 6 Mo 7 O 24 ・4H 2 O)、パラタングステン酸アンモニウム((NH 4 ) 10 W 12 O 41 ・5H 2 O)、メタバナジン酸アンモニウム(NH 4 VO 3 )、硝酸セシウム(CsNO 3 )、硝酸銅(Cu(NO 3 ) 2 ・3H 2 O)、硝酸鉄(Fe(NO 3 ) 3 ・9H 2 O)、三酸化アンチモン(Sb 2 O 3 )、三酸化モリブデン(MoO 3 )及び五酸化バナジウム(V 2 O 5 )で構成された群より選ばれる1種以上である、請求項1に記載の触媒の製造方法。
- 前記スラリーを製造する段階は、共沈法あるいは水熱合成法を用いて金属前駆体からスラリーを製造する、請求項1または2に記載の触媒の製造方法。
- 前記スラリーを110℃〜130℃で8〜20時間乾燥する、請求項1〜3のいずれか1項に記載の触媒の製造方法。
- 前記第1加圧成形した材料を110℃〜130℃で8〜20時間乾燥する、請求項1〜4のいずれか1項に記載の触媒の製造方法。
- 前記第2加圧成形する段階以降に第2加圧成形した材料を不活性担体にコーティングする段階をさらに含む請求項1〜5のいずれか1項に記載の触媒の製造方法。
- 請求項1〜6のいずれか1項の製造方法により製造された触媒が固定された反応器に不飽和アルデヒドを供給し、240〜450℃の温度及び0.1〜10気圧下で気相酸化反応させる段階を含む不飽和カルボン酸の製造方法。
- 前記不飽和アルデヒドとしてメタクロレインを使用してメタクリル酸を製造する請求項7に記載の不飽和カルボン酸の製造方法。
- 前記反応器としてはシェル−&−チューブ熱交換式反応器を用いる請求項7または8に記載の不飽和カルボン酸の製造方法。
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