CN112165988B - 非均相催化剂 - Google Patents
非均相催化剂 Download PDFInfo
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- CN112165988B CN112165988B CN201980035187.XA CN201980035187A CN112165988B CN 112165988 B CN112165988 B CN 112165988B CN 201980035187 A CN201980035187 A CN 201980035187A CN 112165988 B CN112165988 B CN 112165988B
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- catalyst
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- methanol
- methacrolein
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010931 gold Substances 0.000 claims abstract description 29
- 229910052737 gold Inorganic materials 0.000 claims abstract description 28
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 16
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006709 oxidative esterification reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- OBSHSWKHUYGFMF-UHFFFAOYSA-N 3,3-dimethoxy-2-methylprop-1-ene Chemical compound COC(OC)C(C)=C OBSHSWKHUYGFMF-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 238000009736 wetting Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 210000003278 egg shell Anatomy 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229940083577 gold sodium thiosulfate Drugs 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- KZNBHWLDPGWJMM-UHFFFAOYSA-J trisodium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(1+);dihydrate Chemical compound O.O.[Na+].[Na+].[Na+].[Au+].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S KZNBHWLDPGWJMM-UHFFFAOYSA-J 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000014649 Carica monoica Nutrition 0.000 description 1
- 244000132069 Carica monoica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000000701 chemical imaging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- AGHLUVOCTHWMJV-UHFFFAOYSA-J sodium;gold(3+);2-sulfanylbutanedioate Chemical compound [Na+].[Au+3].[O-]C(=O)CC(S)C([O-])=O.[O-]C(=O)CC(S)C([O-])=O AGHLUVOCTHWMJV-UHFFFAOYSA-J 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- -1 thiomalic acid Chemical compound 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B01J35/19—
-
- B01J35/30—
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- B01J35/397—
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- B01J35/40—
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- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- B01J2235/30—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
Abstract
一种包含载体和金的非均相催化剂,其中:(i)所述载体包含氧化铝,(ii)所述催化剂包含0.1wt%至5wt%的金,(iii)至少90wt%的所述金在催化剂体积的外部60%中,和(iv)所述催化剂的颗粒具有200微米至30毫米的平均直径;其中重量百分比是按所述催化剂的重量计。本发明的催化剂适用于产生甲基丙烯酸甲酯(MMA)的方法中,所述方法包含在氧化酯化反应器中用甲醇处理甲基丙烯醛。
Description
背景技术
本发明涉及一种非均相催化剂。催化剂尤其适用于由甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法。
具有负载于二氧化硅上的贵金属与氧化铝和其它元素的组合的非均相催化剂为已知的,参见例如美国专利第US7326806B2号。然而,需要具有经改进的性质的额外催化剂颗粒。
发明内容
本发明涉及一种包含载体和金的非均相催化剂,其中:(i)所述载体包含氧化铝,(ii)所述催化剂包含0.1wt%至5wt%的金,(iii)至少90wt%的所述金在催化剂体积的外部60%中,和(iv)所述催化剂的颗粒具有200微米至30毫米的平均直径;其中重量百分比是按所述催化剂的重量计。
本发明进一步涉及一种包含所述非均相催化剂的颗粒的催化剂床。
本发明进一步涉及一种由甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法;所述方法包含使包含甲基丙烯醛、甲醇和氧气的混合物与包含非均相催化剂的颗粒的催化剂床接触。
具体实施方式
除非另外指示,否则所有百分比组成都为重量百分比(wt%),并且所有温度都以℃为单位。“金属”为周期表第1族到第12族中的元素(不包括氢),加上铝、镓、铟、铊、锡、铅和铋。“催化剂中心”为催化剂颗粒的质心,即,在所有坐标方向上所有点的平均位置。直径为穿过催化剂中心的任何线性尺寸,并且平均直径为所有可能性直径的算术平均值。纵横比为最长直径与最短直径的比率。
优选地,载体具有大于10m2/g、优选地大于30m2/g、优选地大于50m2/g、优选地大于100m2/g、优选地大于120m2/g的表面积。在几乎不包含或不包含金的催化剂的部分中,载体可具有小于50m2/g,优选地小于20m2/g的表面积。优选地,催化剂颗粒包含至少0.1wt%、优选地至少0.2wt%、优选地至少0.3wt%;优选地不超过95wt%、优选地不超过90wt%、优选地不超过80wt%、优选地不超过70wt%、优选地不超过60wt%、优选地不超过50wt%、优选地不超过40wt%、优选地不超过30wt%、优选地不超过20wt%、优选地不超过10wt%、优选地不超过5wt%的氧化铝。优选地,催化剂颗粒为包含上述量的氧化铝的二氧化硅颗粒。优选地,催化剂颗粒为氧化铝颗粒。
优选地,催化剂颗粒的纵横比不超过10∶1、优选地不超过5∶1、优选地不超过3∶1、优选地不超过2∶1、优选地不超过1.5∶1、优选地不超过1.1∶1。颗粒的优选形状包括球形、圆柱形、矩形固体、环形、多叶形(例如苜蓿叶横截面)、具有多个孔的形状和“马车车轮形”,优选地球形。也可以使用不规则形状。
优选地,至少90wt%的金在催化剂体积(即普通催化剂颗粒的体积)的外部60%中、优选地在外部50%中、优选地在外部40%中、优选地在外部30%中、优选地在外部25%中。优选地,对于具有沿着垂直于外表面的线测量的从其内表面到其外表面(颗粒的表面)的恒定距离的体积,计算任何颗粒形状的外部体积。例如,对于球形颗粒,体积的外部x%为球形壳体,其外表面为颗粒的表面并且体积为整个球形体积的x%。优选地,至少95wt%、优选地至少97wt%、优选地至少99wt%的金在催化剂的外部体积中。优选地,至少90wt%(优选地至少95wt%、优选地至少97wt%、优选地至少99wt%)的金在距表面不超过催化剂直径的15%、优选地不超过13%、优选地不超过10%、优选地不超过8%的距离内。距表面的距离是沿着垂直于表面的线测量的。
优选地,催化剂颗粒的平均直径为至少300微米、优选地至少400微米、优选地至少500微米、优选地至少600微米、优选地至少700微米、优选地至少800微米;优选地不超过20毫米、优选地不超过10毫米、优选地不超过5毫米。载体的平均直径和最终催化剂颗粒的平均直径没有显著差异。
优选地,呈催化剂(金和载体)百分比形式的金的量为0.2wt%到5wt%、优选地至少0.3wt%、优选地至少0.5wt%、优选地至少0.7wt%、优选地至少0.9wt%;优选地不超过4wt%、优选地不超过3wt%、优选地不超过2.5wt%。
优选地,通过在二氧化硅颗粒上沉淀铝盐来产生载体。优选地,随后通过煅烧、还原或所属领域的技术人员已知的其它处理将金属盐分解为金属或金属氧化物来处理所得材料。优选地,在载体存在下,金从金属盐的水溶液中沉淀出来。优选地,溶液含有酸,如硝酸、硫酸、盐酸、乙酸或其它酸。优选地,溶液含有含硫酸,例如硫代苹果酸,优选地羧酸,例如柠檬酸或草酸。优选地,含硫酸以1wt%至10wt%(优选地3%至8%)的浓度存在。优选地,羧酸以0.1wt%至25wt%(优选地0.5wt%至15wt%)的量存在。优选地,硫与酸的重量比为0.1∶1至5∶1,优选地0.2∶1至3∶1。优选地,在金前体添加之前,用氢氧化铵洗涤载体,优选地使本体载体中的氯化物含量经去除而降至低于100ppm,优选地低于50ppm的水平。优选地,在载体存在下,铝从金属盐的水溶液中沉淀出来。优选的铝盐包括硝酸铝、硫酸铝、氯化铝、氢氧化铝和氧化铝;优选地硝酸铝、硫酸铝或氯化铝。优选的金盐包括四氯金酸、硫代硫酸金钠、硫代苹果酸金钠和氢氧化金。在一个优选实施例中,通过微湿(incipient wetness)技术产生载体,其中将铝前体盐的水溶液添加到二氧化硅颗粒中,使得孔隙被溶液填充并且随后通过干燥去除水。优选地,随后通过煅烧、还原或所属领域的技术人员已知的其它处理将金属盐分解为金属或金属氧化物来处理所得材料。优选地,通过微湿,随后进行干燥,并且优选地通过煅烧将金添加到氧化铝或氧化铝改性的二氧化硅载体中。
煅烧优选地在250℃到600℃、优选地至少300℃、优选地不超过550℃的温度下进行。优选地,以逐步或连续的方式将温度升高到最终煅烧温度。
在另一个优选实施例中,通过沉积-沉淀产生催化剂,其中将包含氧化铝的多孔二氧化硅浸入含有合适的金前体盐的水溶液中,并且随后通过调节溶液的pH使所述盐与无机氧化物的表面相互作用。随后回收(例如通过过滤)处理过的所得固体,并且随后通过煅烧、还原或所属领域的技术人员已知的其它处理将金盐分解为金属或金属氧化物来将所述固体转化成成品催化剂。
本发明的催化剂适用于一种产生甲基丙烯酸甲酯(MMA)的方法中,所述方法包含在含有催化剂床的氧化酯化反应器(OER)中用甲醇处理甲基丙烯醛。催化剂床包含催化剂颗粒并且位于可通过催化剂床进行流体流动的OER内。催化剂床中的催化剂颗粒通常通过固体壁和通过筛网保持在适当位置。在一些配置中,筛网处于催化剂床的相对端上并且固体壁处于侧面上,但在一些配置中,催化剂床可以被筛网完全包围。催化剂床的优选形状包括圆柱形、矩形固体和圆柱形壳体;优选地圆柱形。OER进一步包含有包含甲基丙烯醛、甲醇和MMA的液相和包含氧气的气相。液相可以进一步包含例如甲基丙烯醛二甲基缩醛(MDA)和异丁酸甲酯(MIB)的副产物。优选地,液相处于40℃到120℃;优选地至少50℃、优选地至少60℃;优选地不超过110℃、优选地不超过100℃的温度下。优选地,催化剂床处于0psig到2000psig(101.3kPa到13890.8kPa);优选地不超过2000kPa、优选地不超过1500kPa的压力下。优选地,催化剂床中的pH为4到10;优选地至少4.5、优选地至少5;优选地不超过9、优选地不超过8、优选地不超过7.5、优选地不超过7、优选地不超过6.5。优选地,催化剂床处于管式连续反应器中。
OER通常产生MMA以及甲基丙烯酸和未反应的甲醇。优选地,以1∶10到100∶1、优选地1∶2到20∶1、优选地1∶1到10∶1的甲醇:甲基丙烯醛摩尔比将甲醇和甲基丙烯醛进料到含有固定床的反应器中。优选地,固定床进一步包含惰性材料。优选的惰性材料包括例如氧化铝、粘土、玻璃、碳化二氧化硅和石英。优选地,惰性材料处于催化剂的尺寸范围或更小范围内。优选地,将反应产物进料到甲醇回收蒸馏塔中,得到富含甲醇和甲基丙烯醛的顶部物料流;优选地,将这种物料流再循环回到OER中。来自甲醇回收蒸馏塔的底部物料流包含MMA、MDA、甲基丙烯酸、盐和水。在本发明的一个实施例中,MDA在包含MMA、MDA、甲基丙烯酸、盐和水的介质中水解。MDA可以在来自甲醇回收蒸馏塔的底部物料流中水解;所述物料流包含MMA、MDA、甲基丙烯酸、盐和水。在另一个实施例中,MDA在从甲醇回收底部物料流分离的有机相中水解。可能有必要向有机相中添加水以确保存在足够的水来进行MDA水解;这些量可以容易地由有机相的组成确定。MDA水解反应器的产物经相分离,并且有机相穿过一个或多个蒸馏塔以产生MMA产物和轻质和/或重质副产物。
实例
实例#1
分批再循环固定床鼓泡塔式反应器操作:
制备包含10wt%甲基丙烯醛、200ppm抑制剂和余量甲醇的150g进料溶液,并放置在充当气体分离容器的300ml反应器中。将容器液体维持在约20℃的温度下。将液体进料以7毫升/分钟从气体分离容器泵送到竖直定向的固定床反应器的底部。将空气和氮气混合以获得7.8mol%的氧气,并将其与液体进料混合,之后进入固定床反应器。固定床反应器为使用外部加热器维持在60℃下的加套1/4”不锈钢管。反应器自身装有2mm的玻璃珠以填充约18英寸的管,随后装有催化剂。反应器顶部处的剩余空隙填充有3mm的玻璃珠。将离开反应器顶部的液体和气体传送到冷凝器中,并排出不可冷凝气体,同时液体再循环回到气体分离容器中。催化剂#1以及其它一些实例都以这种方式运行。
催化剂#1制备:
通过微湿技术,使用5g Norpro 3.2mm的氧化铝球粒作为起始载体材料,并添加到在添加前已搅拌30分钟的由0.19g硫代硫酸金钠、0.2g巯基琥珀酸、0.06g一水柠檬酸和约5g去离子水组成的溶液中来制备催化剂#1。随后将催化剂放入箱式烘箱中,在室温下以约50LPH持续空气吹扫1小时,并且随后使用5℃的匀变温度/分钟在400℃下煅烧并在400℃下保持4小时。
实例#2
分批再循环固定床鼓泡塔式反应器操作:
如实例#1所述使用分批再循环反应器。
催化剂#2制备:
通过微湿技术,使用10g Norpro 3.2mm的氧化铝球粒作为起始载体材料,并添加到在添加前已搅拌30分钟的由在10g去离子水中的0.39g硫代硫酸金钠和0.04g硫代苹果酸组成的溶液中来制备催化剂#2。随后将催化剂放入箱式烘箱中,在120℃下以约50LPH持续空气吹扫1小时,并且随后使用5℃的匀变温度/分钟在400℃下煅烧并在400℃下保持4小时。
实例#3
单程固定床鼓泡塔式反应器操作:
将由20wt%甲基丙烯醛、200ppm抑制剂和余量甲醇组成的进料以40克/小时的速率进料到含有短前段硼硅玻璃珠、随后为5g催化剂的3/8”不锈钢管式反应器中。利用催化剂#2。还以足以在排气口处获得4.5%O2的速率将在氮气中含有8%氧气的气体进料到反应器中。反应器在60℃和160psig下操作。将反应器的产物传送到液气分离器中,并将蒸气传送到冷凝器中,并使液体返回,并且使不可冷凝气体前往排气口。结果描述于下表中。
催化剂#3制备:
通过微湿技术,使用20g富士硅化学株式会社(Fuji Silysia Chemical,Ltd.)CARiACT Q-10载体作为起始材料并将铝添加到载体材料中来制备催化剂#3。具体来说,将13.8g九水合硝酸铝溶解在20g去离子水中。将盐溶液以极小液滴形式添加到转筒型设备中的载体中,以确保所述溶液均匀分布到载体材料。当添加时,所述溶液处于80℃下。随后在60℃下的轻微真空下干燥经改性的载体材料4小时,并且随后通过将温度从环境温度以5℃/分钟逐渐升温到125℃,保持1小时,并且随后以5℃/分钟逐渐升温到250℃并保持1小时,随后以5℃/分钟逐渐升温到350℃并保持1小时,并且最后以5℃/分钟逐渐升温到450℃并保持4小时而在环境压力下的空气中煅烧经改性的载体材料。随后通过微湿技术,利用在10g去离子水中的0.83g硫代硫酸金钠在40℃下将金添加到载体中。在空气中使用与上文相同的加热概况干燥并煅烧所得催化剂。用配备有能量色散光谱(EDS)的扫描电子显微镜(SEM)进行的催化剂分析清楚地表明,存在Al和Au两者的蛋壳沉积,其中Au优选地仅位于Al沉积之处。发现Al和Au蛋壳厚度约为1微米。
比较实例#4
分批再循环固定床鼓泡塔式反应器操作:
如实例#1所述使用分批再循环反应器。
催化剂#4制备:
通过溶解于100g水中而制得水溶液的4.1g硫代硫酸金钠的微湿来制备催化剂#4,并且随后放置在100g富士硅化学株式会社CARiACT Q-20二氧化硅载体材料上。将样品在120℃下干燥1个小时,随后在400℃下煅烧4小时。金负载量在催化剂中大致均匀。
1.归一化MMA选择率为以甲基丙烯醛反应物形式起源的产物中的MMA百分比。
2.距存在至少50wt%的Au的颗粒表面的距离(SEM/EDS)。
3.根据SEM/EDS估算催化剂#3具有0.5wt%的氧化铝。
4.STY是以每千克催化剂每小时的MMA摩尔数计的时空产率。
所有催化剂的金含量均在1.1wt%至1.5wt%的范围内。
对于催化剂#2,约95%的金在外部200微米内,即体积的外部33%内,而对于比较催化剂4,约95%在外部1000微米(体积的外部95%)内
蛋壳实例的SEM/EDS
样品成像和EDS横截面图:SEM-EDS成像在配备有Bruker AXSXFlash6160FlatQUAD能量色散X射线光谱仪(EDS)的Hitachi SU-8230上进行。显微镜的工作距离为15mm,加速电压为15keV,射束电流为20nA。射束限制孔径设置为1或0。典型的X射线计数率在100kcps和200kcps之间。收集图像5分钟,并且图像尺寸为1000×750像素。使用2.1keV下的Au M线,1.5keV下的Al K和2.4keV下的S Ka生成图像。
Claims (3)
1.一种用于制备甲基丙烯酸甲酯的包含载体和金的非均相催化剂,其中:(i)所述载体是包含氧化铝的多孔二氧化硅,所述载体具有大于10m2/g的表面积,且所述载体通过在二氧化硅颗粒上沉淀铝盐后通过干燥和焙烧来产生,得到具有铝壳的二氧化硅载体,(ii)所述催化剂由0.2wt%至3wt%的金、60wt%至95wt%的二氧化硅和0.1wt%至15wt%的氧化铝组成,(iii)至少95wt%的所述金在催化剂体积的外部50%中,至少90wt%的金在距表面不超过催化剂直径的15%,和(iv)所述催化剂的颗粒具有300微米至20毫米的平均直径;其中重量百分比是按所述催化剂的重量计。
2.一种催化剂床,其包含(a)权利要求1所述的包含载体和金的非均相催化剂,(b)包含甲基丙烯醛、甲醇和甲基丙烯酸甲酯的液相,以及(c)包含氧气的气相。
3.一种由甲基丙烯醛和甲醇制备甲基丙烯酸甲酯的方法;所述方法包含使包含甲基丙烯醛、甲醇和氧气的混合物与权利要求2所述催化剂床接触。
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- 2019-06-20 CN CN201980035187.XA patent/CN112165988B/zh active Active
- 2019-06-20 JP JP2020567563A patent/JP2021528231A/ja active Pending
- 2019-06-20 SG SG11202012162PA patent/SG11202012162PA/en unknown
- 2019-06-20 BR BR112020023925-9A patent/BR112020023925A2/pt not_active Application Discontinuation
- 2019-06-20 US US17/252,884 patent/US11813593B2/en active Active
- 2019-06-20 CA CA3103680A patent/CA3103680A1/en active Pending
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CN112165988A (zh) | 2021-01-01 |
KR20210022620A (ko) | 2021-03-03 |
EP3814008A1 (en) | 2021-05-05 |
BR112020023925A2 (pt) | 2021-02-09 |
JP2021528231A (ja) | 2021-10-21 |
US20210121856A1 (en) | 2021-04-29 |
WO2020005689A1 (en) | 2020-01-02 |
US11813593B2 (en) | 2023-11-14 |
CA3103680A1 (en) | 2020-01-02 |
SG11202012162PA (en) | 2021-01-28 |
MX2020012675A (es) | 2021-02-09 |
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