CN115106082A - Composite oxide loaded gold-based alloy catalyst and preparation method and application thereof - Google Patents
Composite oxide loaded gold-based alloy catalyst and preparation method and application thereof Download PDFInfo
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- CN115106082A CN115106082A CN202210822417.0A CN202210822417A CN115106082A CN 115106082 A CN115106082 A CN 115106082A CN 202210822417 A CN202210822417 A CN 202210822417A CN 115106082 A CN115106082 A CN 115106082A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000010931 gold Substances 0.000 title claims abstract description 42
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 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 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 150000001206 Neodymium Chemical class 0.000 claims description 2
- 150000001213 Praseodymium Chemical class 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001216 Samarium Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 159000000009 barium salts Chemical class 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Chemical class 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910052762 osmium Inorganic materials 0.000 claims 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical class [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 6
- 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 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite oxide supported gold-based alloy catalyst and a preparation method and application thereof, belonging to the technical field of catalysts. Firstly, a composite oxide is obtained through a coprecipitation method, a precursor of the oxide is added while loading the gold-based alloy, and then a layer of oxide is modified on the surface, so that the gold-based alloy catalyst loaded by the composite oxide and wrapped by the oxide is obtained. The gold-based alloy catalyst disclosed by the invention keeps higher conversion rate and selectivity, the stability of the gold-based alloy catalyst is obviously improved, the gold-based alloy catalyst is applied to long-term operation of a slurry bed, the loss of metal in the catalyst is not obvious, the activity is better kept, and compared with the reaction of an intermittent reaction kettle, the reaction of the slurry bed is easier to industrially amplify, and the promotion of industrialization is facilitated.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite oxide loaded gold-based alloy catalyst, a preparation method thereof and application thereof in preparing methyl glycolate in a slurry bed.
Background
Methyl glycolate is a very important intermediate for drug synthesis and organic synthesis, and is an excellent solvent for cellulose, resins, and rubbers. Known processes for the large-scale production of methyl glycolate include: the method comprises the following steps of addition of formaldehyde and hydrocyanic acid, free radical addition of methylal and formaldehyde, carbonylation and esterification of formaldehyde and coupling reaction of methyl formate and formaldehyde. However, the method is gradually eliminated due to the disadvantages of high raw material price, serious corrosiveness in the production process, difficult separation of products and the like. Therefore, the development of a green and environment-friendly method for preparing methyl glycolate, which has the advantages of cheap raw materials, wide sources, simple process, and is urgently needed. Currently, the current practice is. The synthesis of methyl glycolate by using ethylene glycol and methanol as starting materials and through one-step oxidation esterification becomes a research focus. In the process, the separation and purification process of the product is simple, the product purity is high, the cost is low, and the process is a green chemical process route with development prospect.
In the prior art, a codeposition method is adopted, an oxide is used for modifying a supported catalyst, reaction is carried out in an intermittent reaction kettle, the conversion rate and the selectivity of preparing methyl glycolate from ethylene glycol are effectively improved, but the stability problem needs to be solved urgently.
Disclosure of Invention
In view of the above, the present invention provides a composite oxide supported gold-based alloy catalyst, and a preparation method and an application thereof. The gold-based alloy catalyst disclosed by the invention keeps higher conversion rate and selectivity, the stability of the gold-based alloy catalyst is obviously improved, the gold-based alloy catalyst is applied to long-term operation of a slurry bed, the loss of metal in the catalyst is not obvious, the activity is better kept, and the method is obviously superior to the result obtained by a batch reactor.
The purpose of the invention is realized by the following modes:
the invention provides a preparation method of a composite oxide loaded gold-based alloy catalyst, which mainly comprises the following steps:
(1) dissolving precursors of two oxides in water, wherein the precursors of the oxides comprise sodium salt, potassium salt, calcium salt, barium salt, chromium salt, magnesium salt, aluminum salt, lanthanum salt, praseodymium salt, neodymium salt, samarium salt and cerium salt, the mass ratio of the precursors of the two oxides is 1:10-10:1, adjusting the pH value of a system to 7.5-10 by using an alkaline aqueous solution, aging, drying, roasting in a mixed gas of oxygen and inert gas at the roasting temperature of 400-800 ℃, and preparing a composite oxide carrier;
(2) and (2) dispersing the composite oxide carrier obtained in the step (1) into an aqueous solution in which a gold salt and a second metal salt are dissolved, adding a precursor of a coating oxide, aging, drying, roasting in a mixed gas of oxygen and an inert gas, and reducing in hydrogen to obtain the composite oxide-loaded gold-based alloy catalyst.
Based on the above technical scheme, preferably, the specific process of drying after aging in step (1) is to heat the obtained solution to 50-70 ℃, stir for 1-5h, evaporate the water, and then dry the obtained precipitate at 150 ℃ below 100 ℃.
Based on the above technical solution, preferably, at least one of the precursors of the two oxides in step (1) is a precursor of an alkaline oxide, and the other one is one of chlorides, nitrates, sulfates, acetates, and aluminum isopropoxide of sodium, potassium, zinc, barium, chromium, magnesium, iron, calcium, copper, cobalt, nickel, aluminum, lanthanum, praseodymium, neodymium, samarium, and cerium.
Based on the above technical solution, preferably, the alkaline aqueous solution in step (1) is one of aqueous solutions of ammonia, potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate.
Based on the technical scheme, preferably, the volume percentage of oxygen in the mixed gas of oxygen and inert gas in the step (1) is 10-50%, the inert gas comprises argon and nitrogen, the roasting temperature rise rate is 1-10 ℃/min, and the roasting time is 2-10 h.
Based on the technical scheme, preferably, the gold salt in the step (2) is tetrachloroauric acid, gold chloride, Au (en) 2 Cl 3 The second metal salt is one of platinum, ruthenium, rhodium, palladium and osmiumOne of water soluble salts of iridium, iron, cobalt, nickel, copper and zinc.
Based on the above technical scheme, preferably, the gold loading amount in the gold-based alloy catalyst in the step (2) is 0.1-10 wt%, and the second metal loading amount in the gold-based alloy catalyst is 0.1-5 wt%.
Based on the above technical scheme, preferably, the precursor of the coating oxide in step (2) is one of chlorides, nitrates, sulfates, acetates, ethyl orthosilicate and aluminum isopropoxide of sodium, potassium, zinc, barium, chromium, magnesium, iron, calcium, copper, cobalt, nickel, aluminum, lanthanum, praseodymium, neodymium, samarium and cerium, and the loading amount of the coating oxide is 1-20 wt%.
Based on the technical scheme, preferably, the aging condition in the step (2) is 50-80 ℃ for 1-5 h.
Based on the technical scheme, preferably, the volume percentage of the oxygen in the mixed gas of the oxygen and the inert gas in the step (2) is 10-50%, the inert gas comprises argon and nitrogen, the roasting temperature is 400-600 ℃, the roasting time is 2-10h, the reduction temperature is 200-400 ℃, and the reduction time is 1-4 h.
In another aspect, the invention provides a composite oxide-supported gold-based alloy catalyst prepared by the above preparation method.
The invention also provides a method for preparing methyl glycolate by using the gold-based alloy catalyst loaded by the composite oxide, which comprises the steps of placing the gold-based alloy catalyst loaded by the composite oxide in a slurry bed reactor, pumping methanol and ethylene glycol, introducing air, and reacting at 60-150 ℃ to obtain the methyl glycolate.
Based on the technical scheme, preferably, the mass ratio of the methanol to the ethylene glycol is 0.1-50, the reaction temperature is 110-130 ℃, and the pressure is 0.1-5 MPa.
Compared with the prior art, the invention has the following beneficial effects:
the composite oxide used in the invention enhances the strong interaction between the metal and the carrier, the electronic effect of gold is obviously influenced after the second metal is added, higher conversion rate and selectivity are kept, and the interface effect between the metal and the oxide is greatly exerted after the second metal is wrapped by the oxide, so that the stability of the composite oxide is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
FIG. 1 is a comparative graph of stability tests of different catalysts in slurry bed catalysis of ethylene glycol to produce methyl glycolate.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Comparative example 1 preparation of catalyst 1% Au/MgAlOx
Preparing a composite oxide: adding aluminum nitrate and magnesium nitrate in a mass ratio of 1:1 into water, adjusting the pH value of the solution to about 8 by adding ammonia water, heating the solution to 60 ℃, continuously stirring for 2 hours, raising the temperature to 80 ℃, evaporating water, drying the obtained precipitate at 120 ℃, and roasting at 650 ℃ to obtain the composite oxide MgAlOx.
Preparation of a supported catalyst: putting the prepared chloroauric acid solution into a 250mL beaker, adding ultrapure water, stirring, adding a composite oxide MgAlOx to enable the theoretical loading capacity of gold on the composite oxide to be 1%, adjusting the pH value of the solution to be about 7 by ammonia water, aging for 3h, washing with deionized water, and performing suction filtration. The sample was placed in an oven at 80 ℃ to dry for 3 hours. The catalyst was then calcined at 500 ℃ for 4 hours in an air atmosphere to give a catalyst labeled 1% Au/MgAlOx.
200g of catalyst is taken and placed in a slurry bed reactor, a mixed solution (10: 1) of methanol and glycol is pumped into the slurry bed reactor at the speed of 5ml/min, the system pressure is kept at 0.5MPa during the reaction, the air flow rate is 5L/min, and the reaction temperature is 120 ℃. The product was condensed and stored in a liquid storage tank, and samples were taken at regular intervals for analysis, with the results shown in Table 1.
Comparative example 2 catalyst (1% Au/MgAlOx) @ SiO 2 Preparation of
Preparing a composite oxide: adding aluminum nitrate and magnesium nitrate in a mass ratio of 1:1 into water, adjusting the pH value of the solution to about 8 by adding ammonia water, heating the solution to 60 ℃, continuously stirring for 2 hours, raising the temperature to 80 ℃ and evaporating water. And then drying the obtained precipitate at 120 ℃, and roasting at 650 ℃ to obtain the composite oxide MgAlOx.
Preparation of a supported catalyst: putting the prepared chloroauric acid solution in a 250mL beaker, adding ultrapure water, stirring, adding a composite oxide MgAlOx to enable the theoretical load of gold on the composite oxide to be 1%, adjusting the pH of the solution to be about 7 by ammonia water, heating the solution to 70 ℃, then dropwise adding 1mL of tetraethoxysilane, aging for 3 hours, washing by deionized water, and carrying out suction filtration. The sample was placed in an oven at 80 ℃ to dry for 3 hours. The catalyst was subsequently calcined at 500 ℃ for 4 hours in an air atmosphere to give a catalyst designated (1% Au/MgAlOx) @ SiO 2 。
200g of catalyst is taken and placed in a slurry bed reactor, a mixed solution (10: 1) of methanol and glycol is pumped into the slurry bed reactor at the speed of 5ml/min, the system pressure is kept at 0.5MPa during the reaction, the air flow rate is 5L/min, and the reaction temperature is 120 ℃. The product was condensed and stored in a liquid storage tank, and samples were taken at regular intervals for analysis, with the results shown in Table 1.
EXAMPLE 1 catalyst (1% Au0.1% Pd/MgAlOx) @ SiO 2 Preparation of
Preparation of the composite oxide carrier: adding aluminum nitrate and magnesium nitrate in a mass ratio of 1:1 into water, adjusting the pH value of the solution to about 8 by adding ammonia water, heating the solution to 60 ℃, continuously stirring for 2 hours, raising the temperature to 80 ℃, evaporating water, drying the obtained precipitate at 120 ℃, and roasting at 650 ℃ to obtain the composite oxide MgAlOx.
Preparation of a supported catalyst: taking prepared chlorineAdding the gold acid and chloropalladate solution into a 250mL beaker, adding ultrapure water, stirring, adding a composite oxide MgAlOx to enable the theoretical loading of gold on the composite oxide to be 1% and the theoretical loading of palladium on the composite oxide to be 0.1%, adjusting the pH of the solution to be about 7 by ammonia water, heating the solution to 70 ℃, then dropwise adding 1mL of tetraethoxysilane, aging for 3h, washing by deionized water, and carrying out suction filtration. The sample was dried in an oven at 80 ℃ for 3 hours. The catalyst was subsequently calcined at 500 ℃ for 4 hours in an air atmosphere and then reduced at 300 ℃ for 2 hours in a hydrogen atmosphere to give a catalyst designated (1% Au0.1% Pd/MgAlOx) @ SiO 2 。
200g of catalyst is taken and placed in a slurry bed reactor, a mixed solution (10: 1) of methanol and glycol is pumped into the slurry bed reactor at the speed of 5ml/min, the system pressure is kept at 0.5MPa during the reaction, the air flow rate is 5L/min, and the reaction temperature is 120 ℃. The product was condensed and stored in a liquid storage tank, and samples were taken at regular intervals for analysis, with the results shown in Table 1.
EXAMPLE 2 catalyst (1% Au0.1% Pt/MgAlOx) @ SiO 2 Preparation of
Preparation of the composite oxide carrier: adding aluminum nitrate and magnesium nitrate in a mass ratio of 1:1 into water, adjusting the pH value of the solution to about 8 by adding ammonia water, heating the solution to 60 ℃, continuously stirring for 2 hours, raising the temperature to 80 ℃, evaporating water, drying the obtained precipitate at 120 ℃, and roasting at 650 ℃ to obtain the composite oxide MgAlOx.
Preparation of a supported catalyst: putting prepared chloroauric acid and chloroplatinic acid solution into a 250mL beaker, adding ultrapure water, stirring, adding a composite oxide MgAlOx to enable the theoretical loading capacity of gold on the composite oxide to be 1% and the theoretical loading capacity of platinum on the composite oxide to be 0.1%, adjusting the pH value of the solution to be about 7 by ammonia water, heating the solution to 70 ℃, then dropwise adding 1mL of tetraethoxysilane, aging for 3h, washing with deionized water, and carrying out suction filtration. The sample was dried in an oven at 80 ℃ for 3 hours, and then the catalyst was calcined at 500 ℃ for 4 hours in an air atmosphere and reduced at 300 ℃ for 2 hours in a hydrogen atmosphere to obtain a catalyst designated (1% Au0.1% Pt/MgAlOx) @ SiO 2 。
200g of catalyst is taken and placed in a slurry bed reactor, a mixed solution (10: 1) of methanol and glycol is pumped into the slurry bed reactor at the speed of 5ml/min, the system pressure is kept at 0.5MPa during the reaction, the air flow rate is 5L/min, and the reaction temperature is 120 ℃. The product was condensed and stored in a liquid storage tank, and samples were taken at regular intervals for analysis, with the results shown in Table 1.
EXAMPLE 3 catalyst (1% Au0.3% Ni/MgAlOx) @ SiO 2 Preparation of
Preparation of the composite oxide carrier: adding aluminum nitrate and magnesium nitrate in a mass ratio of 1:1 into water, adjusting the pH value of the solution to about 8 by adding ammonia water, heating the solution to 60 ℃, continuously stirring for 2 hours, raising the temperature to 80 ℃, evaporating water, drying the obtained precipitate at 120 ℃, and roasting at 650 ℃ to obtain the composite oxide MgAlOx.
Preparation of a supported catalyst: putting prepared chloroauric acid and nickel nitrate solution into a 250mL beaker, adding ultrapure water, stirring, adding a composite oxide MgAlOx to enable the theoretical loading capacity of gold on the composite oxide to be 1% and the theoretical loading capacity of nickel on the composite oxide to be 0.3%, adjusting the pH value of the solution to be about 7 by ammonia water, heating the solution to 70 ℃, then dropwise adding 1mL of tetraethoxysilane, aging for 3h, washing with deionized water, and carrying out suction filtration. The sample was dried in an oven at 80 ℃ for 3 hours, and then the catalyst was calcined at 500 ℃ for 4 hours in an air atmosphere and then reduced at 450 ℃ for 2 hours in a hydrogen atmosphere to obtain a catalyst designated as (1% Au0.3% Ni/MgAlOx) @ SiO 2 。
200g of catalyst is taken and placed in a slurry bed reactor, a mixed solution (10: 1) of methanol and glycol is pumped into the slurry bed reactor at the speed of 5ml/min, the system pressure is kept at 0.5MPa during the reaction, the air flow rate is 5L/min, and the reaction temperature is 120 ℃. The product was condensed and stored in a stock solution tank, and samples were taken at regular intervals for analysis, and the ethylene glycol conversion rate and methyl glycolate selectivity as well as the stability results of the catalyst are shown in table 1 and fig. 1.
TABLE 1 conversion of ethylene glycol and product selectivity for 3 hours of reaction of different catalysts in a slurry bed
As can be seen from the data of fig. 1 and table 1, the catalysts prepared in examples 1 to 3 have not only higher conversion of ethylene glycol and selectivity of methyl glycolate but also very excellent catalytic stability, as compared to comparative examples 1 to 2.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the composite oxide supported gold-based alloy catalyst is characterized by mainly comprising the following steps of:
(1) dissolving precursors of two oxides in water, wherein the precursors of the oxides comprise sodium salt, potassium salt, calcium salt, barium salt, chromium salt, magnesium salt, aluminum salt, lanthanum salt, praseodymium salt, neodymium salt, samarium salt and cerium salt, the mass ratio of the precursors of the two oxides is 1:10-10:1, adjusting the pH value of a system to 7.5-10 by using an alkaline aqueous solution, aging, drying, roasting in a mixed gas of oxygen and inert gas at the roasting temperature of 400-800 ℃, and preparing a composite oxide carrier;
(2) and (2) dispersing the composite oxide carrier obtained in the step (1) into an aqueous solution in which a gold salt and a second metal salt are dissolved, adding a precursor of a coating oxide, aging, drying, roasting in a mixed gas of oxygen and an inert gas, and reducing in hydrogen to obtain the composite oxide-loaded gold-based alloy catalyst.
2. The method according to claim 1, wherein at least one of the precursors of the two oxides in step (1) is a precursor of an alkaline oxide, and the other is one of chlorides, nitrates, sulfates, acetates, and aluminum isopropoxide of sodium, potassium, zinc, barium, chromium, magnesium, iron, calcium, copper, cobalt, nickel, aluminum, lanthanum, praseodymium, neodymium, samarium, and cerium.
3. The preparation method according to claim 1, wherein the volume percentage of oxygen in the mixed gas of oxygen and inert gas in the step (1) is 10-50%, the inert gas comprises argon and nitrogen, the roasting temperature rise rate is 1-10 ℃/min, and the roasting time is 2-10 h.
4. The method according to claim 1, wherein the gold salt in the step (2) is tetrachloroauric acid, gold chloride, Au (en) 2 Cl 3 The second metal salt is one of water-soluble salts of platinum, ruthenium, rhodium, palladium, osmium, iridium, iron, cobalt, nickel, copper and zinc.
5. The method of claim 1, wherein the gold loading in the gold-based alloy catalyst in step (2) is 0.1 to 10 wt% and the second metal loading in the gold-based alloy catalyst is 0.1 to 5 wt%.
6. The preparation method according to claim 1, wherein the precursor of the coating oxide in the step (2) is one of chlorides, nitrates, sulfates, acetates, ethyl orthosilicate and aluminum isopropoxide of sodium, potassium, zinc, barium, chromium, magnesium, iron, calcium, copper, cobalt, nickel, aluminum, lanthanum, praseodymium, neodymium, samarium and cerium, and the loading of the coating oxide is 1-20 wt%.
7. The method according to claim 1, wherein the volume percentage of oxygen in the mixed gas of oxygen and inert gas in step (2) is 10-50%, the inert gas comprises argon and nitrogen, the calcination temperature is 400-.
8. A complex oxide-supported gold-based alloy catalyst produced by the production method described in any one of claims 1 to 7.
9. A method for preparing methyl glycolate by using the composite oxide supported gold-based alloy catalyst of claim 8, wherein the composite oxide supported gold-based alloy catalyst is placed in a slurry bed reactor, methanol and ethylene glycol are pumped, air is introduced, and the reaction is carried out at 60-150 ℃ to obtain the methyl glycolate.
10. The method as claimed in claim 9, wherein the mass ratio of methanol to ethylene glycol is 0.1-50, the reaction temperature is 110-130 ℃, and the pressure is 0.1-5 MPa.
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| CN114029053A (en) * | 2021-11-22 | 2022-02-11 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol |
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| US20030060655A1 (en) * | 2001-06-04 | 2003-03-27 | Toshio Hayashi | Catalyst for the preparation of carboxylic esters and method for producing carboxylic esters |
| JP2004137180A (en) * | 2002-10-16 | 2004-05-13 | Nippon Shokubai Co Ltd | Method for producing carboxylate |
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| CN114011405A (en) * | 2021-11-22 | 2022-02-08 | 中国科学院大连化学物理研究所 | Preparation method of composite oxide supported catalyst and application of composite oxide supported catalyst in preparation of methyl glycolate from ethylene glycol |
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