CN114602498A - Sea urchin shaped In2O3Cu-Ag loaded bimetallic alloy catalyst and preparation method and application thereof - Google Patents
Sea urchin shaped In2O3Cu-Ag loaded bimetallic alloy catalyst and preparation method and application thereof Download PDFInfo
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- CN114602498A CN114602498A CN202210229529.5A CN202210229529A CN114602498A CN 114602498 A CN114602498 A CN 114602498A CN 202210229529 A CN202210229529 A CN 202210229529A CN 114602498 A CN114602498 A CN 114602498A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 239000000956 alloy Substances 0.000 title claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 241000257465 Echinoidea Species 0.000 title description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017770 Cu—Ag Inorganic materials 0.000 claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011068 loading method Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 150000002471 indium Chemical class 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229960001124 trientine Drugs 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 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 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- WYCFMBAHFPUBDS-UHFFFAOYSA-L silver sulfite Chemical compound [Ag+].[Ag+].[O-]S([O-])=O WYCFMBAHFPUBDS-UHFFFAOYSA-L 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 20
- 239000003345 natural gas Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to sea urchin-like In2O3A supported Cu-Ag bimetallic alloy catalyst and a preparation method and application thereof. The carrier of the catalyst is In with a sea urchin-like structure2O3The active components are Cu and Ag. The preparation method comprises the following steps: (1) preparing an indium salt and a bicarbonate salt into an aqueous solution, and adding a surfactant; (2) adding alcohol and amine into the aqueous solution prepared In the step (1), and preparing echinoid In by hydrothermal method2O3(ii) a (3) Preparing a Cu-Ag aqueous solution from a silver salt and a copper salt; (4) loading Cu-Ag into echinoid In2O3In H2Reducing In the mixed atmosphere of/Ar to obtain sea urchin-shaped In2O3Loading Cu-Ag bimetallic alloy catalyst. Sea urchin-like In provided by the invention2O3The supported Cu-Ag bimetallic alloy catalyst can be used for preparing acetic acid by catalytically converting methane and carbon dioxide, and has good catalytic activity and selectivity.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, In particular to sea urchin-shaped In2O3A Cu-Ag loaded bimetallic alloy catalyst, a preparation method and application thereof.
Background
China provides carbon emission reduction targets for actively coping with global climate change, wherein the carbon emission strives to reach a peak value 2030 years ago, and strives to realize carbon neutralization 2060 years ago; the method has the advantages that the method puts higher requirements on energy consumption and transformation while showing the responsibility of responsible countries. Natural gas plays a key role in the national energy strategy, and in recent years, with the rapid increase of natural gas consumption, the external dependence degree is correspondingly increased. In order to deal with climate change, the aims of carbon peak reaching and carbon neutralization in China are fulfilled, the development and utilization of marine natural gas, particularly natural gas in south China sea are accelerated, and the method is an energy transformation development direction according with the national situation.
The natural gas resource in the south China sea area has rich oil and gas resources, and the natural gas resource in the south China sea area has large reserve volume, so that the natural gas resource is an important guarantee for the development of the natural gas industry in China. However, the natural gas from south China sea contains high concentration of CO2The corresponding composition is significantly different from natural gas in inland regions: CO of typical gas field in south China sea2The content is generally 20-80%. This type of CO-containing2Often referred to as carbon-rich natural gas, typically requires removal of CO2And then the product is supplied for production and life. The traditional development and utilization of the carbon-rich natural gas in south China sea causes a great amount of greenhouse gas emission, and is not beneficial to carbon emission reduction, so that a new technology for carbon-rich natural gas utilization needs to be developed urgently to support the high-quality development of the marine oil and gas industry in China (China Pet Process Pe,2020,22(2): 1-9).
The large-scale natural gas chemical industry mainly prepares chemicals such as methanol, urea, ethylene glycol and the like through synthesis gas. For CH4、CO2Two typical greenhouse gases, the industry has been around new technologies and new processes, mainly through reforming, gasification, etc. processes to convert to syngas (CO + H)2) Further converted into energy chemical products such as chemicals, fuels and the like. Methanol is the main chemical of synthesis gasOne of the products is connected with a synthesis gas high-efficiency utilization technology by a related technology, so that large-scale commercial utilization is possible; meanwhile, the synthesis gas is used for preparing high-value chemicals, such as direct preparation of olefin/aromatic hydrocarbon from the synthesis gas, hydroformylation of the synthesis gas and the like. At present, CO2-CH4The technology for preparing synthesis gas by dry reforming and the preparation of chemical products by synthesis gas are research hotspots in the field, more basic researches are carried out, and the proposed new catalyst and new process scheme provide a solid technical foundation for the direct utilization of the carbon-rich natural gas in south China sea (China science: chemistry, 2020,50(7): 816-.
With CH4、CO2The direct conversion of the raw materials into acetic acid is a reaction with the atom utilization rate of 100 percent and can comprehensively utilize CO2And CH4And (4) resources. CH (CH)4、CO2The direct conversion into acetic acid can realize the activation of the CO which is a small molecular substance difficult to be activated2And CH4The conversion of (1) and simultaneously reduces the influence of the two main greenhouse gases on the environment, and has research values in various aspects such as environmental protection, science, economy and the like (ACCcatal, 2021,11, 3384-.
Wilcox et al investigated the direct synthesis of acetic acid from methane and carbon dioxide by introducing 95% CO by volume at 725 ℃ under 100atm2And 5% CH4，CH4Also only 1.6x 10-6(Catal day,2003,88, 83-90). Increased ZrO by Yufeng Li et al2Increasing CH by Lewis acidity of catalyst4And CO2Yield of synthesized acetic acid. The sulfated catalyst has purer ZrO2The selectivity of acetic acid is improved by about 14 times, and after the catalyst is placed in a fixed bed at 500 ℃ for normal pressure reaction for 20 hours, the space-time yield of the acetic acid is 0.7 mu mol gcat -1·h-1(New J.Chem.,2021,45,8978-8985)。
Disclosure of Invention
The invention aims to provide a method for promoting the dispersion of active components by utilizing the structure similar to echinoid indium oxide and strong interaction between the echinoid indium oxide and the active components to overcome the defects of poor selectivity of the existing reaction for preparing acetic acid from methane and carbon dioxide and high reaction pressureSea urchin shaped In2O3The invention also provides a preparation method of the supported Cu-Ag bimetallic alloy catalyst, and an application of the supported Cu-Ag bimetallic alloy catalyst in preparation of acetic acid from methane and carbon dioxide. The catalyst prepared by the invention has the reaction performance of catalyzing methane and carbon dioxide to prepare acetic acid, can generate acetic acid with high selectivity under the normal pressure reaction condition, and has good application prospect in the field of preparing chemicals with high added value from methane and carbon dioxide.
The technical scheme of the invention is as follows: sea urchin-shaped In2O3The Cu-Ag supported bimetallic alloy catalyst is characterized In that the carrier is In with a sea urchin-like structure2O3The active components are Cu and Ag, wherein the load mass of the copper is In2O31-5% of the carrier, and In as the silver loading mass2O30.1-5% of the carrier by mass.
The invention also provides the sea urchin-shaped In prepared by the method2O3The method for loading the Cu-Ag bimetallic alloy catalyst comprises the following specific steps:
(1) preparing an indium salt and a bicarbonate salt into an aqueous solution, adding a surfactant, and stirring;
(2) adding alcohol and amine into the aqueous solution prepared in the step (1), stirring, carrying out hydrothermal reaction, cooling, centrifuging, washing, and carrying out vacuum drying;
(3) preparing silver salt and copper salt into Cu-Ag aqueous solution, adding the solid obtained in the step (2) into the Cu-Ag aqueous solution, carrying out water bath ageing, centrifuging, washing, vacuum drying, and dissolving the prepared solid in H2Reducing In-Ar mixed atmosphere to obtain sea urchin-shaped In2O3Loading Cu-Ag bimetallic alloy catalyst.
Preferably, the indium salt in the step (1) is one of indium nitrate, indium chloride and indium sulfate; the bicarbonate salt is one of sodium bicarbonate, calcium bicarbonate, ammonium bicarbonate or potassium bicarbonate; the surfactant is one of sodium dodecyl sulfate or sodium dodecyl sulfate.
Preferably, in the step (1), the molar ratio of the indium salt to the bicarbonate salt is 1 (2-10), and the molar ratio of the indium salt to the surfactant is 1 (1-9).
Preferably, the alcohol in the step (2) is one of ethanol, isopropanol, n-butanol, glycerol, ethylene glycol, glycol or 1, 2-ethylene glycol; the amine is one of triethylenetetramine, triethylenediamine or trientine.
Preferably, in the step (2), the molar ratio of the alcohol to the amine is (2-20): 1, and the molar ratio of the alcohol to the indium salt is (6-200): 1; the temperature of the hydrothermal reaction is 120-260 ℃, and the time of the hydrothermal reaction is 6-24 h.
Preferably, the silver salt in step (3) is one of silver nitrate, silver chloride, silver sulfate or silver sulfite; the copper salt is one of copper sulfate, copper nitrate, copper chloride, copper citrate, copper acetylacetonate or copper oxalate.
Preferably, the temperature of the water bath in the step (3) is 30-80 ℃, and the aging time is 1-8 h; the vacuum drying temperature is 50-80 ℃, and the drying time is 2-24 h; h2H in the mixed gas of/Ar2Is H in25 to 95 percent of the total volume of the/Ar mixed gas; the reduction temperature is 400-600 ℃, and the reduction time is 0.5-8 h.
The invention also provides the echinoid In2O3The Cu-Ag loaded bimetallic alloy catalyst is applied to the preparation of acetic acid from methane and carbon dioxide. The method is characterized in that: the reaction temperature of the fixed bed is 300-700 ℃, and the reaction space velocity of the fixed bed is 283-2200 h-1And in the reaction process, the volume ratio of the methane to the carbon dioxide is 1 (0.7-1.2).
Has the advantages that:
the invention prepares a heterogeneous catalyst which takes echinoid indium oxide as a carrier and bimetallic alloy as an active component and is uniformly and stably dispersed.
Detailed Description
The present invention is described in more detail below with reference to examples. These examples are only illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
Step 1, 1mmol of indium nitrate and 2mmol of NaHCO3Adding into deionized water containing 1mmol sodium dodecyl sulfate, and stirring;
step 2, adding 0.2mol of ethylene glycol and 0.1mol of triethylenetetramine into the solution, stirring, heating for 6 hours at 120 ℃, centrifuging, washing, and drying for 2 hours at 50 ℃ in vacuum;
step 3, preparing 0.001mmol silver nitrate and 0.02mmol copper sulfate into water solution, adding the substance obtained in the step 2, carrying out water bath at 30 ℃ for 1H, centrifuging, washing, carrying out vacuum drying at 50 ℃ for 2H, and carrying out volume ratio of the prepared solid at 400 ℃ to 5% of H2Reducing for 0.5h In the mixed atmosphere of/Ar to obtain sea urchin-shaped In2O3The Cu-Ag supported bimetallic alloy catalyst has copper loading of 1.1% and silver loading of 0.1%;
step 4, setting the space velocity of the fixed bed to 283h-1Then raising the temperature to 300 ℃, introducing methane and carbon dioxide with the volume ratio of 1:0.7, and analyzing the gas phase product by chromatography, wherein the selectivity of acetic acid is 90.41 percent, and the space-time yield of acetic acid is 342 mu mol gcat -1·h-1。
Example 2
Step 1, 30mmol indium chloride and 120mmol Ca (HCO)3)2Adding 60mmol sodium dodecyl sulfate ion water, and stirring;
step 2, adding 0.2mol of n-butanol and 0.1mol of triethylenediamine into the solution, stirring, heating at 160 ℃ for 12h, centrifuging, washing, and vacuum drying at 50 ℃ for 10 h;
step 3, preparing 0.8mmol of silver sulfate and 3.25mmol of copper chloride into aqueous solution, adding the solid obtained in the step (2), carrying out water bath at 50 ℃ for 6H, centrifuging, washing, carrying out vacuum drying at 50 ℃ for 10H, and carrying out volume ratio of the prepared solid at 450 ℃ to 10% of H2Reducing for 4h under the mixed atmosphere of/He to obtain echinoid In2O3The Cu-Ag supported bimetallic alloy catalyst has copper supported in the amount of 5 wt% and silver supported in the amount ofThe loading capacity is 2.1 percent of the mass of the carrier;
step 4, setting the space velocity of the fixed bed to 356h-1Then raising the temperature to 400 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1, and analyzing the gas phase product by chromatography, wherein the selectivity of acetic acid is 91.14 percent, and the space-time yield of the acetic acid is 345 mu mol gcat -1·h-1。
Example 3
Step 1, 60mmol of indium chloride and 240mmol of NH4HCO3Adding the mixture into deionized water containing 240mmol of lauryl sodium sulfate, and stirring;
step 2, adding 0.4mol of glycerol and 0.1mol of trientine into the solution, stirring, heating for 10 hours at 160 ℃, centrifuging, washing, and drying for 12 hours at 50 ℃ in vacuum;
step 3, preparing aqueous solution of 1.3mmol of silver sulfite and 2.9mmol of copper citrate, adding the solid obtained in the step (2), carrying out water bath at 50 ℃ for 7.5H, centrifuging, washing, carrying out vacuum drying at 50 ℃ for 8H, and carrying out volume ratio of the prepared solid at 500 ℃ to 25% of H2Reducing for 4.5h under the mixed atmosphere of/He to obtain echinoid In2O3The Cu-Ag supported bimetallic alloy catalyst comprises a Cu-Ag supported bimetallic alloy catalyst, wherein the loading amount of copper is 2.3% of the mass of a carrier, and the loading amount of silver is 1.7% of the mass of the carrier;
step 4, setting the airspeed of the fixed bed to 483h-1Then raising the temperature to 500 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1.1, and analyzing the gas phase product by chromatography, wherein the selectivity of acetic acid is 91.56 percent, and the space-time yield of the acetic acid is 346 mu mol gcat -1·h-1。
Example 4
Step 1, 79mmol of indium chloride and 474mmol KHCO3Adding the mixture into deionized water containing 474mmol of lauryl sodium sulfate, and stirring;
step 2, adding 1mol of glycol and 0.1mol of triethylenetetramine into the solution, stirring, heating for 12h at 180 ℃, centrifuging, washing, and vacuum drying for 8h at 60 ℃;
step 3, preparing 2.6mmol of silver nitrate and 3.3mmol of copper acetylacetonate into aqueous solution, adding the solid obtained in the step 2, and carrying out water bath at 60 ℃ for 5 hoursCentrifuging, washing, vacuum drying at 60 deg.C for 8 hr to obtain solid with volume ratio of 50% H at 500 deg.C2Reducing for 5h under the mixed atmosphere of/He to obtain echinoid In2O3The Cu-Ag supported bimetallic alloy catalyst comprises a Cu-Ag supported bimetallic alloy catalyst, wherein the loading amount of copper is 1.9% of the mass of a carrier, and the loading amount of silver is 2.6% of the mass of the carrier;
step 4, setting the space velocity of the fixed bed to 594h-1Then raising the temperature to 600 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1, and carrying out chromatographic analysis on a gas phase product, wherein the selectivity of acetic acid is 91.69 percent, and the space-time yield of acetic acid is 347 mu mol gcat -1·h-1。
Example 5
Step 1, 76mmol of indium sulfate and 760mmol of NaHCO3Adding the mixture into deionized water containing 608mmol of sodium dodecyl sulfate, and stirring;
step 2, adding 1, 2-ethylene glycol and triethylenediamine 0.1mol into the solution, stirring, heating for 8h at 180 ℃, centrifuging, washing, and vacuum drying for 12h at 60 ℃;
step 3, preparing aqueous solution of 18.2mmol of silver nitrate and 8.2mmol of copper oxalate, adding the solid obtained in the step 2, carrying out water bath at 80 ℃ for 3H, centrifuging, washing, carrying out vacuum drying at 60 ℃ for 8H, and carrying out volume ratio of the prepared solid at 550 ℃ to 75% of H2Reducing for 6h under the mixed atmosphere of/He to obtain echinoid In2O3The Cu-Ag bimetallic alloy catalyst is loaded, wherein the loading amount of copper is 1.3 percent of the mass of the carrier, and the loading amount of silver is 5 percent of the mass of the carrier;
step 4, setting the airspeed of the fixed bed to 667h-1Then raising the temperature to 600 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1.2, and analyzing the gas phase product by chromatography, wherein the selectivity of acetic acid is 91.78 percent, and the space-time yield of acetic acid is 347 mu mol gcat -1·h-1。
Example 6
Step 1, 20mmol of indium chloride and 40mmol of NaHCO3Adding the mixture into deionized water containing 160mmol of sodium dodecyl sulfate, and stirring;
step 2, adding 2mol of ethanol and 0.1mol of triethylenetetramine into the solution, stirring, heating for 24h at 260 ℃, centrifuging, washing, and vacuum-drying for 24h at 80 ℃;
step 3, preparing aqueous solution of 0.3mmol of silver nitrate and 1.2mmol of copper nitrate, adding the solid obtained in the step 2, carrying out water bath at 80 ℃ for 8 hours, centrifuging, washing, carrying out vacuum drying at 80 ℃ for 24 hours, and carrying out volume ratio of the prepared solid at 600 ℃ to 95% of H2Reducing for 8h under the mixed atmosphere of/He to obtain echinoid In2O3The Cu-Ag supported bimetallic alloy catalyst comprises a Cu-Ag supported bimetallic alloy catalyst, wherein the loading amount of copper is 2.7% of the mass of a carrier, and the loading amount of silver is 1.3% of the mass of the carrier;
step 4, setting the space velocity of the fixed bed to 2200h-1Then raising the temperature to 700 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1.2, and carrying out chromatographic analysis on a gas phase product to obtain an acetic acid selectivity of 92.82 percent and an acetic acid space-time yield of 351 mu mol gcat -1·h-1。
Comparative example 1
Step 1, 56mmol of indium nitrate and 224mmol of NaHCO3Adding the mixture into deionized water containing 224mmol of sodium dodecyl sulfate, and stirring;
step 2, adding 0.8mol of ethanol and 0.1mol of triethylenetetramine into the solution, stirring, heating for 6 hours at 120 ℃, centrifuging, washing, and drying for 2 hours at 50 ℃ in vacuum;
step 3, preparing 5.7mmol of copper nitrate into an aqueous solution, adding the substance obtained in the step 2, carrying out water bath at 30 ℃ for 1H, centrifuging, washing, carrying out vacuum drying at 50 ℃ for 2H, and carrying out volume ratio of the prepared solid at 600 ℃ to 5% of H2Reducing for 1.5h under the mixed atmosphere of/He to obtain echinoid In2O3A supported Cu catalyst, wherein the loading amount of copper is 4.7 percent of the mass of the carrier, and the loading amount of silver is 0 percent of the mass of the carrier;
step 4, setting the airspeed of the fixed bed to 667h-1Then raising the temperature to 600 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1, and analyzing the gas phase product by chromatography, wherein the selectivity of acetic acid is 47.65 percent, and the space-time yield of the acetic acid is 180 mu mol gcat -1·h-1。
Comparative example 2
Step 1, 69mmol of indium nitrate hydrate and 276mmol of NaHCO3Adding into deionized water containing 276mmol sodium dodecyl sulfate, and stirring;
step 2, adding 1mol of ethanol and 0.1mol of triethylenetetramine into the solution, stirring, heating for 6 hours at 120 ℃, centrifuging, washing, and drying for 2 hours at 50 ℃ in vacuum;
step 3, preparing 4.2mmol of silver nitrate into aqueous solution, adding the substance obtained in the step 2, carrying out water bath at 30 ℃ for 1H, centrifuging, washing, carrying out vacuum drying at 50 ℃ for 2H, and carrying out volume ratio of the prepared solid at 600 ℃ to 5% of H2Reducing for 2h under the mixed atmosphere of/He to obtain echinoid In2O3The supported Ag catalyst comprises copper with the loading amount of 0% of the mass of the carrier and silver with the loading amount of 4.7% of the mass of the carrier;
step 4, setting the airspeed of the fixed bed to 667h-1Then raising the temperature to 600 ℃, introducing methane and carbon dioxide with the volume ratio of 1:1, and carrying out chromatographic analysis on a gas phase product to obtain the product with the acetic acid selectivity of 50.34 percent and the acetic acid space-time yield of 190 mu mol gcat -1·h-1。
TABLE 1 results of catalyst Performance testing
Claims (10)
1. Sea urchin-shaped In2O3The Cu-Ag supported bimetallic alloy catalyst is characterized In that the carrier is In with a sea urchin-like structure2O3The active components are Cu and Ag, wherein the load mass of the copper is In2O31-5% of the carrier, and In as the silver loading mass2O30.1-5% of the carrier by mass.
2. A method for producing echinoid In according to claim 12O3The method for loading the Cu-Ag bimetallic alloy catalyst comprises the following specific steps:
(1) preparing an indium salt and a bicarbonate salt into an aqueous solution, adding a surfactant, and stirring;
(2) adding alcohol and amine into the aqueous solution prepared in the step (1), stirring, carrying out hydrothermal reaction, cooling, centrifuging, washing, and carrying out vacuum drying;
(3) preparing silver salt and copper salt into Cu-Ag aqueous solution, adding the solid obtained in the step (2) into the Cu-Ag aqueous solution, carrying out water bath ageing, centrifuging, washing, vacuum drying, and dissolving the prepared solid in H2Reducing In-Ar mixed atmosphere to obtain sea urchin-shaped In2O3Loading Cu-Ag bimetallic alloy catalyst.
3. The method of claim 2, wherein: the indium salt in the step (1) is one of indium nitrate, indium chloride or indium sulfate; the bicarbonate salt is one of sodium bicarbonate, calcium bicarbonate, ammonium bicarbonate or potassium bicarbonate; the surfactant is one of sodium dodecyl sulfate or sodium dodecyl sulfate.
4. The method of claim 2, wherein: the molar ratio of the indium salt to the bicarbonate salt in the step (1) is 1 (2-10), and the molar ratio of the indium salt to the surfactant is 1 (1-9).
5. The method of claim 2, wherein: the alcohol in the step (2) is one of ethanol, isopropanol, n-butanol, glycerol, ethylene glycol, glycol or 1, 2-ethylene glycol; the amine is one of triethylenetetramine, triethylenediamine or trientine.
6. The method of claim 2, wherein: in the step (2), the molar ratio of the alcohol to the amine is (2-20): 1, and the molar ratio of the alcohol to the indium salt is (6-200): 1; the temperature of the hydrothermal reaction is 120-260 ℃, and the time of the hydrothermal reaction is 6-24 h.
7. The method of claim 2, wherein: the silver salt in the step (3) is one of silver nitrate, silver chloride, silver sulfate or silver sulfite; the copper salt is one of copper sulfate, copper nitrate, copper chloride, copper citrate, copper acetylacetonate or copper oxalate.
8. The method of claim 2, wherein: the temperature of the water bath in the step (3) is 30-80 ℃, and the aging time is 1-8 h; the vacuum drying temperature is 50-80 ℃, and the drying time is 2-24 h; h2H in the mixed gas of/Ar2Is H in25 to 95 percent of the total volume of the/Ar mixed gas; the reduction temperature is 400-600 ℃, and the reduction time is 0.5-8 h.
9. Sea urchin-like In according to claim 12O3The Cu-Ag loaded bimetallic alloy catalyst is applied to the preparation of acetic acid from methane and carbon dioxide.
10. Use according to claim 1, characterized in that: the reaction temperature is 300-700 ℃, and the reaction space velocity is 283-2200 h-1The volume ratio of the methane to the carbon dioxide is 1 (0.7-1.2).
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| CN117839692A (en) * | 2024-01-05 | 2024-04-09 | 江西师范大学 | Co-deposition of In with Au and Ag 2 O 3 Photocatalyst, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006014834A1 (en) * | 2004-07-28 | 2006-02-09 | The Regents Of The University Of California | Process for oxidation of methane to acetic acid |
| CN113663716A (en) * | 2021-09-28 | 2021-11-19 | 南京工业大学 | Indium oxide loaded metal monatomic catalyst and application thereof |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006014834A1 (en) * | 2004-07-28 | 2006-02-09 | The Regents Of The University Of California | Process for oxidation of methane to acetic acid |
| CN113663716A (en) * | 2021-09-28 | 2021-11-19 | 南京工业大学 | Indium oxide loaded metal monatomic catalyst and application thereof |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
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| CHUNYAN TU ET AL.: "Insight into Acetic Acid Synthesis from the Reaction of CH4 and CO2" * |
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| CN117839692A (en) * | 2024-01-05 | 2024-04-09 | 江西师范大学 | Co-deposition of In with Au and Ag 2 O 3 Photocatalyst, preparation method and application thereof |
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