CN111589466A - Synthesis and application of copper wire mordenite catalyst - Google Patents
Synthesis and application of copper wire mordenite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000012265 solid product Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000012495 reaction gas Substances 0.000 claims description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 66
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- 239000003345 natural gas Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
- C01B39/265—Mordenite type using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
-
- 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
Abstract
The synthesis of copper wire mordenite catalyst belongs to the field of catalyst synthesis, and is characterized by comprising the following steps: dissolving a template agent in a sodium hydroxide solution to obtain a solution I; adding an aluminum source into the solution I, and dissolving to obtain a solution II; adding a silicon source into the solution II, and uniformly mixing to form a gel mixture; adding a copper nitrate solution into the gel mixture, transferring the gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle in a constant-temperature oven for crystallization; after crystallization is finished, centrifugally separating, washing with deionized water, drying and roasting the crystallized solid product in a muffle furnace to obtain the copper wire mordenite catalyst. The synthetic method is simple, industrial large-scale production is facilitated, the synthesized copper wire mordenite catalyst can catalyze methane to prepare methanol through low-temperature selective oxidation, the reaction condition is mild, the methane conversion rate is high, the methanol selectivity is good, and the application prospect is good.
Description
Technical Field
The invention belongs to the field of catalyst synthesis, and particularly relates to synthesis and application of a copper wire mordenite catalyst.
Background
Methane is a main component of natural gas, the conversion and application of methane are important research directions in the field of natural gas chemical industry, and particularly, with the development of unconventional natural gas resources such as shale gas, chemicals prepared by methane catalytic conversion are widely concerned.
Methanol is an extremely important organic chemical raw material, can be used for producing formaldehyde, acetic acid, methyl tert-butyl ether (MBTE), Methyl Methacrylate (MMA) and the like, and has wide application in the fields of chemical industry, medicine, textile and the like. The concept of "methanol economy" was proposed by George a. Olah, who won't be a chemical prize, i.e. methanol can be used as an energy storage material and fuel, partly replacing fossil fuels that are widely used at present. Therefore, methanol and its downstream products have wide applications.
At present, the method of catalytic hydrogenation of carbon monoxide is mainly adopted for industrially preparing methanol, and the utilization rate of the indirect conversion of carbon atoms by methane is low and the energy consumption is high. In principle, it is feasible to obtain synthesis gas and then synthesize methanol from any carbon resource, such as natural gas, coal and biomass through gasification, but the direct selective oxidation of natural gas to prepare methanol is the most atomic and economical reaction, and the preparation of methanol from natural gas and cheap and easily available oxygen also has good economic benefits.
Disclosure of Invention
The invention aims to provide synthesis and application of a copper wire mordenite catalyst.
The synthesis of the copper mordenite catalyst comprises the following steps:
dissolving a template agent in a sodium hydroxide solution to obtain a solution I;
adding an aluminum source into the solution I, and dissolving to obtain a solution II;
adding a silicon source into the solution II, and uniformly mixing to form a gel mixture;
adding a copper nitrate solution into the gel mixture, transferring the gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle in a constant-temperature oven for crystallization; after crystallization is finished, the crystallized solid product is centrifugally separated, washed by deionized water, dried and roasted in a muffle furnace to obtain the copper wire mordenite catalyst.
Preferably, in the synthesis of the copper mordenite catalyst, the template agent is tetraethylammonium hydroxide or tetraethylammonium bromide.
Preferably, in the synthesis of the copper mordenite catalyst, the aluminum source is sodium aluminate or aluminum nitrate.
Preferably, in the synthesis of the copper mordenite catalyst, the silicon source is silica sol.
Preferably, in the synthesis of the copper mordenite catalyst, the crystallization temperature is 120-.
The application of the copper mordenite catalyst comprises the steps of placing the copper mordenite catalyst with 20-40 meshes in a fixed bed reactor, introducing oxygen for activation, then introducing nitrogen, adjusting to the reaction temperature, and switching to reaction gas.
Preferably, the copper mordenite catalyst is applied, and the reaction gas is a mixed gas of methane, water and oxygen; reaction temperature of 150 ℃ 220-oC, the reaction pressure is 0.1-2 MPa.
Preferably, the partial pressure ratio of the methane, the water and the oxygen is (1-5): (0.1-2): 1.
The synthesis and application of the copper mordenite catalyst have the advantages that the synthesis method is simple, the industrial scale-up production is facilitated, the synthesized copper mordenite catalyst can catalyze methane to prepare methanol through low-temperature selective oxidation, the reaction condition is mild, the methane conversion rate is high, the methanol selectivity is good, and the application prospect is good.
Detailed Description
The synthesis and use of the copper mordenite catalyst of the present invention is described in detail below with reference to the examples.
Example one
Firstly, 1.1g of sodium hydroxide is dissolved in 80g of deionized water to prepare a sodium hydroxide solution, then 0.26g of tetraethyl ammonium hydroxide is dissolved in the sodium hydroxide solution, 0.93g of sodium aluminate is added, 40g of silica sol is added after the sodium aluminate is completely dissolved by stirring, and a gel mixture is formed after uniform mixing. And adding a copper nitrate solution into the gel mixture, uniformly stirring, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a constant-temperature oven for crystallization at 160 ℃ for 36 hours, after crystallization is finished, centrifugally separating a solid product, washing the solid product with deionized water, drying the solid product at 110 ℃, and roasting the solid product in a muffle furnace at 550 ℃ for 6 hours to obtain the copper wire mordenite catalyst.
Screening a 20-mesh copper mordenite catalyst in the first embodiment of the invention is used for catalyzing a reaction for preparing methanol from methane, filling 1g of the screened catalyst into a fixed bed reactor, introducing oxygen for activation, introducing inert gas for full replacement, adjusting the temperature to 200 ℃, introducing reaction gas, namely methane, water and oxygen, at a partial pressure ratio of 1: 0.5:1, adjusting the reaction pressure to 0.3MPa to realize that the conversion rate of methane is 21.8% and the selectivity of methanol is 97.9%.
Example two
Firstly, 1.1g of sodium hydroxide is dissolved in 80g of deionized water to prepare a sodium hydroxide solution, then 0.37g of tetraethylammonium bromide is dissolved in the sodium hydroxide solution, 1.2g of aluminum nitrate is added, 40g of silica sol is added after the aluminum nitrate is completely dissolved by stirring, and a gel mixture is formed after uniform mixing. And adding a copper nitrate solution into the gel mixture, uniformly stirring, transferring the gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the gel mixture in a constant-temperature oven for crystallization at 180 ℃ for 24 hours, after crystallization is finished, centrifugally separating a solid product, washing the solid product with deionized water, drying the solid product at 120 ℃, and roasting the solid product in a muffle furnace at 500 ℃ for 8 hours to obtain the copper wire mordenite catalyst.
Screening the copper mordenite catalyst of the second embodiment of 20 meshes, and using the copper mordenite catalyst in a reaction for preparing methanol by catalyzing methane, filling 1g of the screened catalyst into a fixed bed reactor, introducing oxygen for activation, introducing inert gas for full replacement, adjusting the temperature to 220 ℃, introducing reaction gas, wherein the partial pressure ratio of methane, water and oxygen is 1: 0.2:1, and adjusting the reaction pressure to 0.5MPa to realize that the conversion rate of methane is 16.3% and the selectivity of methanol is 93.2%.
EXAMPLE III
Firstly, 1.1g of sodium hydroxide is dissolved in 80g of deionized water to prepare a sodium hydroxide solution, then 0.26g of tetraethyl ammonium hydroxide is dissolved in the sodium hydroxide solution, 1.12g of sodium aluminate is added, 48g of silica sol is added after the sodium aluminate is completely dissolved by stirring, and a gel mixture is formed after uniform mixing. And adding a copper nitrate solution into the gel mixture, uniformly stirring, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a constant-temperature oven for crystallization for 48 hours at 120 ℃, after crystallization is finished, centrifugally separating a solid product, washing the solid product with deionized water, drying the solid product at 110 ℃, and roasting the solid product in a muffle furnace for 5 hours at 600 ℃ to obtain the copper wire mordenite catalyst.
Screening the copper mordenite catalyst of the third embodiment of 20 meshes, and using the copper mordenite catalyst in a reaction for preparing methanol by catalyzing methane, filling 1g of the screened catalyst into a fixed bed reactor, introducing oxygen for activation, introducing inert gas for full replacement, adjusting the temperature to 180 ℃, introducing reaction gas, wherein the partial pressure ratio of methane, water and oxygen is 5: 2:1, adjusting the reaction pressure to 2MPa to realize the conversion rate of methane to 12.6% and the selectivity of methanol to 91.7%.
Example four
Firstly, 1.1g of sodium hydroxide is dissolved in 80g of deionized water to prepare a sodium hydroxide solution, then 0.37g of tetraethylammonium bromide is dissolved in the sodium hydroxide solution, 1.3g of sodium aluminate is added, 50g of silica sol is added after the sodium aluminate is completely dissolved by stirring, and a gel mixture is formed after uniform mixing. And adding a copper nitrate solution into the gel mixture, uniformly stirring, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a constant-temperature oven for crystallization for 36 hours at 150 ℃, after crystallization is finished, centrifugally separating a solid product, washing the solid product with deionized water, drying the solid product at 120 ℃, and roasting the solid product in a muffle furnace for 5 hours at 600 ℃ to obtain the copper wire mordenite catalyst.
Screening a 40-mesh copper mordenite catalyst described in the fourth embodiment of the invention, when used in a reaction for preparing methanol from methane, 1g of the screened catalyst is filled in a fixed bed reactor, oxygen is introduced for activation, then inert gas is introduced for sufficient replacement, the temperature is adjusted to 190 ℃, then the partial pressure ratio of methane, water and oxygen is introduced as a reaction gas at 2: 0.1:1, the reaction pressure is adjusted to 1MPa, the conversion rate of methane is 23.6%, and the selectivity of methanol is 98.3%.
EXAMPLE five
Firstly, 1.1g of sodium hydroxide is dissolved in 80g of deionized water to prepare a sodium hydroxide solution, then 0.31g of tetraethylammonium hydroxide is dissolved in the sodium hydroxide solution, 1.44g of aluminum nitrate is added, 48g of silica sol is added after the aluminum nitrate is completely dissolved by stirring, and a gel mixture is formed after uniform mixing. And adding a copper nitrate solution into the gel mixture, uniformly stirring, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a constant-temperature oven for crystallization for 48 hours at 140 ℃, after crystallization is finished, centrifugally separating a solid product, washing the solid product with deionized water, drying the solid product at 120 ℃, and roasting the solid product in a muffle furnace for 7 hours at 560 ℃ to obtain the copper wire mordenite catalyst.
Screening a 40-mesh copper mordenite catalyst, which is used in a reaction for preparing methanol by catalyzing methane, 1g of the screened catalyst is filled in a fixed bed reactor, oxygen is introduced for activation, then inert gas is introduced for sufficient replacement, the temperature is adjusted to 160 ℃, then the partial pressure ratio of methane, water and oxygen is introduced as reaction gas is 3: 1.5:1, the reaction pressure is adjusted to 1MPa, the conversion rate of methane is 20.8%, and the selectivity of methanol is 93.2%.
Claims (8)
1. The synthesis of copper wire mordenite catalyst is characterized by comprising the following steps:
dissolving a template agent in a sodium hydroxide solution to obtain a solution I;
adding an aluminum source into the solution I, and dissolving to obtain a solution II;
adding a silicon source into the solution II, and uniformly mixing to form a gel mixture;
adding a copper nitrate solution into the gel mixture, transferring the gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and placing the stainless steel reaction kettle in a constant-temperature oven for crystallization; after crystallization is finished, centrifugally separating, washing with deionized water, drying and roasting the crystallized solid product in a muffle furnace to obtain the copper wire mordenite catalyst.
2. The synthesis of a copper mordenite catalyst as claimed in claim 1, wherein: the template agent is tetraethyl ammonium hydroxide or tetraethyl ammonium bromide.
3. The synthesis of a copper mordenite catalyst as claimed in claim 1, wherein: the aluminum source is sodium aluminate or aluminum nitrate.
4. The synthesis of a copper mordenite catalyst as claimed in claim 1, wherein: the silicon source is silica sol.
5. The synthesis of a copper mordenite catalyst as claimed in claim 1, wherein: the crystallization temperature is 180 ℃ plus 120 ℃, the crystallization time is 24-48 h, the drying temperature is 120 ℃ plus 110 ℃, the roasting temperature is 600 ℃ plus 500 ℃, and the roasting time is 5-8 h.
6. Use of a copper mordenite catalyst as claimed in claims 1 to 5, wherein: placing the copper wire light zeolite catalyst with 20-40 meshes in a fixed bed reactor, introducing oxygen for activation, then introducing nitrogen, adjusting to the reaction temperature, and switching to reaction gas.
7. Use of a copper mordenite catalyst as claimed in claim 6, wherein: the reaction gas is a mixed gas of methane, water and oxygen; reaction temperature of 150 ℃ 220-oC, the reaction pressure is 0.1-2 MPa.
8. Use of a copper mordenite catalyst as claimed in claim 7, wherein: the partial pressure ratio of the methane, the water and the oxygen is (1-5) to (0.1-2) to 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112973784A (en) * | 2021-02-24 | 2021-06-18 | 南开大学 | Preparation method and application of copper modified molecular sieve catalyst |
| CN113955768A (en) * | 2021-11-24 | 2022-01-21 | 陕西延长石油（集团）有限责任公司 | Preparation method of Cu/MOR molecular sieve and application of Cu/MOR molecular sieve in preparation of ethanol by direct oxidation of methane |
| CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
| CN115672384A (en) * | 2022-10-13 | 2023-02-03 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Copper-ruthenium mordenite catalyst for preparing methanol by partial oxidation of coal bed gas, preparation method and application |
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| CN112973784A (en) * | 2021-02-24 | 2021-06-18 | 南开大学 | Preparation method and application of copper modified molecular sieve catalyst |
| CN112973784B (en) * | 2021-02-24 | 2023-11-28 | 南开大学 | Method for preparing methanol by methane oxidation |
| CN113955768A (en) * | 2021-11-24 | 2022-01-21 | 陕西延长石油（集团）有限责任公司 | Preparation method of Cu/MOR molecular sieve and application of Cu/MOR molecular sieve in preparation of ethanol by direct oxidation of methane |
| CN113955768B (en) * | 2021-11-24 | 2023-03-10 | 陕西延长石油（集团）有限责任公司 | Preparation method of Cu/MOR molecular sieve and application of Cu/MOR molecular sieve in preparation of ethanol by direct oxidation of methane |
| CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
| CN115069285B (en) * | 2022-06-14 | 2024-01-16 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane and preparation method and application thereof |
| CN115672384A (en) * | 2022-10-13 | 2023-02-03 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Copper-ruthenium mordenite catalyst for preparing methanol by partial oxidation of coal bed gas, preparation method and application |
| CN115672384B (en) * | 2022-10-13 | 2024-03-22 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Copper ruthenium mordenite catalyst for preparing methanol by coal bed gas partial oxidation, preparation method and application |
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