CN113797951A - Short-period preparation method of catalyst for methane oxidative coupling reaction, catalyst for methane oxidative coupling reaction and application of catalyst - Google Patents
Short-period preparation method of catalyst for methane oxidative coupling reaction, catalyst for methane oxidative coupling reaction and application of catalyst Download PDFInfo
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- CN113797951A CN113797951A CN202010552727.6A CN202010552727A CN113797951A CN 113797951 A CN113797951 A CN 113797951A CN 202010552727 A CN202010552727 A CN 202010552727A CN 113797951 A CN113797951 A CN 113797951A
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- catalyst
- supported catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 42
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 60
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005470 impregnation Methods 0.000 claims abstract description 52
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000011343 solid material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 61
- 238000001354 calcination Methods 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 125000005587 carbonate group Chemical group 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- MCYSFVUDODFQPV-UHFFFAOYSA-K lanthanum(3+) trichlorate Chemical class [La+3].[O-][Cl](=O)=O.[O-][Cl](=O)=O.[O-][Cl](=O)=O MCYSFVUDODFQPV-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003375 plant hormone Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000012990 sonochemical synthesis Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/232—Carbonates
-
- 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 invention relates to the field of catalysts, and discloses a short-period preparation method of a catalyst for methane oxidative coupling reaction, a catalyst for methane oxidative coupling reaction and application thereof. The preparation method comprises the following steps: carrying out microwave impregnation on the carrier by using a precursor impregnation liquid of lanthanum oxycarbonate, and then drying and roasting the impregnated solid material in sequence to obtain the supported catalyst; the precursor impregnation liquid of the lanthanum oxycarbonate contains soluble salt of lanthanum, a soluble carbon source and water; wherein the carrier is halloysite; wherein the soluble carbon source is carbonate and/or bicarbonate, and the pH value of the impregnation liquid is 8-14. The preparation time of the catalyst can be greatly reduced, the problem of long period of the existing preparation process is solved, and the catalyst provided by the invention has higher reaction conversion rate and selectivity when being used for methane oxidative coupling reaction.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a microwave preparation method of a supported catalyst loaded with lanthanum oxycarbonate, the supported catalyst loaded with lanthanum oxycarbonate prepared by the microwave preparation method, the supported catalyst loaded with lanthanum oxycarbonate, application of the supported catalyst loaded with lanthanum oxycarbonate in methane oxidative coupling reaction, and a method for preparing carbon dioxide and hydrocarbon from methane.
Background
Ethylene is a compound consisting of two carbon atoms and four hydrogen atoms. The two carbon atoms are connected by a double bond.
Ethylene is a basic chemical raw material of synthetic fiber, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride), synthetic ethanol (alcohol), is also used for manufacturing vinyl chloride, styrene, ethylene oxide, acetic acid, acetaldehyde, ethanol, explosive and the like, can be used as a ripener for fruits and vegetables, and is a proven plant hormone.
Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of the petrochemical industry, and the ethylene product accounts for more than 75 percent of petrochemical products and occupies an important position in national economy. Ethylene production has been used worldwide as one of the important indicators for the development of petrochemical in one country.
In recent years, the discovery and exploitation of shale gas have revolutionized the development and utilization of natural gas. Therefore, the method for preparing ethane and ethylene by methane oxidative coupling, which is the most direct, effective and economically competitive natural gas utilization method, is increasingly receiving attention. Since the oxidative coupling reaction of methane is a strongly exothermic reaction and is carried out at high temperature, no industrial production is available so far, and therefore, the development of a methane oxidative coupling catalyst with excellent performance has practical significance.
However, the existing catalyst preparation process is complicated, the preparation time is long, and the industrial production method is not facilitated.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a microwave preparation method of a supported catalyst loaded with lanthanum oxycarbonate, the supported catalyst loaded with lanthanum oxycarbonate prepared by the microwave preparation method, the supported catalyst loaded with lanthanum oxycarbonate, the application of the supported catalyst loaded with lanthanum oxycarbonate in methane oxidative coupling reaction and a method for preparing carbon dioxide and above hydrocarbons from methane. The preparation time of the catalyst can be greatly reduced, the problem of long period of the existing preparation process is solved, and the catalyst provided by the invention has higher reaction conversion rate and selectivity when being used for methane oxidative coupling reaction.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a supported catalyst, the method comprising: carrying out microwave impregnation on the carrier by using a precursor impregnation liquid of lanthanum oxycarbonate, and then drying and roasting the impregnated solid material in sequence to obtain the supported catalyst;
the precursor impregnation liquid of the lanthanum oxycarbonate contains soluble salt of lanthanum, a soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is a carbonate and/or bicarbonate;
wherein the pH value of the impregnation liquid is 8-14.
In a second aspect the present invention provides a supported catalyst prepared by a process as described above.
The third aspect of the present invention provides a supported catalyst comprising a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxycarbonate;
the catalyst also comprises an auxiliary agent element loaded on the carrier, wherein the auxiliary agent element comprises barium element and strontium element.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in an oxidative coupling reaction of methane.
In a fifth aspect, the present invention provides a method for producing hydrocarbons from methane, the method comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions for the oxidative coupling of methane;
alternatively, the supported catalyst is prepared as described above and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of the oxidative coupling of methane reaction.
The invention can obtain the following beneficial effects:
(1) according to the invention, halloysite is used as a carrier, lanthanum oxycarbonate is used as an active component, and the active component is loaded on the carrier by combining a microwave method, so that the preparation time of the catalyst is effectively shortened, a good foundation is laid for industrial amplification production, and more importantly, the obtained catalyst also shows better catalytic performance.
(2) The catalyst provided by the invention takes halloysite as a carrier and lanthanum oxycarbonate as an active component, and still has high reaction conversion rate and selectivity at a low catalytic temperature, for example, below 500 ℃ when used in the oxidative coupling reaction of methane.
(3) The halloysite carrier in the catalyst provided by the invention has a hollow fiber tubular nano structure, and due to the special hollow fiber tubular nano structure and the characteristic that the surface charges of the inner tube and the outer tube are different, the dispersion of active components and the generation of active oxygen sites are facilitated, and the halloysite carrier shows good catalytic performance when being used for methane oxidation coupling reaction.
(4) The carrier halloysite in the catalyst provided by the invention has wide sources and low cost, does not need any treatment, can be directly used as a catalyst carrier, and simplifies the preparation process of the catalyst.
(5) In a preferable condition, the catalyst is loaded with the auxiliary element, so that the catalytic performance of the catalyst is further improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for the preparation of a supported catalyst, the process comprising: carrying out microwave impregnation on the carrier by using a precursor impregnation liquid of lanthanum oxycarbonate, and then drying and roasting the impregnated solid material in sequence to obtain the supported catalyst;
the precursor impregnation liquid of the lanthanum oxycarbonate contains soluble salt of lanthanum, a soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is a carbonate and/or bicarbonate;
wherein the pH value of the impregnation liquid is 8-14.
Halloysite is a natural aluminosilicate clay mineral, is mainly used for researches on antibacterial, chemical templates, lithium ion batteries and the like, and has a hollow tubular nano structure, the diameter of the hollow tubular nano structure is nano-scale, and the length of the hollow tubular nano structure is between nano-scale and micron-scale; the halloysite has different chemical compositions on the inner wall and the outer wall, the outer wall is made of silicon oxide, the inner wall is made of aluminum oxide, the structure is unique, the charges on the surfaces of the halloysite are different, the outer wall is negatively charged, and the inner wall is positively charged.
The inventor of the invention finds that the supported catalyst is obtained by using halloysite as a carrier and performing microwave impregnation on the halloysite in an impregnation liquid containing a soluble salt of lanthanum, a carbon source (carbonate and/or bicarbonate) and water under an alkaline condition, and then sequentially drying and roasting the impregnated solid material, so that the preparation time of the catalyst is effectively shortened, and the obtained catalyst can perform methane oxidative coupling reaction at a lower temperature while maintaining higher catalytic performance.
The present invention does not impose undue requirements on the specific size of the halloysite. However, the inventors of the present invention have found that when the halloysite of the hollow tubular nanostructure has an inner diameter of 10 to 20nm (for example, may be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and any combination of ranges and all values within ranges), an outer diameter of 40 to 70nm (for example, may be 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, and any combination of ranges and all values within ranges), and a length of 200-1000nm (for example, may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and any combination of ranges and all values within ranges), the catalytic performance of the catalyst prepared therefrom can be further improved.
According to the present invention, the soluble salt of lanthanum may be any of the existing soluble salts of lanthanum, such as, but not limited to, lanthanum chloride, lanthanum chlorate and lanthanum nitrate, preferably lanthanum nitrate.
According to the present invention, the carbonate and/or bicarbonate may be any of the existing soluble carbonates and/or bicarbonates, for example, but not limited to, at least one of a carbonate, an alkali metal bicarbonate, ammonium carbonate and ammonium bicarbonate; preferably at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate. When the carbon source is selected from alkali metal carbonate and/or bicarbonate, alkali metal elements can be further introduced into the catalyst, so that the performance of the catalyst is further improved.
According to the invention, the pH of the impregnation liquid may be 8, 9, 10, 11, 12, 13, 14, preferably 9-12, for example 9, 9.5, 10, 10.5, 11, 11.5, 12.
According to the invention, when the added carbon source can enable the pH value of the system to reach the level, the additional pH regulator can not be introduced any more, and if the added carbon source can not enable the pH value of the system to reach the level, the additional pH regulator can be further introduced to adjust the pH value.
According to the present invention, the amount of the precursor of lanthanum oxycarbonate may be selected from a wide range, and is preferably such that the lanthanum oxycarbonate is contained in the obtained catalyst in an amount of 0.5 to 60 parts by weight (for example, may be 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight), preferably 2 to 30 parts by weight, more preferably 5 to 15 parts by weight, relative to 100 parts by weight of the carrier on a dry weight basis.
According to the invention, the impregnation may be an isovolumetric impregnation or an over-volumetric impregnation.
According to the present invention, the power of the microwave can be changed in a wide range, preferably, the power of the microwave is 300-1000W (for example, 300W, 400W, 500W, 600W, 700W, 800W, 900W, 1000W), preferably 400-800W.
According to the invention, in addition to controlling the pH as above during microwave impregnation, the temperature and time for other conditions, such as microwave impregnation, may be varied within a wide range. Preferably, the microwave impregnation temperature is room temperature, for example, 20-40 ℃, for example, can be 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃. Preferably, the microwave immersion time is 1-20min, for example, 1min, 3min, 5min, 7min, 9min, 11min, 13min, 15min, 17min, 19min, 20min, preferably 5-10 min.
According to the invention, the temperature of the drying can vary within wide limits, preferably the temperature of the drying is 80 to 180 ℃, for example 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, preferably 80 to 100 ℃.
According to the invention, the drying time can vary within wide limits, preferably the drying time is 12-24h, for example 12h, 14h, 16h, 18h, 20h, 22h, 24h, preferably 12-15 h.
According to the present invention, the temperature of the calcination may be varied within a wide range, and preferably, the temperature of the calcination is 450-.
According to the invention, the calcination time can vary within wide limits, preferably the calcination time is 2 to 8 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, preferably 2 to 6 hours, more preferably 2 to 4 hours.
According to the present invention, the atmosphere for the calcination is not particularly limited, and is preferably an air atmosphere or a carbon dioxide atmosphere.
According to the present invention, in order to further improve the catalytic performance of the prepared supported catalyst, it is preferable that the calcination process is raised to the calcination endpoint temperature at a temperature rise rate of 1 to 10 ℃/min, preferably 1 to 5 ℃/min, and then the calcination is performed for a predetermined time.
According to the present invention, in order to further improve the performance of the prepared supported catalyst, preferably, the method further comprises: and loading the auxiliary agent element on the carrier.
Preferably, the auxiliary element is a metal element, a semimetal element, a nonmetal element or a combination thereof, more preferably any one or any combination of Li, Na, K, Cs, Ce, Y, Ba, Ti, Ru, Rh, Ni, Sr, Ag and Pt, for example, a combination of Ba and Sr.
The method of supporting the auxiliary element on the support is not particularly limited in the present invention, and may be carried out by methods known to those skilled in the art, for example, mixing, precipitation/co-precipitation, impregnation, sol-gel, template/surface-derived metal oxide synthesis, solid state synthesis of mixed metal oxides, microemulsion technology, solvothermal synthesis, sonochemical synthesis, combustion synthesis, and the like.
The method of providing the auxiliary element may be selected by those skilled in the art according to the supporting method, for example, when the supporting method is adopted, the carrier may be impregnated with an impregnation solution containing a soluble salt of the auxiliary element, so as to complete the supporting, and this step may be performed together with or separately from the impregnation of the carrier with the impregnation solution of the precursor of lanthanum oxycarbonate, and after all of the auxiliary element is supported on the carrier, the carrier may be sequentially dried and calcined.
In accordance with the present invention, the amount of the compound containing a promoter element may be selected within a wide range, and in order to further enhance the performance of the supported catalyst, it is preferred that it be used in an amount such that the promoter element is present in the resulting catalyst in an amount of 0.01 to 5 parts by weight, and all ranges therebetween, such as about 0.1 to 4 parts by weight, about 1 to 3 parts by weight, and any specific value therebetween, for example, about 0.01 parts by weight, about 0.02 parts by weight, about 0.5 parts by weight, about 1 part by weight, about 2 parts by weight, about 3 parts by weight, about 4 parts by weight, or about 5 parts by weight, relative to 100 parts by weight of the support on a dry weight basis.
In a second aspect, the present invention provides a supported catalyst prepared by a process as described above.
In a third aspect, the present invention provides a supported catalyst, which comprises a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxycarbonate;
the catalyst also comprises an auxiliary agent element loaded on the carrier, wherein the auxiliary agent element comprises barium element and strontium element.
The present invention does not impose undue requirements on the specific size of the halloysite. However, the inventors of the present invention have found that when the halloysite of the hollow tubular nanostructure has an inner diameter of 10 to 20nm (for example, may be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and any combination of ranges and all values within ranges), an outer diameter of 40 to 70nm (for example, may be 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, and any combination of ranges and all values within ranges), and a length of 200-1000nm (for example, may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and any combination of ranges and all values within ranges), the catalytic performance of the catalyst prepared therefrom can be further improved.
According to the invention, the lanthanum oxycarbonate may be present, for example, in an amount of 0.5 to 60 parts by weight, preferably 2 to 30 parts by weight, more preferably 5 to 15 parts by weight, relative to 100 parts by weight of the support on a dry weight basis; the content of the auxiliary agent is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on the auxiliary agent element.
According to the present invention, in order to further improve the performance of the supported catalyst, it is preferable that the auxiliary element further includes any one or any combination of Li, Na, K, Cs, Ce, Y, Ti, Ru, Rh, Ni, Ag, and Pt.
According to the present invention, the preparation method of the catalyst preferably comprises: carrying out microwave impregnation on the carrier by using impregnation liquid containing a precursor of lanthanum oxycarbonate and a precursor of an auxiliary agent element, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
the precursor of the lanthanum oxycarbonate comprises a soluble salt of lanthanum and a soluble carbon source;
wherein the carrier is halloysite;
wherein the soluble carbon source is a carbonate and/or bicarbonate;
wherein the pH value of the impregnation liquid is 8-14.
The details of the preparation process according to the present invention have been fully described above in the first aspect, and the present invention will not be repeated herein in order to avoid unnecessary repetition.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in an oxidative coupling reaction of methane.
According to the present invention, the catalyst of the present invention may be used in a continuous flow reactor to produce C2+ hydrocarbons from methane (e.g., natural gas). The continuous flow reactor may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or an ebullating bed reactor. The catalyst may be arranged in layers in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullating bed).
In a fifth aspect, the present invention provides a process for the preparation of carbon two and above hydrocarbons from methane, the process comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions for the oxidative coupling of methane;
alternatively, the supported catalyst is prepared as described above and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of the oxidative coupling of methane reaction.
According to the present invention, the catalyst may be molded before being loaded in the reactor, and the molding method is not particularly limited and may be a method conventionally used in the art. Preferably, the molding condition is that the mixture is crushed and sieved by a 40-60 mesh sieve after tabletting.
According to the present invention, the conditions for the oxidative coupling of methane reaction are not particularly limited, and may be conventionally selected in the art, and the conditions for the oxidative coupling of methane reaction may include a reaction temperature of 400-. In order to increase the methane conversion, it is preferred that the molar ratio of the amounts of methane and oxygen is 2 to 10: 1, preferably 3 to 8: 1.
embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents and apparatus used are those which are not specified by the manufacturer and are conventional products commercially available.
The drying box is produced by Shanghai-Hengchang scientific instruments Co., Ltd, and has the model of DHG-9030A.
The muffle furnace is manufactured by CARBOLITE corporation, model CWF 1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A. Methane conversion and selectivity to carbon and above hydrocarbons were calculated based on product composition, including ethane, ethylene, propane, propylene, butane, butenes.
Example 1
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
According to the load capacity of lanthanum oxycarbonate of 10 weight percent, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a precursor impregnation liquid of lanthanum oxycarbonate, the pH value of the impregnation liquid is adjusted to 11, halloysite (with the inner diameter of 15nm, the outer diameter of 65nm and the length of 600nm) is added into the impregnation liquid, the mixture is uniformly stirred at room temperature and is placed into a microwave reactor, and 600W treatment is carried out for 5 min. And then heating to 80 ℃ to volatilize water, placing the mixture in a 100 ℃ oven for drying for 12h, then transferring the mixture to a muffle furnace for roasting, wherein the heating rate is 3 ℃/min, the roasting is carried out in the air at 550 ℃, and the roasting time is 2 h. And (3) reducing the temperature to room temperature, tabletting, sieving to obtain a 40-60 mesh part, and obtaining the methane oxidative coupling catalyst Cat-1, wherein the catalyst has a characteristic peak of lanthanum oxycarbonate as shown by XRD.
Example 2
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
According to the load capacity of 15 wt% of lanthanum oxycarbonate, lanthanum nitrate hexahydrate and ammonium bicarbonate are dissolved in deionized water to obtain a lanthanum oxycarbonate precursor impregnation liquid, the pH value of the impregnation liquid is adjusted to 9, halloysite (the inner diameter is 10nm, the outer diameter is 40nm, and the length is 1000nm) is added into the impregnation liquid, the mixture is uniformly stirred at room temperature, and the mixture is placed into a microwave reactor and treated for 10min at 400W. And then heating to 80 ℃ to volatilize water, placing in an oven at 80 ℃ for drying for 15h, then transferring to a muffle furnace for roasting, wherein the heating rate is 1 ℃/min, roasting in air at 500 ℃ for 4 h. And (3) reducing the temperature to room temperature, tabletting, sieving to obtain a 40-60 mesh part, and obtaining the methane oxidative coupling catalyst Cat-2, wherein the catalyst has a characteristic peak of lanthanum oxycarbonate as shown by XRD.
Example 3
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
According to the load capacity of 5 wt% of lanthanum oxycarbonate, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a lanthanum oxycarbonate precursor impregnation liquid, the pH value of the impregnation liquid is adjusted to 11, halloysite (with the inner diameter of 20nm, the outer diameter of 70nm and the length of 200nm) is added into the impregnation liquid, the mixture is uniformly stirred at room temperature and is placed into a microwave reactor, and the treatment is carried out for 7min at 800W. And then heating to 80 ℃ to volatilize water, placing in a 90 ℃ oven for drying for 13h, then transferring to a muffle furnace for roasting, wherein the heating rate is 5 ℃/min, and roasting in air at 525 ℃ for 3 h. And (3) reducing the temperature to room temperature, tabletting, sieving to obtain a 40-60 mesh part, and obtaining the methane oxidative coupling catalyst Cat-3, wherein the catalyst has a characteristic peak of lanthanum oxycarbonate as shown by XRD.
Example 4
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The preparation of catalyst Cat-4 was carried out in accordance with the procedure of example 1, except that the halloysite had an inner diameter of 30nm, the microwave power was 1000W, the lanthanum oxycarbonate supported at 20% by weight, and the catalyst had a characteristic peak of lanthanum oxycarbonate as characterized by XRD.
Example 5
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The catalyst Cat-5 was prepared according to the method of example 1, except that barium nitrate was dissolved in deionized water, strontium nitrate was dissolved in deionized water, and then mixed with a precursor impregnation solution of lanthanum oxycarbonate, and the pH was adjusted to perform microwave impregnation treatment, according to the loading of barium element of 0.2 wt% and the loading of strontium element of 0.2 wt%. The catalyst is calcined according to the method of example 1, and the catalyst is characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Example 6
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
Catalyst Cat-6 was prepared according to the method of example 5, except that potassium nitrate was dissolved in deionized water in an amount of 0.2 wt% based on the amount of potassium, aqueous solutions of barium nitrate, strontium nitrate and potassium nitrate were mixed with the precursor impregnation solution of lanthanum oxycarbonate, and the pH was adjusted to perform microwave impregnation. The catalyst is calcined according to the method of example 1, and the catalyst is characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Example 7
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The preparation of catalyst Cat-7 was carried out as in example 5, except that potassium nitrate was replaced by silver nitrate, the amount of potassium element supported was the same as that of barium element on a molar basis, and the catalyst was characterized by XRD to have a characteristic lanthanum oxycarbonate peak.
Example 8
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The preparation of catalyst Cat-8 was carried out according to the method of example 1, except that calcination was carried out in a nitrogen atmosphere and the catalyst was characterized by XRD to have a characteristic lanthanum oxycarbonate peak.
Example 9
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The preparation of catalyst Cat-9 was carried out as in example 1, except that the rate of heating to the calcination temperature was 8 ℃/min, and the catalyst was characterized by XRD to have a characteristic lanthanum oxycarbonate peak.
Example 10
This example illustrates the catalyst and the method of preparation of the catalyst provided by the present invention.
The preparation of catalyst Cat-10 was carried out in the same manner as in example 1, except that the calcination temperature was 750 ℃ and the catalyst was characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Comparative example 1
This comparative example serves to illustrate a reference catalyst and a process for its preparation.
The preparation of catalyst Cat-D-1 was carried out as in example 1, except that the support was replaced by saponite during the preparation.
Comparative example 2
This comparative example serves to illustrate a reference catalyst and a process for its preparation.
The preparation of catalyst Cat-D-2 was carried out as in example 1, except that the pH of the impregnation solution was not adjusted.
Comparative example 3
This comparative example serves to illustrate a reference catalyst and a process for its preparation.
The catalyst Cat-D-3 was prepared according to the method of example 1, except that ammonium carbonate was replaced with an equal amount of glycine, and calcination was carried out in a nitrogen atmosphere while the pH of the impregnation solution was not adjusted.
Test example 1
This test example serves to illustrate the catalytic performance of the catalysts of the invention
0.2g of the catalyst Cat-1 was charged in a fixed bed quartz reactor under normal pressure conditions at a methane to oxygen molar ratio of 4:1, a methane space velocity of 60000ml/gh, and an activation temperature for oxidative coupling of methane, a methane conversion rate and a carbon and above hydrocarbon selectivity as shown in Table 1.
Test examples 2 to 10
This test example serves to illustrate the catalytic performance of the catalysts of the invention
Ethylene and ethane were produced by oxidative coupling of methane according to the method of test example 1, except that catalysts Cat-2 to Cat-10 were used, respectively, and the activation temperature and methane conversion rate of the oxidative coupling reaction of methane and the selectivity for hydrocarbons of carbon and above are shown in Table 1.
Comparative test examples 1 to 3
Ethylene ethane was produced by oxidative coupling of methane in the same manner as in test example 1, except that catalysts Cat-D-1 to Cat-D-3 were used, and the activation temperature and methane conversion rate of the oxidative coupling reaction of methane and the selectivity for hydrocarbons of carbon and above were as shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalyst prepared by the method is used for the oxidative coupling reaction of methane, the oxidative coupling reaction of methane can obtain higher methane conversion rate and hydrocarbon selectivity of carbon two or more at lower initial temperature.
Comparing example 2 with example 4, it can be seen that the halloysite size is not in the preferred range and increased amounts of active component are required to achieve substantially the same catalytic effect.
Comparing example 2 with examples 5 to 7, it can be seen that the catalyst initiation temperature can be further reduced and the catalytic performance of the resulting catalyst can be further improved when the promoter element is supported.
Comparing example 2 with example 8, it can be seen that the catalyst initiation temperature can be further lowered and the catalytic performance of the resulting catalyst can be further improved in the preferred calcination atmosphere.
Comparing example 2 with examples 9 to 10, it can be seen that the catalyst initiation temperature can be further lowered and the catalytic performance of the resulting catalyst can be further improved at the preferred calcination temperature rise rate calcination temperature.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A method of preparing a supported catalyst, the method comprising: carrying out microwave impregnation on the carrier by using a precursor impregnation liquid of lanthanum oxycarbonate, and then drying and roasting the impregnated solid material in sequence to obtain the supported catalyst;
the precursor impregnation liquid of the lanthanum oxycarbonate contains soluble salt of lanthanum, a soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is a carbonate and/or bicarbonate;
wherein the pH value of the impregnation liquid is 8-14.
2. The method as claimed in claim 1, wherein the power of the microwave is 300-;
preferably, the microwave impregnation temperature is 20-40 ℃ and the time is 1-20 min.
3. The method of claim 1 or 2, wherein the impregnation solution has a pH value of 9-12; and/or
The soluble carbon source is at least one of alkali metal carbonate, alkali metal bicarbonate, ammonium carbonate and ammonium bicarbonate.
4. The method as claimed in any one of claims 1 to 3, wherein the halloysite is a hollow nanotube structure having an inner diameter of 10-20nm, an outer diameter of 40-70nm and a length of 200-1000 nm.
5. The process according to any one of claims 1 to 4, wherein the amount of the precursor of lanthanum oxycarbonate is such that the lanthanum oxycarbonate is contained in the resulting supported catalyst in an amount of 0.5 to 60 parts by weight, preferably 2 to 30 parts by weight, relative to 100 parts by weight of the support on a dry weight basis.
6. The method of any of claims 1-5, wherein the drying conditions comprise: the temperature is 80-180 ℃, and the time is 12-24 hours; and/or
The roasting conditions comprise: the temperature is 450 ℃ and 600 ℃, and the time is 2-8 hours;
preferably, the calcination is performed in an atmosphere of air or carbon dioxide.
7. The method according to any one of claims 1 to 6, wherein the temperature of the dried material is raised to the roasting temperature at a rate of 1-10 ℃/min.
8. The method of any of claims 1-7, wherein the method further comprises: supporting an auxiliary element on the carrier;
preferably, the auxiliary element is a metal element, a semimetal element, a nonmetal element or a combination thereof, and more preferably any one or any combination of Li, Na, K, Cs, Ce, Y, Ba, Ti, Ru, Rh, Ni, Sr, Ag and Pt;
preferably, the promoter element is used in an amount such that the promoter element is present in an amount of 0.01 to 5 parts by weight, based on 100 parts by weight of the carrier on a dry weight basis, in the resulting supported catalyst.
9. A supported catalyst, characterized in that it is obtained by a process according to any one of claims 1 to 8.
10. A supported catalyst, which is characterized by comprising a carrier and an active component supported on the carrier, wherein the carrier is halloysite; the active component comprises lanthanum oxycarbonate;
the catalyst also comprises an auxiliary agent element loaded on the carrier, wherein the auxiliary agent element comprises barium element and strontium element.
11. The supported catalyst of claim 10, wherein the lanthanum oxycarbonate is present in an amount of 0.5 to 60 parts by weight relative to 100 parts by weight of the support on a dry weight basis; the content of the auxiliary agent element is 0.01-5 parts by weight.
12. The supported catalyst of claim 10 or 11, wherein the halloysite is a hollow nanotube structure with an inner diameter of 10-20nm, an outer diameter of 40-70nm, and a length of 200-1000 nm.
13. The supported catalyst of any of claims 10-11, wherein the promoter element further comprises any one or any combination of Li, Na, K, Cs, Ce, Y, Ti, Ru, Rh, Ni, Ag, and Pt.
14. The supported catalyst of any one of claims 10-13, wherein the supported catalyst is prepared by a process comprising: carrying out microwave impregnation on the carrier by using impregnation liquid containing a precursor of lanthanum oxycarbonate and a precursor of an auxiliary agent element, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
the precursor of the lanthanum oxycarbonate comprises a soluble salt of lanthanum and a soluble carbon source;
wherein the carrier is halloysite;
wherein the soluble carbon source is a carbonate and/or bicarbonate;
wherein the pH value of the impregnation liquid is 8-14.
15. Use of a supported catalyst according to any one of claims 9 and 10 to 14 in an oxidative coupling reaction of methane.
16. A method for producing carbon dioxide and hydrocarbons from methane, the method comprising: contacting methane with the supported catalyst of any one of claims 9 and 10-14 in the presence of oxygen and under conditions of a methane oxidative coupling reaction;
alternatively, a supported catalyst is prepared according to the process of any one of claims 1 to 8, and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of the oxidative coupling reaction of methane.
17. The process according to claim 16, wherein the molar ratio of the amounts of methane and oxygen is 2-10: 1, preferably 3-8: 1;
and/or the contact temperature is 400-800 ℃; the space velocity of the methane is 5000-100000 mL/(g.h).
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| CN115487841A (en) * | 2022-08-18 | 2022-12-20 | 华东师范大学 | Catalyst applied to hydrogenation of blast furnace gas to prepare synthesis gas and preparation method thereof |
| WO2024067658A1 (en) * | 2022-09-27 | 2024-04-04 | 中国石油化工股份有限公司 | Lanthanum oxycarbonate catalyst, preparation method therefor and use thereof |
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