CN113797951B - Short-period preparation method of catalyst for oxidative coupling reaction of methane, catalyst for oxidative coupling reaction of methane and application of catalyst - Google Patents
Short-period preparation method of catalyst for oxidative coupling reaction of methane, catalyst for oxidative coupling reaction of methane and application of catalyst Download PDFInfo
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- CN113797951B CN113797951B CN202010552727.6A CN202010552727A CN113797951B CN 113797951 B CN113797951 B CN 113797951B CN 202010552727 A CN202010552727 A CN 202010552727A CN 113797951 B CN113797951 B CN 113797951B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000005691 oxidative coupling reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 32
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 32
- 238000005470 impregnation Methods 0.000 claims abstract description 30
- KGDJAQAMSDMZCD-UHFFFAOYSA-M hydrogen carbonate lanthanum(3+) oxygen(2-) Chemical compound C([O-])(O)=O.[O-2].[La+3] KGDJAQAMSDMZCD-UHFFFAOYSA-M 0.000 claims abstract description 29
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 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 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 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
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 53
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910052788 barium Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052697 platinum 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
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 3
- 238000010304 firing Methods 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
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 4
- 239000000463 material Substances 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 238000001354 calcination Methods 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 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
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 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 group 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
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application 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
- 238000007796 conventional method 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
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MCYSFVUDODFQPV-UHFFFAOYSA-K lanthanum(3+) trichlorate Chemical compound [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 compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 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
- 229910052755 nonmetal Inorganic materials 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
- 239000000843 powder Substances 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
- 230000005070 ripening Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 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
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber 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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a short-period preparation method of a catalyst for methane oxidative coupling reaction, the catalyst for methane oxidative coupling reaction and application thereof. The preparation method comprises the following steps: carrying out microwave impregnation on a carrier by using a precursor impregnation liquid of lanthanum oxide carbonate, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst; wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, 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 impregnating solution is 8-14. The catalyst provided by the invention can greatly reduce the preparation time, solves the problem of long period of the existing preparation process, and has higher reaction conversion rate and selectivity when being used for the oxidative coupling reaction of methane.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a microwave preparation method of a lanthanum oxide carbonate-supported catalyst, the lanthanum oxide carbonate-supported catalyst prepared by the microwave preparation method, the lanthanum oxide carbonate-supported catalyst, application of the lanthanum oxide carbonate-supported catalyst in a methane oxidative coupling reaction, and a method for preparing carbon two or more hydrocarbons 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 for synthetic fibre, synthetic rubber, synthetic plastics (polyethylene and polyvinyl chloride) and synthetic alcohol (alcohol), and can be used for preparing chloroethylene, styrene, ethylene oxide, acetic acid, acetaldehyde, alcohol and explosive, etc., and can be used as ripening agent of fruit and vegetable, 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 petrochemical industry, and the ethylene product accounts for more than 75% of petrochemical products and plays an important role in national economy. Ethylene production has been worldwide used as one of the important markers for the level of petrochemical development in a country.
In recent years, the discovery and exploitation of shale gas brings revolutionary promotion to the development and utilization of natural gas. Therefore, the method is also receiving more and more attention as the most direct and effective natural gas utilization method with high economic competitiveness, namely, the method for preparing ethane and ethylene by oxidative coupling of methane. Since the oxidative coupling reaction of methane is a strong exothermic reaction and is carried out at high temperature, no industrial production has been developed 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 method production of the catalyst 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 lanthanum oxide carbonate supported catalyst, the lanthanum oxide carbonate supported catalyst prepared by the microwave preparation method, the lanthanum oxide carbonate supported catalyst, application of the lanthanum oxide carbonate supported catalyst in methane oxidative coupling reaction and a method for preparing carbon two or more hydrocarbons from methane. The catalyst provided by the invention can greatly reduce the preparation time, solves the problem of long period of the existing preparation process, and has higher reaction conversion rate and selectivity when being used for the oxidative coupling reaction of methane.
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 a carrier by using a precursor impregnation liquid of lanthanum oxide carbonate, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate;
wherein the pH value of the impregnating solution is 8-14.
In a second aspect the present invention provides a supported catalyst prepared by the process as described above.
The third aspect of the 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 oxide carbonate;
the catalyst also comprises an auxiliary element supported on the carrier, wherein the auxiliary element comprises a barium element and a strontium element.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in the oxidative coupling of methane.
In a fifth aspect, the invention provides a process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a 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 oxidative coupling of methane.
The invention has the following beneficial effects:
(1) According to the invention, halloysite is used as a carrier, lanthanum oxide carbonate 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 large-scale 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 oxide carbonate as an active component, and has higher reaction conversion rate and selectivity at a lower catalytic temperature, for example, below 500 ℃ when being used for methane oxidative coupling reaction.
(3) The halloysite carrier in the catalyst provided by the invention has a hollow fiber tubular nanostructure, and has the characteristics of different charges on the surfaces of the special hollow fiber tubular nanostructure and the inner and outer tubes, so that the halloysite carrier is more beneficial to the dispersion of active components and the generation of active oxygen sites, and has good catalytic performance when being used for methane oxidative coupling reaction.
(4) The halloysite carrier 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) Under the preferable condition, the catalyst is loaded with the auxiliary agent element, so that the catalytic performance of the catalyst is further improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a method for preparing a supported catalyst, the method comprising: carrying out microwave impregnation on a carrier by using a precursor impregnation liquid of lanthanum oxide carbonate, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor impregnating solution of lanthanum oxide carbonate contains lanthanum soluble salt, soluble carbon source and water;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate;
wherein the pH value of the impregnating solution is 8-14.
Halloysite is a natural aluminosilicate clay mineral which is mainly used for researches on antibacterial, chemical templates, lithium ion batteries and the like, and has a hollow tubular nano structure, wherein the diameter is in a nano level, and the length is in a nano level to a micro level; the chemical compositions of the inner wall and the outer wall of halloysite are different, the outer wall is silicon oxide, the inner wall is aluminum oxide, the structure is unique, the surface charges of halloysite are different, the outer wall is negatively charged, and the inner wall is positively charged.
The inventor of the present invention found in the research that by using halloysite as a carrier, under alkaline conditions, the halloysite is subjected to microwave impregnation in an impregnation liquid containing lanthanum soluble salt, a carbon source (carbonate and/or bicarbonate) and water, and then the impregnated solid material is dried and baked in sequence, the supported catalyst is obtained, the preparation time of the catalyst is effectively shortened, and the obtained catalyst can also be subjected to methane oxidative coupling reaction at a lower temperature, and meanwhile, the higher catalytic performance is maintained.
The invention has no excessive requirements on the specific size of halloysite. The inventors of the present invention have found that when the hollow tubular nanostructure halloysite has an inner diameter of 10-20nm (e.g., can be 10nm, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and any combination and all values within the range) and an outer diameter of 40-70nm (e.g., can be 40, 45, 50, 55, 60, 65, 70nm, and any combinations of ranges and all values within ranges), and a length of 200-1000nm (e.g., which may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and any combinations 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 various existing soluble salts of lanthanum, for example, 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 a variety of soluble carbonates and/or bicarbonates available, for example, but not limited to, at least one of carbonate, 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 selects alkali metal carbonate and/or bicarbonate, alkali metal element 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 fluid 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 above level, no additional acid-base regulator can be introduced, and if the added carbon source can not enable the pH value of the system to reach the above level, the additional acid-base regulator can be further introduced to regulate the pH value.
According to the present invention, the amount of the precursor of lanthanum oxycarbonate may be selected within a wide range, and preferably, the amount thereof is such that the content of lanthanum oxycarbonate in the resultant catalyst is 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 overdose impregnation.
The power of the microwaves according to the invention can vary within a wide range, preferably the power of the microwaves is 300-1000W (e.g. 300W, 400W, 500W, 600W, 700W, 800W, 900W, 1000W), preferably 400-800W.
In accordance with the present invention, the temperature and time of microwave impregnation may be varied within a wide range for other conditions, such as the temperature and time of microwave impregnation, in addition to controlling the pH as above during microwave impregnation. Preferably, the microwave impregnation temperature is room temperature, for example, 20-40 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃,40 ℃. Preferably, the microwave soaking time is 1-20min, for example, 1min, 3min, 5min, 7min, 9min, 11min, 13min, 15min, 17min, 19min, 20min, preferably 5-10min.
The temperature of the drying according to the invention may vary within a wide range, preferably the drying temperature is 80-180 ℃, for example 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, preferably 80-100 ℃.
The drying time may vary within wide limits, preferably is 12-24h, for example 12h, 14h, 16h, 18h, 20h, 22h, 24h, preferably 12-15h.
The temperature of the calcination may vary within a wide range according to the present invention, and preferably the temperature of the calcination is 450-600 ℃, for example, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃,500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃,500 ℃, and preferably 500-550 ℃.
The calcination time may vary within a wide range according to the invention, preferably the calcination time is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, preferably 2-6h, more preferably 2-4h.
According to the present invention, the atmosphere of the firing 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 end temperature at a temperature raising rate of 1 to 10 c/min, preferably 1 to 5 c/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 semi-metal element, a non-metal element, or a combination thereof, more preferably any one of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt or any combination thereof, for example, a combination of Ba and Sr.
The method of supporting the auxiliary element on the carrier 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/coprecipitation, impregnation, sol-gel, template/surface-derived metal oxide synthesis, solid state synthesis of mixed metal oxide, microemulsion technology, solvothermal synthesis, sonochemical synthesis, combustion synthesis, and the like.
The person skilled in the art can select the form of supply of the auxiliary element according to the method of loading, for example, when loading is performed by the method of impregnation, the carrier can be impregnated with an impregnating solution containing a soluble salt of the auxiliary element to complete the loading, and this step can be performed together with the impregnation of the carrier with a precursor impregnating solution of lanthanum oxycarbonate, or separately, and after all of the load is performed on the carrier, drying and calcination are sequentially performed.
The amount of the compound containing an auxiliary element according to the present invention may be selected within a wide range, and in order to further improve the performance of the supported catalyst, it is preferable that the amount thereof is such that the auxiliary element is contained in the resultant catalyst in an amount of 0.01 to 5 parts by weight, and all ranges therebetween, for example, about 0.1 to 4 parts by weight, about 1 to 3 parts by weight, and any specific values 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 carrier on a dry weight basis.
In a second aspect, the present invention provides a supported catalyst prepared by the process as described above.
In a third aspect, the present invention provides a supported catalyst comprising a support and an active component supported on the support, wherein the support is halloysite; the active component comprises lanthanum oxide carbonate;
the catalyst also comprises an auxiliary element supported on the carrier, wherein the auxiliary element comprises a barium element and a strontium element.
The invention has no excessive requirements on the specific size of halloysite. The inventors of the present invention have found that when the hollow tubular nanostructure halloysite has an inner diameter of 10-20nm (e.g., can be 10nm, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, and any combination and all values within the range) and an outer diameter of 40-70nm (e.g., can be 40, 45, 50, 55, 60, 65, 70nm, and any combinations of ranges and all values within ranges), and a length of 200-1000nm (e.g., which may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, and any combinations 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 in an amount of, for example, 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 carrier on a dry weight basis; the content of the auxiliary agent in terms of the auxiliary agent element is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 1 to 3 parts by weight.
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 of Li, na, K, cs, ce, Y, ti, ru, rh, ni, ag and Pt or any combination thereof.
According to the present invention, the preparation method of the catalyst preferably comprises: carrying out microwave impregnation on a carrier by using an impregnating solution containing a precursor of lanthanum oxide carbonate and a precursor of an auxiliary agent element, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor of lanthanum oxide carbonate comprises a soluble salt of lanthanum and a soluble carbon source;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate;
wherein the pH value of the impregnating solution is 8-14.
Details of the preparation process according to the present invention are fully described in the first aspect above, and in order to avoid unnecessary repetition, the present invention is not repeated here.
In a fourth aspect, the present invention provides the use of a supported catalyst as described above in the oxidative coupling 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 ebullated 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 ebullated bed).
In a fifth aspect, the present invention provides a process for producing carbon two or more hydrocarbons from methane, the process comprising: contacting methane with a supported catalyst as described above in the presence of oxygen and under conditions of oxidative coupling of methane;
alternatively, a 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 oxidative coupling of methane.
The method for molding the catalyst before loading the catalyst into the reaction apparatus according to the present invention is not particularly limited, and may be a conventional method in the art. Preferably, the molding condition is that the powder is crushed and sieved by a 40-60 mesh sieve after tabletting.
According to the present invention, the conditions for the oxidative coupling reaction of methane are not particularly limited and may be selected conventionally in the art, and the conditions for the oxidative coupling reaction of methane may include a reaction temperature of 400 to 800 ℃ (for example, may be 400 ℃, 430 ℃, 450 ℃, 470 ℃,500 ℃), a reaction pressure of normal pressure, and a space velocity of methane of 5000 to 100000 ml/(g.h), preferably 10000 to 80000 ml/(g.h). In order to increase the methane conversion, the molar ratio of methane to oxygen is preferably from 2 to 10:1, preferably 3-8:1.
embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
Analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under the model number 7890A. Methane conversion and selectivity to hydrocarbons of two or more carbons including ethane, ethylene, propane, propylene, butane, butene are calculated based on the composition of the product.
Example 1
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to the lanthanum oxide carbonate loading amount of 10 wt%, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 11, halloysite (with the inner diameter of 15nm, the outer diameter of 65nm and the length of 600 nm) is added into the impregnating solution, and the impregnating solution is stirred uniformly at room temperature, placed into a microwave reactor and treated for 5min at 600W. Then heating to 80 ℃ to volatilize water, placing in a 100 ℃ oven to dry for 12 hours, then moving into a muffle furnace to bake, heating at a speed of 3 ℃/min, and baking in air at 550 ℃ for 2 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-1, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 2
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to the lanthanum oxide carbonate loading amount of 15 wt%, lanthanum nitrate hexahydrate and ammonium bicarbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 9, halloysite (with the inner diameter of 10nm, the outer diameter of 40nm and the length of 1000 nm) is added into the impregnating solution, and the impregnating solution is stirred uniformly at room temperature, placed into a microwave reactor and treated for 10min at 400W. Then heating to 80 ℃ to volatilize water, placing in an 80 ℃ oven to dry for 15 hours, then moving into a muffle furnace to bake, heating up at a speed of 1 ℃/min, and baking in air at 500 ℃ for 4 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-2, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 3
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
According to lanthanum oxide loading of 5 wt%, lanthanum nitrate hexahydrate and ammonium carbonate are dissolved in deionized water to obtain a precursor impregnating solution of lanthanum oxide carbonate, the pH value of the impregnating solution is adjusted to 11, halloysite (with the inner diameter of 20nm, the outer diameter of 70nm and the length of 200 nm) is added into the impregnating solution, and the impregnating solution is stirred uniformly at room temperature, placed into a microwave reactor and treated for 7min at 800W. Then heating to 80 ℃ to volatilize water, placing in a 90 ℃ oven to dry for 13 hours, then moving into a muffle furnace to bake, heating at a speed of 5 ℃/min, and baking in air at 525 ℃ for 3 hours. Cooling to room temperature, tabletting, sieving to obtain 40-60 mesh part to obtain methane oxidative coupling catalyst Cat-3, and XRD characterization of the catalyst with lanthanum oxide carbonate characteristic peak.
Example 4
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-4 was prepared as in example 1, except that halloysite had an inner diameter of 30nm, a microwave power of 1000W, and a lanthanum oxycarbonate loading of 20 wt%, and the catalyst had a characteristic peak of lanthanum oxycarbonate as characterized by XRD.
Example 5
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-5 was prepared as in 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 after adjusting the pH, microwave impregnation treatment was performed, according to the amount of barium element of 0.2 wt% and the amount of strontium element of 0.2 wt%. Calcination was performed as in example 1, and the catalyst was characterized by XRD to have lanthanum oxycarbonate characteristic peaks.
Example 6
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-6 was prepared as in example 5 except that potassium nitrate was dissolved in deionized water according to a potassium element loading of 0.2 wt%, an aqueous solution of barium nitrate, strontium nitrate and potassium nitrate was mixed with a precursor impregnation solution of lanthanum oxycarbonate, and a microwave impregnation treatment was performed after adjusting the pH. Calcination was performed as in example 1, and the catalyst was characterized by XRD to have lanthanum oxycarbonate characteristic peaks.
Example 7
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-7 was prepared as in example 5, except that potassium nitrate was replaced with silver nitrate, the loading of potassium element was the same as that of barium element on a molar basis, and the catalyst was characterized by XRD to have a characteristic peak of lanthanum oxycarbonate.
Example 8
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-8 was prepared as in example 1 except that calcination was performed under a nitrogen atmosphere, and the catalyst was characterized by XRD as having lanthanum oxycarbonate characteristic peaks.
Example 9
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-9 was prepared as in example 1, except that the temperature was raised to the calcination temperature at a rate of 8℃per minute, and the catalyst was characterized by XRD as having a characteristic peak of lanthanum oxycarbonate.
Example 10
This example is used to illustrate the catalyst provided by the present invention and a method for preparing the same.
Catalyst Cat-10 was prepared as in example 1, except that the calcination temperature was 750℃and the catalyst had a characteristic peak of lanthanum oxycarbonate as characterized by XRD.
Comparative example 1
This comparative example is used to illustrate the reference catalyst and its preparation method.
The preparation of catalyst Cat-D-1 was carried out in the same manner as in example 1, except that the support was replaced with calcareous soapstone during the preparation.
Comparative example 2
This comparative example is used to illustrate the reference catalyst and its preparation method.
The preparation of catalyst Cat-D-2 was carried out in the same manner as in example 1 except that the pH of the impregnation liquid was not adjusted.
Comparative example 3
This comparative example is used to illustrate the reference catalyst and its preparation method.
The catalyst Cat-D-3 was prepared as in example 1, except that ammonium carbonate was replaced with an equal amount of glycine, the pH of the impregnation solution was not adjusted, and calcination was performed under a nitrogen atmosphere.
Test example 1
This test example is used to demonstrate the catalytic performance of the catalysts of the present invention
0.2g of catalyst Cat-1 is filled into a fixed bed quartz reactor, the molar ratio of methane to oxygen is 4:1 under normal pressure, the space velocity of methane is 60000ml/gh, and the activation temperature and methane conversion rate of the oxidative coupling reaction of methane and the hydrocarbon selectivity of two or more carbon are shown in Table 1.
Test examples 2 to 10
This test example is used to demonstrate the catalytic performance of the catalysts of the present invention
Ethylene ethane was produced by oxidative coupling of methane in the same manner as in test example 1, except that catalysts Cat-2 to Cat-10 were used, respectively, and the activation temperature and methane conversion of the oxidative coupling reaction of methane and the hydrocarbon selectivity of two or more carbon atoms were as 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 of the oxidative coupling reaction of methane and hydrocarbon selectivities of two or more were as shown in Table 1.
TABLE 1
As can be seen from Table 1, when the catalyst prepared by the invention 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 two or more carbon atoms at lower initial temperature.
As can be seen from comparing example 2 with example 4, the halloysite size is not within the preferred range and an increased amount of active component is required to achieve substantially the same catalytic effect.
Comparing example 2 with examples 5 to 7, it can be seen that the starting temperature of the catalyst can be further lowered and the catalytic performance of the resulting catalyst can be further improved in the case of supporting the auxiliary element.
Comparing example 2 with example 8, it can be seen that the starting temperature of the catalyst can be further lowered under a preferable calcination atmosphere, and the catalytic performance of the resulting catalyst can be further improved.
Comparing example 2 with examples 9 to 10, it can be seen that the starting temperature of the catalyst can be further lowered and the catalytic performance of the resulting catalyst can be further improved at the calcination temperature at the preferred calcination temperature increase rate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (23)
1. A method for preparing a supported catalyst, comprising: carrying out microwave impregnation on a carrier by using a precursor impregnation liquid of lanthanum oxide carbonate, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
the precursor impregnating solution of lanthanum oxide contains soluble salt of lanthanum, soluble carbon source and water, and the dosage of the precursor of lanthanum oxide is such that the content of lanthanum oxide is 0.5-60 parts by weight relative to 100 parts by weight of carrier calculated by dry weight in the obtained supported catalyst;
wherein the carrier is halloysite, and the halloysite is of a hollow nanotube structure;
wherein the soluble carbon source is carbonate and/or bicarbonate;
wherein the pH value of the impregnating solution is 8-14.
2. The method of claim 1, wherein the microwave has a power of 300-1000W.
3. The method of claim 1, wherein the microwave impregnation is at a temperature of 20-40 ℃ for a time of 1-20min.
4. The method of claim 1, wherein the impregnating solution has a pH 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.
5. The method according to any one of claims 1 to 4, wherein the halloysite hollow nanotubes have an inner diameter of 10 to 20nm, an outer diameter of 40 to 70nm, and a length of 200 to 1000nm.
6. 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 content is 2 to 30 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis in the resulting supported catalyst.
7. The method of any of claims 1-4, wherein the drying conditions comprise: the temperature is 80-180 ℃ and the time is 12-24 hours; and/or
The roasting conditions include: the temperature is 450-600 ℃ and the time is 2-8 hours.
8. The method of any one of claims 1-4, wherein the firing is performed under an atmosphere of air or carbon dioxide.
9. The method of claim 7, wherein the dried material is warmed to the firing temperature at a rate of 1-10 ℃/min.
10. The method according to any one of claims 1-4, wherein the method further comprises: and loading the auxiliary agent element on the carrier.
11. The method of claim 10, wherein the adjunct element is a metallic element, a semi-metallic element, a non-metallic element, or a combination thereof.
12. The method of claim 10, wherein the adjunct element is any one or any combination of Li, na, K, cs, ce, Y, ba, ti, ru, rh, ni, sr, ag and Pt.
13. The method according to claim 10, wherein the auxiliary element is used in such an amount that the content of the auxiliary element is 0.01 to 5 parts by weight relative to 100 parts by weight of the carrier on a dry weight basis in the resulting supported catalyst.
14. A supported catalyst, characterized in that it is obtainable by the process according to any one of claims 1 to 13.
15. The supported catalyst is characterized by comprising a carrier and an active component supported on the carrier, wherein the carrier is halloysite, and the halloysite is of a hollow nanotube structure; the active component comprises lanthanum oxide carbonate, wherein the content of the lanthanum oxide carbonate is 0.5-60 parts by weight relative to 100 parts by weight of a carrier calculated by dry weight;
the catalyst also comprises an auxiliary element supported on the carrier, wherein the auxiliary element comprises a barium element and a strontium element.
16. The supported catalyst according to claim 15, wherein the content of the auxiliary element is 0.01 to 5 parts by weight per 100 parts by weight of the carrier on a dry weight basis.
17. The supported catalyst of claim 15, wherein the halloysite hollow nanotubes have an inner diameter of 10-20nm, an outer diameter of 40-70nm, and a length of 200-1000nm.
18. The supported catalyst of any one of claims 15-17, 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.
19. The supported catalyst according to any one of claims 15 to 17, wherein the preparation method of the supported catalyst comprises: carrying out microwave impregnation on a carrier by using an impregnating solution containing a precursor of lanthanum oxide carbonate and a precursor of an auxiliary agent element, and then sequentially drying and roasting the impregnated solid material to obtain the supported catalyst;
wherein the precursor of lanthanum oxide carbonate comprises a soluble salt of lanthanum and a soluble carbon source;
wherein the carrier is halloysite;
wherein the soluble carbon source is carbonate and/or bicarbonate;
wherein the pH value of the impregnating solution is 8-14.
20. Use of a supported catalyst according to any one of claims 14 and 15 to 19 in a methane oxidative coupling reaction.
21. A process for producing hydrocarbons of carbon two or more from methane, the process comprising: contacting methane with the supported catalyst of any one of claims 14 and 15-19 in the presence of oxygen and under conditions of an oxidative coupling reaction of methane;
alternatively, a supported catalyst is prepared according to the process of any one of claims 1-13, and then methane is contacted with the resulting supported catalyst in the presence of oxygen and under conditions of oxidative coupling of methane.
22. The method of claim 21, wherein the molar ratio of methane to oxygen is 2-10:1, a step of;
and/or, the contact temperature is 400-800 ℃; the space velocity of methane is 5000-100000 mL/(g.h).
23. The method of claim 21, wherein the molar ratio of methane to oxygen is 3-8:1.
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| CN1458865A (en) * | 2000-09-18 | 2003-11-26 | 联合碳化化学及塑料技术公司 | Catalyst for oxidative dehydrogenation of hydrocarbons |
| CN108380175A (en) * | 2018-02-28 | 2018-08-10 | 中国科学院广州地球化学研究所 | A kind of carbonic acid gas lanthanum-halloysite composite material and its preparation method and application |
| CN109420517A (en) * | 2017-08-30 | 2019-03-05 | 北京化工大学 | A kind of method that methane low temperature conversion prepares higher hydrocarbon |
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| CN1458865A (en) * | 2000-09-18 | 2003-11-26 | 联合碳化化学及塑料技术公司 | Catalyst for oxidative dehydrogenation of hydrocarbons |
| CN109420517A (en) * | 2017-08-30 | 2019-03-05 | 北京化工大学 | A kind of method that methane low temperature conversion prepares higher hydrocarbon |
| CN108380175A (en) * | 2018-02-28 | 2018-08-10 | 中国科学院广州地球化学研究所 | A kind of carbonic acid gas lanthanum-halloysite composite material and its preparation method and application |
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