CN114733560A - Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by synthesis gas one-step method - Google Patents
Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by synthesis gas one-step method Download PDFInfo
- Publication number
- CN114733560A CN114733560A CN202110020271.3A CN202110020271A CN114733560A CN 114733560 A CN114733560 A CN 114733560A CN 202110020271 A CN202110020271 A CN 202110020271A CN 114733560 A CN114733560 A CN 114733560A
- Authority
- CN
- China
- Prior art keywords
- composite catalyst
- molecular sieve
- metal oxide
- aromatic hydrocarbon
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 claims abstract description 84
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 83
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims description 39
- 239000012266 salt solution Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000011651 chromium Substances 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000012716 precipitator Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000003701 mechanical milling Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 230000002779 inactivation Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 5
- 238000005899 aromatization reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- -1 firstly Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VXLCNTLWWUDBSO-UHFFFAOYSA-N Ethiazide Chemical compound ClC1=C(S(N)(=O)=O)C=C2S(=O)(=O)NC(CC)NC2=C1 VXLCNTLWWUDBSO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 241001275899 Salta Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 229910001677 galaxite Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/391—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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 technical field of aromatic hydrocarbon preparation, and particularly relates to a composite catalyst, a preparation method and application thereof, and a method for preparing aromatic hydrocarbon by using a synthesis gas one-step method. The composite catalyst comprises the following components in a mass ratio of 1-5: 1 and a molecular sieve, wherein the molecular formula of the metal oxide is MnxZnyCrzAl0.1O4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z is 0.3-1.5, and the molecular sieve is HZSM-5 molecular sieve. The composite catalyst provided by the invention is used for preparing aromatic hydrocarbon by a synthesis gas one-step method, the CO conversion rate is more than or equal to 19 percent, the aromatic hydrocarbon selectivity is more than or equal to 75.8 percent, and the aromatic hydrocarbon space-time yield is more than or equal to 0.07 g/h.gcat(ii) a Meanwhile, the composite catalyst provided by the invention has higher stability and longer service life, and the composite catalyst can stably run for 100 hours without obvious inactivation.
Description
Technical Field
The invention relates to the technical field of aromatic hydrocarbon preparation, and particularly relates to a composite catalyst, a preparation method and application thereof, and a method for preparing aromatic hydrocarbon by using a synthesis gas one-step method.
Background
Aromatic hydrocarbon is an important basic organic chemical raw material, and derivatives thereof are widely used in chemical products such as fuels, petrifaction products, chemical fibers, plastics, rubber and the like and fine chemicals. At present, aromatic hydrocarbon is mainly produced by using petroleum as a raw material and mainly comes from a catalytic reforming process unit of an oil refinery. In addition, the aromatic hydrocarbon production process in the petroleum route also comprises an aromatic hydrocarbon extraction technology, a heavy aromatic hydrocarbon lightening technology and a light hydrocarbon aromatization technology. For countries with energy structures rich in coal and lean in oil, such as China, aromatics can also be produced through coal chemical engineering routes. In the technology for preparing aromatic hydrocarbon in the coal chemical industry, the process for directly preparing aromatic hydrocarbon by taking methanol, dimethyl ether or synthesis gas as a platform product in the coal chemical industry as a raw material opens up a new process route for producing aromatic hydrocarbon by coal, can effectively relieve the contradiction between insufficient supply of aromatic hydrocarbon and excessive production capacity of methanol, and has good development prospect.
The existing methanol synthesis catalyst is difficult to match with an aromatization catalyst, so that the preparation of aromatic hydrocarbon by the coal route is mainly carried out by a sectional method, namely the preparation of methanol and the aromatization process are carried out separately.
At present, a Zn-Cr metal oxide prepared by a coprecipitation mode and a ZSM-5 molecular sieve are physically mixed to be used as one of good catalysts for preparing aromatic hydrocarbon by a synthesis gas one-step method, but the preparation of the aromatic hydrocarbon by the synthesis gas one-step method is troubled by low CO conversion rate and low aromatic hydrocarbon selectivity for a long time.
CN107469857A discloses a catalyst for directly converting synthetic gas into arene, which is a composite catalyst A + B, wherein the catalyst A and the catalyst B are compounded together in a mechanical mixing mode, and the active component of the catalyst A is an active metal oxide selected from MnO and MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4The catalyst is ZSM-5 molecular sieve or metal modified ZSM-5 molecular sieve. The composite catalyst realizes the one-step direct conversion of the synthesis gas to prepare the aromatic hydrocarbon, and has higher product yield and selectivity, the selectivity of the aromatic hydrocarbon can reach 50-85%, and the selectivity of the byproduct methane is less than 15%.
CN107262142A discloses a catalyst for one-step synthesis of aromatic hydrocarbon, which comprises 20-60 parts by weight of methanol synthesis catalyst and 40-80 parts by weight of nano flaky ZSM-5 molecular sieve. The catalyst is suitable for preparing aromatic hydrocarbon by catalyzing synthesis gas in a fluidized bed reactor, and the reaction pressure is 0.5-5MPa at the temperature of 350-550℃ and the H2The aromatic hydrocarbon can be directly obtained under the condition that the molar ratio of the aromatic hydrocarbon to CO is 1-4, the selectivity is stabilized at 50-95 percent, and the selectivity of a liquid phase product is 88-95 percent.
CN110496639A discloses a CO2The catalyst for directly preparing the aromatic hydrocarbon by hydrogenation comprises zinc-aluminum spinel oxide and an acidic molecular sieve in a mass ratio of 1:5-5:1, wherein the zinc-aluminum spinel oxide optionally contains at least one of chromium, zirconium, copper, manganese, indium, gallium and silicon, and the acidic molecular sieve is selected from a ZSM-5 molecular sieve and/or a ZSM-11 molecular sieve; the catalyst has high arene selectivity and stable performance.
Therefore, a new composite catalyst for preparing aromatic hydrocarbons by using a synthesis gas one-step method is needed, and the composite catalyst can effectively improve the CO conversion rate and the selectivity of the aromatic hydrocarbons, so that the space-time yield of the aromatic hydrocarbons is effectively improved.
Disclosure of Invention
The invention aims to solve the problem that the catalyst for preparing aromatic hydrocarbon by a synthesis gas one-step method in the prior art cannot simultaneously meet the requirements of high CO conversion rate and high aromatic hydrocarbon selectivity, and provides a composite catalyst, a preparation method and application thereof, and a method for preparing aromatic hydrocarbon by a synthesis gas one-step method, wherein the composite catalyst has more active sites and CO adsorption sites, and effectively improves the CO conversion rate and the aromatic hydrocarbon selectivity; meanwhile, the preparation method of the composite catalyst is simple and is convenient for industrial production.
In order to achieve the above object, a first aspect of the present invention provides a composite catalyst, which is a catalyst compositeThe oxidant comprises the following components in a mass ratio of 1-5: 1 and a molecular sieve, wherein the molecular formula of the metal oxide is MnxZnyCrzAl0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z is 0.3-1.5, and the molecular sieve is HZSM-5 molecular sieve.
The second aspect of the invention provides a preparation method of a composite catalyst, which comprises the following steps of mixing metal oxide and a molecular sieve in a proportion of 1-5: 1, carrying out physical mixing to obtain a composite catalyst;
wherein the molecular formula of the metal oxide is MnxZnyCrzAl0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z ═ 0.3 to 1.5; wherein the molecular sieve is an HZSM-5 molecular sieve.
Preferably, the metal oxide is prepared by the following method:
(1) coprecipitating an aluminum salt solution and a first precipitator at 25-50 ℃ to obtain a first mixture;
(2) heating the first mixture to 70-80 ℃, adding a mixed salt solution containing manganese, zinc and chromium, adding a second precipitator for coprecipitation, and adjusting the pH value to 7-8.5 to obtain a second mixture;
(3) and aging, filtering, washing, drying and roasting the second mixture in sequence to obtain the metal oxide.
The third aspect of the invention provides an application of the composite catalyst provided by the first aspect and/or the composite catalyst prepared by the preparation method provided by the second aspect in preparation of aromatic hydrocarbon by a synthesis gas one-step method.
The fourth aspect of the invention provides a method for preparing aromatic hydrocarbon by a synthesis gas one-step method, which comprises the step of preparing H-containing aromatic hydrocarbon by using a synthesis gas in the presence of a composite catalyst2And the synthetic gas of CO is subjected to conversion reaction to obtain aromatic hydrocarbon, wherein the composite catalyst is subjected to hydrogenation reduction before the conversion reaction; wherein the composite catalyst is the composite catalyst provided by the first aspect and/or the composite catalyst prepared by the preparation method provided by the second aspect.
Compared with the prior art, the invention has the following advantages:
(1) according to the composite catalyst provided by the invention, the mass ratio of the metal oxide to the molecular sieve is limited, and particularly, Al element and Mn element are introduced into the metal oxide, so that the conversion rate of CO and the selectivity of aromatic hydrocarbon are effectively improved, namely, the Al element is used as a dispersing active component, the grain size of the prepared metal oxide is within 10nm, more active sites can be exposed, the surface oxygen vacancy concentration of the metal oxide is improved, and the CO conversion rate and the stability of the composite catalyst are improved; mn element is used as an active auxiliary agent to adjust the activity of the metal oxide, increase the adsorption sites of CO on the surface of the metal oxide, reduce the hydrogenation reaction of olefin and an intermediate, and improve the selectivity of aromatic hydrocarbon;
(2) in the preferable situation, the invention also optimizes the silicon-aluminum ratio of the molecular sieve, adopts a double-template oriented synthesis method, and adjusts the composition of the template agent to reduce the value of b axis/a axis in the molecular sieve, thereby greatly improving the selectivity of aromatic hydrocarbon;
(3) the composite catalyst provided by the invention is used for preparing aromatic hydrocarbon by a synthesis gas one-step method, the CO conversion rate is more than or equal to 19 percent, the aromatic hydrocarbon selectivity is more than or equal to 75.8 percent, and the aromatic hydrocarbon space-time yield is more than or equal to 0.07 g/h.gcat;
(4) The composite catalyst provided by the invention has higher stability and service life, and the composite catalyst can stably run for 100 hours without obvious inactivation phenomenon, namely, after the composite catalyst is used for 100 hours, the CO conversion rate is kept above 17%, the selectivity of aromatic hydrocarbon and olefin is kept above 73%, and the space-time yield of aromatic hydrocarbon is kept at 0.06 g/h.gcatThe above.
Drawings
FIG. 1 is an SEM photograph of metal oxide A1 obtained in example 1;
FIG. 2 is a TEM image of metal oxide A1 obtained in example 1;
FIG. 3 is an SEM picture of molecular sieve Z1 prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these 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.
The first aspect of the present invention provides a composite catalyst comprising, by mass, 1 to 5:1 and a molecular sieve, wherein the molecular formula of the metal oxide is MnxZnyCrzAl0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z is 0.3-1.5, and the molecular sieve is HZSM-5 molecular sieve.
The inventor of the present invention found out that: the main reason why the CO conversion rate is low in the process of preparing aromatic hydrocarbon by using a synthesis gas one-step method is that the exposure amount of active sites of metal oxides is small, and the reduction of crystal grains of the metal oxides is one of effective methods for improving the active sites, but the reaction temperature for preparing the aromatic hydrocarbon by using the synthesis gas is generally higher than the optimal roasting temperature for obtaining small-crystal-grain oxides, metal oxide particles slowly agglomerate in the using process, and the activity of a catalyst is gradually reduced. In order to reduce ZnCr2O4The particle size of the metal oxide is increased, the surface oxygen vacancy concentration of the metal oxide is increased, the CO conversion rate and the stability of the catalyst are increased, a dispersed active component Al element is introduced, the blocking effect of Al can induce the oxide to form smaller crystal grains in the roasting process, and the oxide has larger specific surface area, is beneficial to the exposure of active sites (oxygen vacancies) and increases the CO conversion rate.
On the other hand, the factor for improving the CO conversion rate often enhances the phenomenon of local hydrogen enrichment on the surface of the metal oxide, which leads to the hydrogenation of olefin or the hydrogenation of a precursor to generate byproducts such as methane and the like, the unavoidable existence of olefin generated in the molecular sieve in the process of preparing aromatic hydrocarbon from synthesis gas diffuses out of the molecular sieve pore channel, then enters the molecular sieve pore channel again along with the diffusion of the molecular sieve to aromatize, if the hydrogenation of olefin on the surface of the oxide is too strong, the C can cause the aromatization2-C4The olefin generates corresponding alkane, the concentration of the aromatization precursor is reduced, and the selectivity of the aromatic hydrocarbon product is reduced. For this purpose, Mn element is introduced as a co-promoter component, and Mn is isomorphously extractedSubstituting Zn to form Mn-ZnCr2O4The introduction of Mn increases the adsorption of CO on the oxide surface, and increases the adsorption state of CO on the oxide surface, so that dissociated H can be consumed+Form CHxO intermediates, reduced "local hydrogen enrichment" with respect to H2The dissociation contribution of (A) is small, and hydrogenation of an intermediate or hydrogenation of olefin is avoided to a certain extent, so that the selectivity of aromatic hydrocarbon is improved.
In some embodiments of the present invention, preferably, the composite catalyst comprises a catalyst component and a catalyst component in a mass ratio of 1 to 5:1 with a molecular sieve; further preferably, the composite catalyst comprises the following components in a mass ratio of 1-3: 1 and a molecular sieve. The preferable conditions are adopted, so that the surface oxygen vacancy concentration and the CO adsorption sites of the composite catalyst are improved, and the CO conversion rate and the aromatic selectivity are improved.
In the present invention, the compound has the formula MnxZnyCrzAl0.1zO4Has a spinel structure of 0<x<1,0<y<1.6,1<z<2,(x+y)/z=0.3-1.5。
To further reduce the grain size of the metal oxide, the oxygen vacancy concentration and the CO adsorption sites at the surface of the metal oxide are increased. Preferably, the metal oxide has the formula of MnxZnyCrzAl0.1zO4Wherein, 0<x<0.4,0.7<y<1.6,1<z<2,(x+y)/z=0.5-1.2。
According to the invention, preferably, in the molecular sieve, the ratio of silicon to aluminum is 20-100: 1, e.g., 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and any intermediate values therebetween, preferably 30-80: 1, wherein silicon is SiO2In terms of moles of aluminum as Al2O3In terms of moles. The preferable conditions are adopted, and the shape-selective catalytic effect on the aromatic hydrocarbon is better, so that the CO conversion rate and the aromatic hydrocarbon selectivity are improved.
Preferably, in the molecular sieve, the length of the b axis is 20-600nm, preferably 50-100 nm; the thickness in the b-axis direction is 100-500nm, preferably 200-500 nm. The optimized conditions are adopted to reduce the value of b axis/a axis of the molecular sieve and greatly improve the selectivity of aromatic hydrocarbon.
In the present invention, the b-axis length and the b-axis thickness are both the b-axis length and the b-axis thickness of a unit cell in the molecular sieve, unless otherwise specified.
Preferably, the molecular sieve has a pore volume of 0.1-0.2cm3In terms of/g, preferably from 0.12 to 0.15cm3/g。
Preferably, the grain diameter of the metal oxide is less than or equal to 10nm, preferably 5-10 nm; the specific surface area is more than or equal to 180m2Per g, preferably 180-2(ii) in terms of/g. Wherein the grain diameter and the specific surface area of the metal oxide are both obtained by a TEM image of the metal oxide.
The composite catalyst provided by the invention has higher CO conversion rate and aromatic selectivity, and preferably, the particle size of the composite catalyst is 20-40 meshes.
The second aspect of the invention provides a preparation method of the composite catalyst, wherein the metal oxide and the molecular sieve are mixed in a ratio of 1-5: 1, carrying out physical mixing and granulation to obtain the composite catalyst;
wherein the molecular formula of the metal oxide is MnxZnyCrzA0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z ═ 0.3 to 1.5; wherein the molecular sieve is an HZSM-5 molecular sieve.
According to the invention, the metal oxide is preferably mixed with the molecular sieve in a ratio of 1 to 3: 1 to obtain the composite catalyst. The preferable conditions are adopted, so that the catalytic activity of the composite catalyst is improved.
In the present invention, the method for producing the metal oxide has a wide range of choice as long as the molecular formula of the metal oxide satisfies the above-mentioned definition. Preferably, the invention adopts fractional precipitation to prepare the metal oxide, namely, firstly, the aluminum salt and the precipitator which are dispersed active components are coprecipitated, then the reaction temperature is adjusted, then the mixed salt containing manganese salt, zinc salt and chromium salt is added to be coprecipitated with the precipitator, and the fractional precipitation is used to improve the dispersion effect of the active components.
According to the present invention, preferably, the metal oxide is prepared by the following method:
(1) coprecipitating an aluminum salt solution and a first precipitator at 25-50 ℃ to obtain a first mixture;
(2) heating the first mixture to 70-80 ℃, adding a mixed salt solution containing manganese, zinc and chromium, adding a second precipitator for coprecipitation, and adjusting the pH value to 7-8.5 to obtain a second mixture;
(3) and sequentially aging, filtering, washing, drying and roasting the second mixture to obtain the metal oxide.
In the present invention, the aluminum salt solution refers to an aqueous solution containing an aluminum salt, and preferably, the concentration of the aluminum salt in the aluminum salt solution is 0.5 to 10mol/L, preferably 0.5 to 5 mol/L.
In the present invention, the aluminum salt has a wide selection range as long as the aluminum salt is soluble in water or soluble in water by the action of an auxiliary. Preferably, the aluminium salt is selected from at least one of aluminium nitrate, aluminium chloride and aluminium sulphate, preferably aluminium nitrate, for example: al (NO)3)3·9H2O。
In the present invention, the mixed salt solution containing manganese, zinc and chromium refers to an aqueous solution of a mixed salt containing manganese, zinc and chromium, unless otherwise specified. Preferably, the concentration of the mixed salt in the mixed salt solution is 0.5 to 10mol/L, preferably 0.5 to 5mol/L, wherein the respective concentrations of manganese, zinc and chromium are not limited as long as the sum of the concentrations of manganese, zinc and chromium satisfies 0.5 to 10 mol/L.
In the present invention, the mixed salt containing manganese, zinc and chromium has a wide selection range as long as the mixed salt containing manganese, zinc and chromium is soluble in water or is soluble in water under the action of an auxiliary agent. Preferably, the mixed salt containing manganese, zinc and chromium is selected from at least one of nitrates, sulfates and hydrochlorides containing manganese, zinc and chromium, preferably nitrates containing manganese, zinc and chromium, for example: cr (NO)3)3·5H2O、Zn(NO3)2·9H2O、Mn(NO3)2。
In the present invention, the first precipitant and the second precipitant have a wide range of selection, as long as the first precipitant and the second precipitant are each independently coprecipitated with a metal salt. Preferably, the first and second precipitating agents are the same or different, preferably the same. Further preferably, the first precipitant and the second precipitant are each independently selected from at least one of ammonium carbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, aqueous ammonia, sodium hydroxide, and potassium hydroxide, preferably from at least one of ammonium carbonate, ammonium bicarbonate, and aqueous ammonia. The preferable conditions are adopted, so that the precipitant can be removed completely from the metal oxide, even if a certain amount of precipitant remains in the washing process, the ammonium salt and the like can be removed in the roasting process.
In the present invention, the first precipitant and the second precipitant are each independently present in the form of an aqueous solution without special description, and preferably, the concentration of the first precipitant and the second precipitant in the aqueous solution of the first precipitant and the second precipitant is 0.5 to 10mol/L, preferably 0.5 to 5 mol/L.
According to the present invention, preferably, in step (1), the molar ratio of the aluminum salt solution to the first precipitant is from 0.95 to 1.55: 1, wherein the aluminum salt solution is Al3+And (6) counting. The preferred conditions are adopted, which is beneficial to ensuring all Al in the aluminum salt solution3+Co-precipitating with the first precipitant.
Preferably, in the step (2), the first mixture is heated to 70-80 ℃, and aluminum-containing precipitates in part of the first mixture are dissolved, mixed with a mixed salt solution containing manganese, zinc and chromium, and then coprecipitated with a second precipitator to obtain a coprecipitate containing aluminum, manganese, zinc and chromium; and simultaneously, regulating the pH value to 7-8.5 to ensure that all metal salt ions and the second precipitator are subjected to coprecipitation to obtain a second mixture. The preferable conditions are adopted, so that the crystal grains of the metal oxide are more favorably reduced, and the dispersity, the oxygen vacancy concentration and the active sites of the metal oxide are improved.
In the present invention, the aging in step (3) is performed to ensure that the precursor forms a structural unit with uniform size. Preferably, in step (3), the aging conditions include: the temperature is 50-100 ℃, preferably 60-80 ℃; the time is 1-15h, preferably 4-10 h.
In the present invention, there is a wide range of options for the manner of filtration, washing and drying, and the present invention is not described herein in detail.
In the present invention, the suction filtration is to separate the aged product from solid and liquid, wash the obtained filter cake to remove residual alkali solution on the surface of the filter cake, wash the filter cake until the filter cake is neutral, and then dry the washed filter cake, wherein the drying conditions include: the temperature is 80-150 ℃, preferably 85-120 ℃; the time is 1-20h, preferably 5-15 h.
Preferably, the conditions of the calcination include: the temperature is 300-600 ℃, and preferably 350-500 ℃; the time is 1-15h, preferably 2-10 h.
In some embodiments of the invention, in the preparation of the HZSM-5 molecular sieve, SiO2:Al2O3:TPAOH:CO(NH2)2:Na2O:H2The molar ratio of O is 20-100: 1: 1-10: 100-120: 1-10: 2000-: 1: 5-10: 105-115: 2-8: 2100-2:Al2O3:TPAOH:CO(NH2)2:Na2O:H2The molar ratio of O is 30-80: 1: 6: 111: 5: 2241.
in the present invention, there is a wide selection range for the preparation process of the HZSM-5 molecular sieve, and preferably, the ZSM-5 molecular sieve is mixed with an ammonium source in a ratio of 1: 5-20, ammonium exchange at 80-190 deg.c for 1-5 hr, filtering, washing, drying at 80-120 deg.c for 8-15 hr, and final roasting at 650 deg.c for 5-10 hr to obtain HZSM-5 molecular sieve.
According to the invention, the physical mixing time is preferably 5 to 60min, preferably 10 to 30 min.
In the present invention, the physical mixing method has a wide range of options as long as the metal oxide and the molecular sieve are uniformly mixed. Preferably, the physical mixing is at least one selected from ball milling and/or mechanical milling, preferably mechanical milling, wherein the mechanical milling is performed in a mortar.
In the present invention, the time of the physical mixing depends on the manner of the physical mixing, and preferably, the time of the mechanical milling is 5 to 60min, preferably 10 to 20 min.
According to the invention, preferably, the granulation is carried out in a granulator. And granulating the mixture of the metal composite oxide and the acidic molecular sieve to obtain the composite catalyst with the particle size of 20-40 meshes.
Preferably, the pressure of the granulation is 0 to 40MPa, preferably 5 to 20 MPa.
The third aspect of the invention provides an application of the composite catalyst provided by the first aspect and/or the composite catalyst prepared by the preparation method provided by the second aspect in preparation of aromatic hydrocarbon by a synthesis gas one-step method.
In the present invention, the aromatic hydrocarbon means at least one of xylene, trimethylbenzene and tetramethylbenzene, unless otherwise specified.
The fourth aspect of the invention provides a method for preparing aromatic hydrocarbon by a synthesis gas one-step method, which comprises the step of preparing H-containing hydrocarbon in the presence of a composite catalyst2And the synthetic gas of CO is subjected to conversion reaction to obtain aromatic hydrocarbon, wherein the composite catalyst is subjected to hydrogenation reduction before the conversion reaction; wherein the composite catalyst is the composite catalyst provided by the first aspect and/or the composite catalyst prepared by the preparation method provided by the second aspect.
According to the invention, preferably, H in the synthesis gas2And CO in a molar ratio of 1-10: 1, preferably 1 to 5: 1.
in the present invention, there is a wide range of choices for the conditions of the conversion reaction. Preferably, the conditions of the conversion reaction include: the temperature is 300-500 ℃, preferably 350-450 ℃; the pressure is 0.5-10MPa, preferably 1-5 MPa; space velocity of 100-8000mL/h gcatIt is preferably 500-6000mL/h gcat。
In some embodiments of the invention, preferably the conversion reaction is carried out in a fixed bed reactor or a moving bed reactor, preferably a fixed bed reactor. The present invention does not impose any limitation on the type of the fixed bed reactor and the moving bed reactor.
In the present invention, the hydrogenation reduction is carried out in H, unless otherwise specified2And (4) carrying out reduction under an atmosphere. Further preferably, the conditions of the hydrogenation reduction include: the temperature is 250-500 ℃, preferably 350-400 ℃; the time is 1-15h, preferably 4-10 h.
The composite catalyst provided by the invention is used in a method for preparing aromatic hydrocarbon by a synthesis gas one-step method, and the conversion rate of CO and the selectivity of the aromatic hydrocarbon are effectively improved, so that the space-time yield of the aromatic hydrocarbon is improved, for example: the CO conversion rate reaches more than 19 percent, the selectivity of aromatic hydrocarbon reaches more than 75.8 percent, and the space-time yield of the aromatic hydrocarbon reaches 0.07 g/h.gcatThe above.
The present invention will be described in detail below by way of examples.
The performance parameters of the metal oxides, molecular sieves and composite catalysts prepared in examples and comparative examples are shown in Table 1.
Example 1
Preparation of Metal oxides:
(1) Mixing 10.125gAl (NO)3)3·9H2Dissolving O in 50mL of deionized water to obtain an aluminum salt solution; reacting the aluminum salt solution with (NH) at 50 DEG4)2CO3Coprecipitating at a molar ratio of 1:1.5 to obtain a first mixture, wherein the aluminum salt solution is Al3+On a molar basis;
(2) 60gCr (NO)3)3·5H2O、17.86gZn(NO3)2·9H2O、10.77gMn(NO3)2Dissolving in 250mL of deionized water, continuously stirring until the solution is completely dissolved, and then metering the volume to 300mL to obtain a mixed salt solution; heating to 70 ℃, adding the mixed salt solution into the first mixture, and then adding (NH)4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a second mixture;
(3) aging the second mixture at 70 ℃ for 5h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 12h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide A1;
wherein, the SEM image of the metal oxide A1 is shown in figure 1, and as can be seen from figure 1, the metal oxide A1 prepared by fractional precipitation is fluffy and takes the shape of nano-crystalline stacked pellets;
a TEM image of the metal oxide A1 is shown in FIG. 2, and it is understood from FIG. 2 that the crystal grain size of the metal compound A1 is 5 to 10nm and the specific surface area is 216m2/g。
Preparation of HZSM-5 molecular sieve:
Carrying out ammonium exchange on a ZSM-5 molecular sieve with a silicon-aluminum ratio of 60 and urea at a mass ratio of 1:10 at 100 ℃ for 5h, then filtering, washing and drying an ammonium exchange product at 100 ℃ for 12h, and finally roasting at 550 ℃ for 8h to obtain a molecular sieve Z1;
among them, the SEM image of molecular sieve Z1 is shown in fig. 3, and it can be seen from fig. 3 that molecular sieve Z1 is a short b-axis molecular sieve.
Preparation of the composite catalyst:
Grinding the metal oxide A1 and the molecular sieve Z1 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 5MPa to obtain the composite catalyst S1.
Example 2
Preparation of Metal oxides:
(1) Mixing 10.125gAl (NO)3)3·9H2Dissolving O in 50mL of deionized water to obtain an aluminum salt solution; reacting the aluminum salt solution with (NH) at 50 DEG C4)2CO3Coprecipitating at a molar ratio of 1:1.5 to obtain a first mixture, wherein the aluminum salt solution is Al3+On a molar basis;
(2) 60gCr (NO)3)3·5H2O、26.79gZn(NO3)2·9H2O、10.77gMn(NO3)2Dissolving in 250mL deionized water, stirring continuously until all the solution is dissolved, and then diluting to 300mL to obtain mixed saltA solution; heating to 70 ℃, adding the mixed salt solution into the first mixture, and then adding (NH)4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a second mixture;
(3) aging the second mixture at 70 ℃ for 10h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 15h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide A2;
wherein, the SEM image of the metal oxide A2 is similar to that of figure 1, and the TEM image of the metal oxide A2 is similar to that of figure 2.
Preparation of HZSM-5 molecular sieve:
Carrying out ammonium exchange on a ZSM-5 molecular sieve with a silicon-aluminum ratio of 60 and urea at a mass ratio of 1:15 at 150 ℃ for 3h, then filtering, washing and drying an ammonium exchange product at 80 ℃ for 15h, and finally roasting at 600 ℃ for 5h to obtain a molecular sieve Z2; wherein, the SEM image of molecular sieve Z2 is similar to that of FIG. 3.
Preparation of the composite catalyst:
Grinding the metal oxide A2 and the molecular sieve Z2 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 8MPa to obtain the composite catalyst S2.
Example 3
Preparation of Metal oxides:
(1) Mixing 10.125gAl (NO)3)3·9H2Dissolving O in 50mL of deionized water to obtain an aluminum salt solution; reacting the aluminum salt solution with (NH) at 50 DEG4)2CO3Coprecipitating at a molar ratio of 1:1.4 to obtain a first mixture, wherein the aluminum salt solution is Al3+On a molar basis;
(2) 60gCr (NO)3)3·5H2O、26.79gZn(NO3)2·9H2O、16.07gMn(NO3)2Dissolving in 250mL of deionized water, continuously stirring until the solution is completely dissolved, and then metering to 270mL to obtain a mixed salt solution; heating to 70 ℃, adding the mixed salt solution into the first mixture, and then adding (NH)4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a second mixture;
(3) aging the second mixture at 70 ℃ for 10h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 15h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide A3;
among them, the SEM image of metal oxide A3 is similar to fig. 1, and the TEM image of metal oxide a2 is similar to fig. 2.
Preparation of HZSM-5 molecular sieve:
Carrying out ammonium exchange on a ZSM-5 molecular sieve with a silicon-aluminum ratio of 60 and urea at a mass ratio of 1:5 at 80 ℃ for 5h, then filtering, washing and drying an ammonium exchange product at 100 ℃ for 12h, and finally roasting at 450 ℃ for 10h to obtain a molecular sieve Z3;
wherein, the SEM image of molecular sieve Z3 is similar to that of FIG. 3.
Preparation of the composite catalyst:
Grinding the metal oxide A3 and the molecular sieve Z3 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 15MPa to obtain the composite catalyst S3.
Example 4
The procedure of example 3 was followed except that the metal oxide was prepared by a one-step precipitation process, namely:
(1) mixing 10.125gAl (NO)3)3·9H2O、60gCr(NO3)3·5H2O、17.86gZn(NO3)2·9H2O、10.77gMn(NO3)2Dissolving in 250mL of deionized water, continuously stirring until the solution is completely dissolved, and then metering the volume to 300mL to obtain a mixed salt solution; mixing the salt solution with (NH) at 70 DEG C4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a mixture;
(2) aging the mixture at 70 ℃ for 5h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 12h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide A4;
grinding the metal oxide A4 and the molecular sieve Z3 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 15MPa to obtain the composite catalyst S4.
Example 5
Following the procedure of example 3, except substituting 40 for the silica to alumina ratio in the preparation of HZSM-5 molecular sieve, molecular sieve Z4 was obtained;
grinding the metal oxide A3 and the molecular sieve Z4 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 15MPa to obtain the composite catalyst S5.
Example 6
According to the method of example 3, except that the mass ratio of the metal oxide A3 to the molecular sieve Z3 was changed to 3:2, a composite catalyst S6 was obtained.
Comparative example 1
The procedure of example 1 was followed except that the metal oxides were prepared differently, namely:
(1) 60gCr (NO)3)3·5H2O、33.41gZn(NO3)2·9H2O、10.127gMn(NO3)2Dissolving in 250mL of deionized water, continuously stirring until the solution is completely dissolved, and then metering the volume to 315mL to obtain a mixed salt solution; heating to 70 deg.C, adding (NH)4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a mixture;
(2) aging the mixture at 70 ℃ for 10h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 15h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide DA 1;
grinding the metal oxide DA1 and the molecular sieve Z1 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 5MPa to obtain the composite catalyst DS 1.
Comparative example 2
The procedure of example 1 was followed except that the metal oxides were prepared differently, namely:
(1) mixing 10.125gAl (NO)3)3·9H2Dissolving O in 24mL of deionized water to obtain an aluminum salt solution; reacting the aluminum salt solution with (NH) at 50 DEG4)2CO3Coprecipitating at a molar ratio of 1:1.5 to obtain a first mixture, wherein the aluminum salt solution is Al3+On a molar basis;
(2) 60gCr (NO)3)3·5H2O、33.41gZn(NO3)2·9H2Dissolving O in 150mL of deionized water, continuously stirring until the O is completely dissolved, and then metering the volume to 315mL to obtain a mixed salt solution; heating to 70 ℃, adding the mixed salt solution into the first mixture, and then adding (NH)4)2CO3Coprecipitating and adjusting the pH value to 7.5 to obtain a second mixture;
(3) aging the second mixture at 70 ℃ for 5h, performing suction filtration, washing a filter cake to be neutral, drying at 90 ℃ for 12h, and finally roasting at 350 ℃ for 4h to obtain a metal oxide DA 2;
grinding the metal oxide DA2 and the molecular sieve Z1 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 5MPa to obtain the composite catalyst DS 2.
Comparative example 3
Following the procedure of example 1, except that the metal oxide A1 was replaced with the metal oxide DA3, i.e., ZnCr2O4Grinding the metal oxide DA3 and the molecular sieve Z1 in a mortar at a mass ratio of 1:1 for 10min for physical mixing, and granulating the product of the physical mixing in a granulator with the pressure of 5MPa to obtain the composite catalyst D3.
Comparative example 4
According to the method of example 6, except that the mass ratio of the metal oxide A3 to the molecular sieve Z3 was replaced by 6:1, a composite catalyst S6 was obtained.
TABLE 1
TABLE 1
Note: 1-mass ratio of metal oxide to molecular sieve.
As can be seen from the data in Table 1, the metal oxide containing Al and Mn provided by the invention has smaller crystal grains, and is more beneficial to improving the oxygen vacancy concentration and CO adsorption sites on the surface of the metal oxide.
Test example 1
The composite catalysts (S1-S6 and DS1-DS4) prepared in examples 1-6 and comparative examples 1-4 are used for preparing aromatic hydrocarbon by a synthesis gas one-step method.
The test method comprises the following steps:
(1) mixing 1g of 20-40 mesh composite catalyst with 1g of 20-40 mesh quartz sand respectively, filling the mixture into a reaction tube, and reducing the mixture for 12 hours at 350 ℃ in a hydrogen atmosphere to obtain a composite catalyst after hydrogenation reduction;
(2) after the reduction is completed, N is used2Purging for 15min at a flow rate of 50mL/min, and introducing synthesis gas (H)2And CO in a molar ratio of 1:1), starting timing when the set reaction pressure is reached, after the conversion reaction is carried out for 36 hours, the main products are aromatic hydrocarbons such as dimethylbenzene and trimethylbenzene, and directly entering the products into a chromatogram for full component analysis, wherein the conversion reaction conditions comprise: the temperature is 380 ℃, the pressure is 2MPa, and the space velocity is 3600 mL/h.gcat。
Wherein, the CO conversion rate and the aromatic selectivity and the aromatic space-time yield are all shown in the table 2.
Wherein, the calculation formula of the CO conversion rate is as follows:
the formula for calculating the selectivity of aromatic hydrocarbon is as follows:
wherein the Saro is the C molar selectivity of the aromatic hydrocarbon.
The calculation formula of the aromatic hydrocarbon space-time yield is as follows:
aromatic hydrocarbon space-time yield ═ GHSV ÷ 22400 × COvol × (1-CO) conversion rate × CO2Selectivity) × 13; wherein, CO2The selectivity was 47-49%.
TABLE 2
CO conversion rate,% | Selectivity for aromatic hydrocarbons,% | Space-time yield of aromatics, g/h.gcat | |
Example 1 | 19.97 | 76.71 | 0.075 |
Example 2 | 21.65 | 77.23 | 0.082 |
Example 3 | 23.68 | 80.26 | 0.093 |
Example 4 | 22.71 | 78.57 | 0.087 |
Example 5 | 21.65 | 80.03 | 0.085 |
Example 6 | 21.78 | 75.87 | 0.081 |
Comparative example 1 | 18.08 | 75.72 | 0.067 |
Comparative example 2 | 16.09 | 68.99 | 0.054 |
Comparative example 3 | 13.41 | 71.43 | 0.047 |
Comparative example 4 | 11.22 | 65.09 | 0.032 |
According to the data in the table 2, the composite catalyst provided by the invention is used for preparing aromatic hydrocarbon by a synthesis gas one-step method, and has higher CO conversion rate and aromatic hydrocarbon selectivity, so that the space-time yield of the aromatic hydrocarbon is effectively improved; in particular, the selectivity of the aromatic hydrocarbon is further improved by optimizing the silicon-aluminum ratio and the b-axis length of the molecular sieve.
Test example 2
The procedure of test example 1 was followed except that the conversion reaction time in step (2) was replaced with 100 hours, wherein the CO conversion, the aromatic selectivity and the aromatic space-time yield are shown in Table 3.
TABLE 3
CO conversion rate,% | Aromatic hydrocarbon selectivity% | Space-time yield of aromatics, g/h.gcat | |
Example 1 | 17.83 | 73.63 | 0.064 |
Example 2 | 19.71 | 75.41 | 0.073 |
Example 3 | 20.44 | 79.04 | 0.079 |
Example 4 | 21.13 | 78.57 | 0.081 |
Example 5 | 19.16 | 78.74 | 0.074 |
Example 6 | 18.44 | 76.25 | 0.069 |
Comparative example 1 | 16.47 | 70.09 | 0.056 |
Comparative example 2 | 14.75 | 69.71 | 0.05 |
Comparative example 3 | 10.19 | 61.64 | 0.031 |
Comparative example 4 | 8.18 | 55.87 | 0.020 |
As can be seen from the comparison between the tables 2 and 3, the composite catalyst provided by the invention has higher stability and service life, namely, after 100 hours of use, the CO conversion rate is kept above 17%, the selectivity of aromatic hydrocarbon and olefin is kept above 73%, and the space-time yield of aromatic hydrocarbon is kept at 0.06 g/h.gcatThe above.
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 (10)
1. A composite catalyst, characterized in that the composite catalyst comprises, by mass, 1-5: 1 and a molecular sieve, wherein the molecular formula of the metal oxide is MnxZnyCrzAl0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z is 0.3-1.5, and the molecular sieve is HZSM-5 molecular sieve.
2. The composite catalyst according to claim 1, wherein the composite catalyst comprises, in a mass ratio of 1-3: 1 with a molecular sieve;
preferably, the metal oxide has the formula of MnxZnyCrzAl0.1zO4Wherein, 0<x<0.4,0.7<y<1.6,1<z<2,(x+y)/z=0.5-1.2。
3. The composite catalyst of claim 1 or 2, wherein the molecular sieve has a silica to alumina ratio of 20-100: 1, preferably 30 to 80:1, wherein silicon is SiO2In terms of moles of aluminum as Al2O3On a molar basis;
preferably, in the molecular sieve, the length of the b axis is 20-600nm, preferably 50-100 nm; the thickness in the direction of the b axis is 100-500nm, preferably 200-500 nm;
preferably, the molecular sieve has a pore volume of 0.1-0.2cm3In g, preferably 0.12 to 0.15cm3/g;
Preferably, the grain size of the metal oxide is less than or equal to 10nm, preferably 5-10 nm; the specific surface area is more than or equal to 180m2Per g, preferably 180-2/g。
4. The composite catalyst according to any one of claims 1 to 3, wherein the particle size of the composite catalyst is 20 to 40 mesh.
5. The preparation method of the composite catalyst is characterized in that the metal oxide and the molecular sieve are mixed in a proportion of 1-5: 1, carrying out physical mixing and granulation to obtain the composite catalyst;
wherein the molecular formula of the metal oxide is Mn with a spinel structurexZnyCrzAl0.1zO4Wherein, 0<x<1,0<y<1.6,1<z<2, (x + y)/z ═ 0.3 to 1.5; wherein the molecular sieve is an HZSM-5 molecular sieve.
6. The production method according to claim 5, wherein the metal oxide is produced by:
(1) coprecipitating an aluminum salt solution and a first precipitator at 25-50 ℃ to obtain a first mixture;
(2) heating the first mixture to 70-80 ℃, adding a mixed salt solution containing manganese, zinc and chromium, adding a second precipitator for coprecipitation, and adjusting the pH value to 7-8.5 to obtain a second mixture;
(3) and sequentially aging, filtering, washing, drying and roasting the second mixture to obtain the metal oxide.
7. The method of claim 6, wherein the first and second precipitating agents are the same or different, preferably the same;
preferably, the first and second precipitants are each independently selected from at least one of ammonium carbonate, ammonium bicarbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, aqueous ammonia, sodium hydroxide and potassium hydroxide, preferably from at least one of ammonium carbonate, ammonium bicarbonate and aqueous ammonia.
8. The process according to any one of claims 5 to 7, wherein the physical mixing is carried out for a period of time of from 5 to 60min, preferably from 10 to 30 min;
preferably, the physical mixing is selected from ball milling and/or mechanical milling.
9. Use of the composite catalyst according to any one of claims 1 to 4 and/or the composite catalyst prepared by the preparation method according to any one of claims 5 to 8 in the preparation of aromatic hydrocarbons by using a synthesis gas one-step method.
10. A method for preparing aromatic hydrocarbon by a synthesis gas one-step method is characterized in that H is contained in the presence of a composite catalyst2Carrying out conversion reaction with the synthetic gas of CO to obtain aromatic hydrocarbon;
wherein the composite catalyst is subjected to hydrogenation reduction prior to the conversion reaction;
wherein the composite catalyst is selected from the composite catalyst of any one of claims 1 to 4 and/or the composite catalyst prepared by the preparation method of any one of claims 5 to 8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110020271.3A CN114733560B (en) | 2021-01-07 | 2021-01-07 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by one-step method from synthesis gas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110020271.3A CN114733560B (en) | 2021-01-07 | 2021-01-07 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by one-step method from synthesis gas |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114733560A true CN114733560A (en) | 2022-07-12 |
CN114733560B CN114733560B (en) | 2024-04-02 |
Family
ID=82273939
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110020271.3A Active CN114733560B (en) | 2021-01-07 | 2021-01-07 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by one-step method from synthesis gas |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114733560B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115608409A (en) * | 2022-11-17 | 2023-01-17 | 陕西延长石油(集团)有限责任公司 | Magnesium-aluminum composite oxide/HZSM-5 bifunctional catalyst and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107469857A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of method of the direct conversion for preparing arene of catalyst and synthesis gas |
CN109420521A (en) * | 2017-09-04 | 2019-03-05 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of Fischer-Tropsch synthesis and its preparation and application |
CN109701602A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | For producing the catalyst system and its application method of hydro carbons |
WO2019095405A1 (en) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | Method for directly producing aromatic hydrocarbons from syngas and for producing low carbon olefins in parallel |
US20190262811A1 (en) * | 2016-10-24 | 2019-08-29 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for synthesizing aromatic hydrocarbons and preparation method therefor |
-
2021
- 2021-01-07 CN CN202110020271.3A patent/CN114733560B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107469857A (en) * | 2016-06-07 | 2017-12-15 | 中国科学院大连化学物理研究所 | A kind of method of the direct conversion for preparing arene of catalyst and synthesis gas |
US20190262811A1 (en) * | 2016-10-24 | 2019-08-29 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for synthesizing aromatic hydrocarbons and preparation method therefor |
CN109420521A (en) * | 2017-09-04 | 2019-03-05 | 中国科学院大连化学物理研究所 | It is a kind of for the catalyst of Fischer-Tropsch synthesis and its preparation and application |
CN109701602A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | For producing the catalyst system and its application method of hydro carbons |
WO2019095405A1 (en) * | 2017-11-15 | 2019-05-23 | 中国科学院大连化学物理研究所 | Method for directly producing aromatic hydrocarbons from syngas and for producing low carbon olefins in parallel |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115608409A (en) * | 2022-11-17 | 2023-01-17 | 陕西延长石油(集团)有限责任公司 | Magnesium-aluminum composite oxide/HZSM-5 bifunctional catalyst and preparation method and application thereof |
CN115608409B (en) * | 2022-11-17 | 2023-11-21 | 陕西延长石油(集团)有限责任公司 | Magnesium-aluminum composite oxide/HZSM-5 dual-function catalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114733560B (en) | 2024-04-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103007985B (en) | Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof | |
CN102451744B (en) | Preparation method of hydrocracking catalyst | |
CN111229303B (en) | Composite catalyst for directly preparing high-value aromatic hydrocarbon from carbon dioxide, preparation method and application | |
CN103055924B (en) | Preparation method of bulk phase hydrocracking catalyst | |
CN105582905A (en) | Modified gamma-alumina support as well as preparation method and application thereof | |
EP3519358A1 (en) | High silica aei zeolite | |
EP3558869B1 (en) | Process to convert synthesis gas to olefins using a bifunctional chromium / zinc oxide-sapo-34 catalyst | |
CN112121847B (en) | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and preparation and application thereof | |
WO2021147213A1 (en) | Core-shell iron-based catalyst used for direct production of aromatic hydrocarbons from syngas, and preparation method and application therefor | |
CN112517012B (en) | CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation | |
CN114733560B (en) | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by one-step method from synthesis gas | |
WO2019183842A1 (en) | Composite catalyst, preparation method therefor and method for preparing ethylene | |
KR102035714B1 (en) | Nickel catalysts for reforming hydrocarbons | |
CN107413343B (en) | Preparation method of magnetic cobaltosic oxide/cobalt hydroxide/reduced graphene oxide ternary heterojunction photocatalyst | |
US20130217569A1 (en) | Stable slurry bed fischer-tropsch catalyst with high surface area and activity | |
CN112191278A (en) | Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof | |
CN112218712B (en) | For the production of C 2 And C 3 Hybrid catalyst for hydrocarbons comprising mixed metal oxide components | |
CN103055923B (en) | Preparation method of hydrocracking catalyst | |
CN112203759A (en) | Hybrid catalyst comprising zeolite and mixed metal oxide components for conversion of synthesis gas to C2 and C3 olefins | |
EP3744424A1 (en) | Organic base modified composite catalyst and method for preparing ethylene by means of hydrogenation of carbon monoxide | |
CN114733565B (en) | Composite catalyst, preparation method and application thereof, and method for preparing low-carbon olefin by one-step synthesis gas | |
KR101219644B1 (en) | Method for manufacturing iron catalyst | |
CN110038617A (en) | A kind of hydrocracking catalyst and preparation method thereof | |
US20100249252A1 (en) | Zr-fe catalysts for fischer-tropsch synthesis | |
CN107519880B (en) | Iron-based Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method of synthesis gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |