CN107297208B - Catalyst and preparation method thereof - Google Patents
Catalyst and preparation method thereof Download PDFInfo
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- CN107297208B CN107297208B CN201710434036.4A CN201710434036A CN107297208B CN 107297208 B CN107297208 B CN 107297208B CN 201710434036 A CN201710434036 A CN 201710434036A CN 107297208 B CN107297208 B CN 107297208B
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- mesoporous carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 123
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000013543 active substance Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000011149 active material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229920006395 saturated elastomer Polymers 0.000 claims description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 208000021302 gastroesophageal reflux disease Diseases 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000670 limiting effect Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000005087 graphitization Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 229910052730 francium Inorganic materials 0.000 description 2
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical materials, in particular to a catalyst and a preparation method thereof. A catalyst is used for preparing low-carbon alcohol from synthesis gas, and comprises a carrier and an active substance loaded on the carrier, wherein the carrier is graphitized mesoporous carbon, and the average pore diameter of the carrier is 2-6 nm; the active material is a metal. The porous structure of the graphitized mesoporous carbon enables the metal to be well dispersed, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the domain limiting effect can be well achieved, the influence of metal agglomeration on the performance of the catalyst is avoided, the catalytic activity and the stability of the catalyst are effectively improved, and the total alcohol selectivity can reach 68.43% when the catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas. The invention also provides a preparation method of the catalyst.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of chemical materials, in particular to a catalyst and a preparation method thereof.
[ background of the invention ]
The explosion of the oil crisis in the 70 th 20 th century causes that major countries in the world are put into the research of oil substitutes, and as major coal countries in China, the energy structure of rich coal and lean oil is more obvious, and the development of clean and efficient fuels is urgent.
The preparation of low carbon alcohol from synthesis gas is one of the clean and efficient ways for utilizing coal. First, low carbon alcohol can be used as fuel, can be burned sufficiently without pollution, and has shock and vibration resistance comparable to MTBE (methyl tert-butyl ether). Moreover, the low-carbon alcohol can also be used as a raw material of a chemical product; wherein, the methanol is the basic raw material for preparing chemical products such as formaldehyde, methylamine, chloromethane and the like, and the separated ethanol, propanol and butanol are also necessary chemical raw materials.
At present, the catalysts for preparing low-carbon alcohol from synthesis gas mainly comprise noble metal catalysts, molybdenum-based catalysts, modified methanol catalysts and modified Fischer-Tropsch catalysts. However, these catalysts have the disadvantage of not having a sufficiently high total alcohol selectivity, and therefore a new solution is urgently needed.
[ summary of the invention ]
In order to overcome the technical problems in the prior art, the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof.
The invention also provides a preparation method of the catalyst, the catalyst is used for preparing low-carbon alcohol from synthesis gas, the preparation method of the catalyst comprises the steps of providing graphitized mesoporous carbon and active substances, using resorcinol-formaldehyde resin as a carbon source and F127 as a template agent to prepare the graphitized mesoporous carbon, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the graphitized mesoporous carbon has a regularly arranged pore channel structure, and the specific surface area of the graphitized mesoporous carbon is 450-500 m-2Per g, pore volume of 0.25-0.5m3(ii)/g, the active material is a metal; the saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g; the above-mentionedPreparing the required catalyst by graphitizing mesoporous carbon and the active substance; the molar ratio of the graphitized mesoporous carbon to the active substance is (2.5-5) to 1; the preparation method of the graphitized mesoporous carbon specifically comprises the following steps: step S111: providing anhydrous sodium carbonate and formaldehyde, mixing and dissolving, adding resorcinol, and reacting at 15-20 ℃ for 1h to obtain a solution A; step S112: providing ethanol and water, stirring uniformly, adding a template agent F127 under vigorous stirring, and mixing with the solution A after dissolution to obtain a system B; step S113: dropwise adding an ethanol water solution of ferric nitrate into the system B, and reacting for 1-3h to obtain a liquid C; step S114: aging the liquid C at room temperature for 48-80h, removing the supernatant, and drying at room temperature for 6-24h to obtain gel D; step S115: reacting the gel D at the temperature of 60-100 ℃ for 12-36h to obtain a polymer E; and step S116: adding polymer E in N2Roasting at the temperature of 700-900 ℃ for 2-4h under the atmosphere to obtain graphitized mesoporous carbon; and preparing the required catalyst by using the graphitized mesoporous carbon and the active substance through an excess impregnation method or an isometric impregnation method.
Preferably, the preparation method of the catalyst further comprises: and (3) carrying out nitric acid reflux treatment on the prepared graphitized mesoporous carbon.
The catalyst provided by the invention for solving the technical problems is prepared by adopting the preparation method of the catalyst, is used for preparing low-carbon alcohol from synthesis gas, and comprises a carrier and an active substance loaded on the carrier, wherein the carrier is graphitized mesoporous carbon, resorcinol-formaldehyde resin is used as a carbon source, F127 is used as a template agent, and the graphitized mesoporous carbon is prepared and has an average pore diameter of 2-6 nm; the graphitized mesoporous carbon has a regularly arranged hexagonal mesoporous pore channel structure, and the specific surface area of the graphitized mesoporous carbon is 450-500m2Per g, pore volume of 0.25-0.5m3The saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g; the active substance is metal, and the molar ratio of the carrier to the active substance is (2.5-5): 1.
Preferably, the saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g.
Preferably, the active substance is a combination of copper, cobalt and cerium.
Preferably, the molar ratio of the copper, the cobalt and the cerium is (3-5): 1-3): 1.
Compared with the prior art, the catalyst provided by the invention adopts graphitized mesoporous carbon as a carrier and metal as an active substance. The porous structure of the graphitized mesoporous carbon enables the metal to be well dispersed, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the domain limiting effect can be well achieved, the influence of metal agglomeration on the performance of the catalyst is avoided, the catalytic activity and the stability of the catalyst are effectively improved, and the total alcohol selectivity can reach 68.43% when the catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas.
The invention also provides a preparation method of the catalyst, which takes the graphitized mesoporous carbon and metal as raw materials, and has low cost and good reproducibility; the prepared catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas, and the total alcohol selectivity can reach 68.43%.
[ description of the drawings ]
FIG. 1 is a schematic flow diagram of a process for preparing a catalyst according to the present invention.
Fig. 2 is a schematic flow chart of step S1 in the method for preparing the catalyst provided by the present invention.
Fig. 3 is a schematic flow chart of step S11 in the method for preparing the catalyst according to the present invention.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example one
A preparation method of a catalyst is used for preparing low-carbon alcohol from synthesis gas. As shown in fig. 1, the preparation method of the catalyst comprises:
step S1: providing graphitized mesoporous carbon and an active substance, wherein the average pore diameter of the graphitized mesoporous carbon is 2-6nm, and the active substance is metal;
step S2: and preparing the required catalyst by using the graphitized mesoporous carbon and the active substance.
Compared with the prior art, the graphitized mesoporous carbon is used as a carrier and metal is used as an active substance, so that the cost is low. And the porous structure of the graphitized mesoporous carbon ensures that the metal is well dispersed, the consistency of the prepared catalyst is ensured, and the repeatability is good. The graphitized mesoporous carbon has a pore channel structure, and pore channel arrangement is regular. In addition, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, and the graphitized mesoporous carbon can well play a limiting effect in the pore diameter range, thereby avoiding the influence of metal agglomeration on the performance of the catalyst and effectively improving the catalytic activity and stability of the catalyst. The catalyst is especially suitable for preparing low carbon alcohol with synthetic gas, total alcohol selectivity up to 68.43%, C2+OH accounts for more than 90% of the total alcohol. Specifically, the average pore diameter of the graphitized mesoporous carbon is 2nm, 2.5nm, 3nm, 3.5nm, 4nm, 4.5nm, 5nm, 5.5nm and 6 nm.
When the average pore diameter of the graphitized mesoporous carbon is larger, the catalytic activity of the catalyst is better, and the stability is lower; when the average pore diameter of the graphitized mesoporous carbon is small, the catalyst activity is poor, and the stability is high. Preferably, the average pore diameter of the graphitized mesoporous carbon is 3-4 nm. Within this range, the catalytic activity and stability of the catalyst can be simultaneously ensured.
The graphitized mesoporous carbon can be purchased directly, and preferably, the preparation method of the catalyst further comprises preparing the graphitized mesoporous carbon. The desired catalyst can be prepared by using the graphitized mesoporous carbon and the active material through a coprecipitation method, an impregnation method, and the like, wherein the impregnation method includes an excess impregnation method and an equal volume impregnation method. In some preferred embodiments, the required catalyst is prepared by an isometric impregnation method using the graphitized mesoporous carbon and the active substance, that is, the preparation of the catalyst is performed by the isometric impregnation method in step S2. The amount of the active substances loaded on the final catalyst can be well determined by adopting an isometric impregnation method, namely the provided active substances are loaded on the carrier; and the active substance has good dispersion uniformity, and the performance of the catalyst can be further improved. It can be understood that when equal volume impregnation is adopted, the saturated water absorption of the carrier, namely the saturated water absorption of the graphitized mesoporous carbon, needs to be measured first. In some preferred embodiments, the graphitized mesoporous carbon has a saturated water absorption of 0.4 to 0.9 mL/g. The saturated water absorption further determines the amount of the active substances which can be loaded to a certain extent; and when equal-volume impregnation is adopted, a solution containing active substances needs to be prepared, and the concentration of the prepared solution containing the active substances can be further determined within the range of the saturated water absorption capacity of the graphitized mesoporous carbon, so that the loading effect is ensured. Specifically, the saturated water absorption capacity of the graphitized mesoporous carbon is 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9 mL/g.
Referring to fig. 2, the step S1 includes:
step S11: preparing the graphitized mesoporous carbon by using resorcinol-formaldehyde resin as a carbon source and F127 as a template agent;
step S12: and preparing a metal salt solution. That is, the corresponding metal salt is weighed and prepared into a solution, and it can be understood that the volume of the prepared solution is consistent with the saturated water absorption capacity of the prepared graphitized mesoporous carbon.
The resorcinol-formaldehyde resin is adopted as a carbon source, so that the cost is low, and the method is suitable for mass production; and F127 is selected as a template agent, so that the required graphitized mesoporous carbon can be ensured to be obtained. The prepared graphitized mesoporous carbon has hexagonal mesoporous channels, good channel order and good pore diameter uniformity.
In some preferred embodiments, a graphitization catalyst needs to be added in step S11, so that the required graphitized mesoporous carbon can be obtained better and more quickly under the catalysis of the graphitization catalyst. The preferred graphitization catalyst is ferric nitrate, and the obtained graphitized mesoporous carbon has high graphitization degree. Preferably, an aqueous ethanol solution of ferric nitrate is selected, wherein the volume ratio of ethanol to water is 1: 1.
In some preferred embodiments, the method of preparing the catalyst further comprises: and (3) carrying out nitric acid reflux treatment on the prepared graphitized mesoporous carbon. Namely, the graphitized mesoporous carbon prepared in the step S11 is subjected to nitric acid reflux treatment. Can be treated by nitric acid refluxThe surface of the graphitized mesoporous carbon is oxidized, and oxygen-containing functional groups such as hydroxyl, carboxyl and the like are introduced, so that the surface hydrophilicity of the graphitized mesoporous carbon can be effectively enhanced, the interaction between the graphitized mesoporous carbon as a carrier and an active substance can be well enhanced, the active substance can be well loaded on the graphitized mesoporous carbon, and the activity of the obtained catalyst is ensured. Specifically, the prepared graphitized mesoporous carbon is ground uniformly and then mixed with 1-3mol/L nitric acid, refluxed for 6 hours at 80-100 ℃, filtered, washed to be neutral, and dried. After nitric acid reflux treatment, the specific surface area of the graphitized mesoporous carbon is 450-500m2Per g, pore volume of 0.25-0.5m3(ii)/g; in some specific embodiments, the graphitized mesoporous carbon has a specific surface area of 470m2Per g, pore volume of 0.42m3/g。
Preferably, the molar ratio of the graphitized mesoporous carbon to the active substance is (2.5-5): 1. The activity of the catalyst is ensured by determining the ratio of the graphitized mesoporous carbon to the active substance. More preferably, the molar ratio of the graphitized mesoporous carbon to the active substance is (3-4.5): 1.
The active material comprises a main metal, and the main metal is copper, iron or a combination of copper and cobalt. When the main metals are copper and iron, the molar ratio of the copper to the iron is preferably (3-5) to (1-3); when the main metals are copper and cobalt, the molar ratio of copper to cobalt is preferably (3-5) to (1-3). In some preferred embodiments, the active material further comprises an auxiliary metal, and the auxiliary metal is one or more of alkali metal and rare earth metal. Preferably, the molar ratio between the primary metal and the promoter metal is (4-8):1, more preferably, the molar ratio between the primary metal and the promoter metal is 6: 1. Alkali metals are namely lithium, sodium, potassium, rubidium, cesium, francium, and rare earth metals are namely scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. That is, the assistant metal is one or more of lithium, sodium, potassium, rubidium, cesium, francium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Wherein, the preferable auxiliary metal is one or more of rare earth metals.
In some preferred embodiments, the active metal is copper, iron, cerium, or a combination of copper, cobalt, and cerium. Most preferably, the active material is a combination of copper, cobalt and cerium, and the active material formed by the combination of the three metals has high catalytic activity. In order to further ensure the catalytic activity, in some preferred embodiments, the molar ratio of the copper, the cobalt and the cerium is (3-5): 1-3): 1. More preferably, the molar ratio of copper, cobalt and cerium is 4:2: 1.
In addition, in the preferred scheme, the graphitization catalyst is ferric nitrate, the active substance is cobalt, and if iron and cobalt exist in the catalyst at the same time, a competitive relationship exists between the iron and the cobalt, so that the catalytic action of the catalyst is influenced. Therefore, at the moment, the prepared graphitized mesoporous carbon is subjected to nitric acid reflux treatment, iron contained in the graphitized mesoporous carbon can be removed, the influence between iron and cobalt is avoided, and the catalytic activity of the catalyst is ensured.
Therefore, after the graphitized mesoporous carbon is prepared through the step S11 or directly purchased, nitric acid reflux treatment is performed on the graphitized mesoporous carbon, the saturated water absorption of the graphitized mesoporous carbon is measured, and then a certain amount of the graphitized mesoporous carbon is weighed for standby.
In step S11, it is preferable to prepare the graphitized mesoporous carbon, please refer to fig. 3, and in some preferred embodiments, step S11 includes:
step S111: providing anhydrous sodium carbonate and formaldehyde, mixing and dissolving, adding resorcinol, and reacting at 15-20 ℃ for 1h to obtain a solution A;
step S112: providing ethanol and water, stirring uniformly, adding a template agent F127 under vigorous stirring, and mixing with the solution A after dissolution to obtain a system B;
step S113: dropwise adding an ethanol water solution of ferric nitrate into the system B, and reacting for 1-3h to obtain a liquid C;
step S114: aging the liquid C at room temperature for 48-80h, removing the supernatant, and drying at room temperature for 6-24h to obtain gel D;
step S115: reacting the gel D at the temperature of 60-100 ℃ for 12-36h to obtain a polymer E;
step S116: adding polymer E in N2Roasting at the temperature of 700 ℃ and 900 ℃ for 2-4h under the atmosphere to obtain the graphitized mesoporous carbon.
In some preferred embodiments, in step S12, copper nitrate, cobalt nitrate, and cerium nitrate are weighed, the molar ratio of copper nitrate, cobalt nitrate, and cerium nitrate is 4:2:1, and the metal salt solution is obtained by dissolving copper nitrate, cobalt nitrate, and cerium nitrate in water. And the volume of the metal salt solution is the same as the saturated water absorption capacity of the weighed graphitized mesoporous carbon. Step S2, the weighed graphitized mesoporous carbon and the metal salt solution are mixed specifically, stirring or ultrasonic treatment can be carried out to ensure uniform mixing, drying is carried out for 12-36h at 40-80 ℃, and then roasting is carried out for 4-6h at 500 ℃ in a nitrogen environment at 300-. Preferably, the product obtained after roasting is naturally cooled to room temperature, and then is tableted and granulated to 40-60 meshes, so that the catalyst which can be directly used finally can be obtained.
Example two
A catalyst is used for preparing low-carbon alcohol from synthesis gas, and comprises a carrier and an active substance loaded on the carrier, wherein the carrier is graphitized mesoporous carbon, and the average pore diameter of the carrier is 2-6 nm; the active material is a metal. The catalyst was prepared by the method of preparation of the catalyst provided in example one. The active substance is loaded in the pore channel or on the pore wall of the graphitized mesoporous carbon.
Compared with the prior art, the catalyst provided by the invention adopts graphitized mesoporous carbon as a carrier and metal as an active substance. The porous structure of the graphitized mesoporous carbon enables the metal to be well dispersed, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the domain limiting effect can be well achieved, the influence of metal agglomeration on the performance of the catalyst is avoided, the catalytic activity and the stability of the catalyst are effectively improved, and the total alcohol selectivity can reach 68.43% when the catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas.
It is understood that the preferred embodiments in this embodiment are the same as those in the first embodiment, and thus, the description thereof is omitted.
Specific experimental groups are further provided below:
experimental group 1
Preparation of the catalyst:
(1) preparing graphitized mesoporous carbon:
a. weighing 0.02g of anhydrous sodium carbonate and 7.4g of formaldehyde, placing the anhydrous sodium carbonate and the formaldehyde into a small beaker, stirring, adding 6.6g of resorcinol after the anhydrous sodium carbonate is dissolved, and reacting for 1 hour at 15-20 ℃ to obtain a solution A;
b. weighing 30g of ethanol and 24g of deionized water in another small beaker, uniformly stirring, adding 4.8g of F127 under vigorous stirring, dissolving, and adding the solution into the solution A obtained in the step a to obtain a system B;
c. dropwise adding 10ml of ethanol aqueous solution of ferric nitrate (the volume ratio of the ferric nitrate to the ethanol is 1:1) into the system (namely the system B), and continuously reacting for 2 hours to obtain liquid C;
d. aging the liquid C at room temperature for 60h, removing the supernatant with a rubber head dropper, and drying at room temperature for 12h to obtain gel D;
e. placing the gel D in an oven at 80 ℃ for thermal polymerization for 24h to obtain a polymer E;
f. transfer Polymer E into a porcelain boat at N2Roasting for 3h at the temperature of 900 ℃ under the atmosphere of 700-.
(2) And (3) nitric acid reflux treatment of graphitized mesoporous carbon: uniformly grinding the product obtained in the step (1) (namely the prepared graphitized mesoporous carbon) and then mixing with 30ml of HNO3Mixing the solutions (the concentration is 2mol/L), refluxing for 6h at 100 ℃, filtering, washing to neutrality, and drying to obtain the carrier.
(3) Measuring the saturated water absorption capacity of the carrier: weighing a certain amount of the carrier obtained in the step (2), adding a metered volume of deionized water, standing overnight, sucking out the upper layer of deionized water by using a rubber head dropper, and measuring the volume, wherein the volume reduction amount is the saturated water absorption amount of a certain amount of graphitized mesoporous carbon. For example, 1g of the carrier is weighed out, and the saturated water absorption capacity is 0.63mL/g when the volume reduction is 0.63 mL.
(4) Preparing a catalyst:
a. weighing the carrier and Cu (NO) according to the molar ratio of 26:4:2:13)2·3H2O、Co(NO3)2·6H2O toAnd Ce (NO)3)3·6H2O；
b. Calculating the volume of the metal salt solution required by equal volume impregnation, and recording as V; for example, 0.2mol of the carrier is weighed, the saturated water absorption of the carrier is 0.63mL/g, and the volume V of the required metal salt solution is 0.2 × 12 × 0.63 × 1.5 mL;
c. weighing Cu (NO) in the step a3)2·3H2O、Co(NO3)2·6H2O and Ce (NO)3)3·6H2Adding deionized water into O to prepare solution (volume of solution is V), further mixing uniformly under ultrasound, adding the carrier weighed in the step a, continuing ultrasound for 1h, drying at 60 ℃ for 24h, and adding N2Roasting for 5h at 400 ℃ in the atmosphere to obtain the required catalyst.
Evaluation of catalyst:
the activity of the catalyst was evaluated by using a MRS-9001 type micro-reactor test device.
The device is controlled and operated by a computer, parameters such as temperature, gas flow, sampling time, electromagnetic valve switching value and the like can be directly set according to test requirements, the temperature error is less than +/-1 ℃, and the flow error is less than +/-1%. A fixed bed metal reactor (stainless steel pipe with the inner diameter of 8mm and the height of 240 mm) is adopted, and a six-way valve is arranged for automatic sampling, so that online sampling and online chromatographic analysis can be performed. In the fixed bed reactor, the catalyst loading was 1 g. 30% of H is used before reaction2/N2The catalyst was reduced by the mixture gas (flow rate 90mL/min) at 400 ℃ under temperature programming. After completion of reduction at N2The reactor was cooled to the reaction temperature and kept stable in the atmosphere, and was switched to synthesis gas (V (H2)/V (co) ═ 100/50), the reaction was started after slowly increasing the pressure to the reaction pressure, and online sampling analysis was performed using a GC-14B gas chromatograph (chromatographic column: Porapak packed column) manufactured by shimadzu corporation of japan, and all the connecting lines were kept at 140 ℃ by a heating tape in order to prevent condensation of the product. The activity evaluation data are the average values of 50h of stable reaction of each catalyst under the experimental conditions.
The evaluation results of the catalyst were:
total alcohol space-time yield of1023.26mg·gcat -1·h-1Total alcohol selectivity was 68.43%; the alcohol distribution was: c1OH 10.34%, C2OH 50.46%, C3OH 23.04%, C4OH 10.56%, C5OH 5.60%, C2+OH (i.e. except C)1The sum over OH) is 89.66%.
Experimental group 2
This experimental group differs from experimental group 1 in that: carrier, Cu (NO)3)2·3H2O、Co(NO3)2·6H2O and Ce (NO)3)3·6H2The molar ratio between O is 23:4:2:1
The evaluation results of the catalyst were:
the total alcohol space-time yield is 1013.45mg gcat -1·h-1Total alcohol selectivity was 65.17%; the alcohol distribution was: c1OH 11.48%, C2OH 50.12%, C3OH 22.43%, C4OH 10.26%, C5OH 5.71%, C2+OH (i.e. except C)1The sum over OH) is 88.52%.
Experimental group 3
This experimental group differs from experimental group 1 in that: carrier, Cu (NO)3)2·3H2O、Co(NO3)2·6H2O and Ce (NO)3)3·6H2The molar ratio between O is 30:4:2: 1.
The evaluation results of the catalyst were:
the total alcohol space-time yield is 1008.33mg gcat -1·h-1Total alcohol selectivity was 64.39%; the alcohol distribution was: c1OH 11.24%, C2OH 50.08%, C3OH 22.12%, C4OH 10.54%, C5OH 6.02%, C2+OH (i.e. except C)1The sum over OH) is 88.76%.
Experimental group 4
This experimental group differs from experimental group 1 in that: in the preparation step c of the graphitized mesoporous carbon, the ethanol aqueous solution of ferric nitrate is replaced by a hydrochloric acid solution of 2mol/L (namely, no graphitizing catalyst is added).
The evaluation results of the catalyst were:
the total alcohol space-time yield is 981.29mg gcat -1·h-1Total alcohol selectivity was 63.02%; the alcohol distribution was: c1OH 15.80%, C2OH content 45.28%, C3OH 19.28%, C4OH 11.87%, C5OH 7.77%, C2+OH (i.e. except C)1The sum of OH) was 84.20%.
Experimental group 5
This experimental group differs from experimental group 1 in that: in the preparation step c of the graphitized mesoporous carbon, the ethanol aqueous solution of ferric nitrate is replaced by a hydrochloric acid solution of 2mol/L (namely, no graphitizing catalyst is added), and the nitric acid reflux treatment of the graphitized mesoporous carbon is not carried out.
The evaluation results of the catalyst were:
the total alcohol space-time yield is 869.14mg gcat -1·h-1Total alcohol selectivity was 55.34%; the alcohol distribution was: c1OH 9.69%, C2OH content 49.50%, C3OH 22.36%, C4OH 11.72%, C5OH 6.74%, C2+OH (i.e. except C)1The sum over OH) is 90.31%.
A comparison of experimental groups 1-5 is shown in Table 1:
TABLE 1 comparative tables for the experimental groups 1-5
Evaluation results of catalysts of experimental groups 1 to 5 the comparative examples are shown in table 2:
the catalyst evaluation results of the experimental groups 1, 4 and 5 show that the addition of the graphitization catalyst and the nitric acid reflux treatment can well improve the catalytic performance, and the total alcohol space-time yield and the total alcohol selectivity are both obviously improved.
As can be seen from the results of comparing the catalyst evaluation results of the experimental groups 1, 2 and 3, when the molar ratio of the carrier, copper, cobalt and cerium was 26:4:2:1, the catalytic effect of the experimental group 1 was the highest, and the total alcohol space-time yield was 1023.26mg gcat -1·h-1The total alcohol selectivity can reach 68.43%.
Compared with the prior art, the catalyst provided by the invention is used for preparing low-carbon alcohol from synthesis gas, and comprises a carrier and an active substance loaded on the carrier, wherein the carrier is graphitized mesoporous carbon, and the average pore diameter of the graphitized mesoporous carbon is 2-6 nm; the active material is a metal. The porous structure of the graphitized mesoporous carbon enables the metal to be well dispersed, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the domain limiting effect can be well achieved, the influence of metal agglomeration on the performance of the catalyst is avoided, the catalytic activity and the stability of the catalyst are effectively improved, and the total alcohol selectivity can reach 68.43% when the catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas.
Further, the molar ratio of the carrier to the active substance is (2.5-5): 1. The activity of the catalyst is ensured by determining the ratio of the graphitized mesoporous carbon to the active substance.
Further, the saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g. The saturated water absorption further determines the amount of the active substances which can be loaded to a certain extent; and the range of the saturated water absorption capacity can be well suitable for preparing the catalyst by adopting an isovolumetric impregnation mode.
Further, the active substance is a combination of copper, cobalt and cerium. The combination of these three metals results in an active material with high catalytic activity.
Furthermore, the molar ratio of the copper to the cobalt to the cerium is (3-5): 1-3):1, so that the catalytic activity of the catalyst can be further ensured.
The invention also provides a preparation method of the catalyst, the catalyst is used for preparing low-carbon alcohol from synthesis gas, the preparation method of the catalyst comprises the steps of providing graphitized mesoporous carbon and active substances, the average pore diameter of the graphitized mesoporous carbon is 2-6nm, and the active substances are metals; and preparing the required catalyst by using the graphitized mesoporous carbon and the active substance. The preparation method of the catalyst takes graphitized mesoporous carbon and metal as raw materials, and has low cost and good reproducibility; the prepared catalyst is particularly suitable for preparing low-carbon alcohol from synthesis gas, and the total alcohol selectivity can reach 68.43%.
Further, the molar ratio of the graphitized mesoporous carbon to the active substance is (2.5-5):1, and the activity of the catalyst is ensured by determining the ratio of the graphitized mesoporous carbon to the active substance.
Further, the required catalyst is prepared by utilizing the graphitized mesoporous carbon and the active substance through an isometric impregnation method. The amount of the active substances loaded on the final catalyst can be well determined by adopting an isometric impregnation method, namely the provided active substances are loaded on the carrier; and the active substance has good dispersion uniformity, and the performance of the catalyst can be further improved.
Further, the preparation method of the catalyst further comprises the following steps of preparing the graphitized mesoporous carbon: and (2) preparing the graphitized mesoporous carbon by using resorcinol-formaldehyde resin as a carbon source and F127 as a template agent. The resorcinol-formaldehyde resin is adopted as a carbon source, so that the cost is low, and the method is suitable for mass production; and F127 is selected as a template agent, so that the required graphitized mesoporous carbon can be ensured to be obtained.
Further, the preparation method of the catalyst further comprises the following steps: and (3) carrying out nitric acid reflux treatment on the prepared graphitized mesoporous carbon. The surface of the graphitized mesoporous carbon can be oxidized by nitric acid reflux treatment, and oxygen-containing functional groups such as hydroxyl, carboxyl and the like are introduced, so that the surface hydrophilicity of the graphitized mesoporous carbon can be effectively enhanced, the interaction between the graphitized mesoporous carbon and an active substance can be well enhanced, the active substance can be well loaded on the graphitized mesoporous carbon, and the activity of the obtained catalyst is ensured.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A preparation method of a catalyst, which is used for preparing low-carbon alcohol from synthesis gas, is characterized in that: the preparation method of the catalyst comprises the steps of providing graphitized mesoporous carbon and active substances, wherein the average pore diameter of the graphitized mesoporous carbon is 2-6nm, the graphitized mesoporous carbon has a regularly arranged pore channel structure, and the specific surface area of the graphitized mesoporous carbon is 450-500 m-2Per g, pore volume of 0.25-0.5m3(ii)/g, the active material is a metal; the saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g; preparing the required catalyst by the graphitized mesoporous carbon and the active substance, wherein the molar ratio of the graphitized mesoporous carbon to the active substance is (2.5-5): 1; the preparation method of the graphitized mesoporous carbon specifically comprises the following steps:
step S111: providing anhydrous sodium carbonate and formaldehyde, mixing and dissolving, adding resorcinol, and reacting at 15-20 ℃ for 1h to obtain a solution A;
step S112: providing ethanol and water, stirring uniformly, adding a template agent F127 under vigorous stirring, and mixing with the solution A after dissolution to obtain a system B;
step S113: dropwise adding an ethanol water solution of ferric nitrate into the system B, and reacting for 1-3h to obtain a liquid C;
step S114: aging the liquid C at room temperature for 48-80h, removing the supernatant, and drying at room temperature for 6-24h to obtain gel D;
step S115: reacting the gel D at the temperature of 60-100 ℃ for 12-36h to obtain a polymer E; and
step S116: adding polymer E in N2Roasting at the temperature of 700-900 ℃ for 2-4h under the atmosphere to obtain graphitized mesoporous carbon;
and preparing the required catalyst by using the graphitized mesoporous carbon and the active substance through an excess impregnation method or an isometric impregnation method.
2. A process for preparing a catalyst as claimed in claim 1, characterized in that: further comprising: and (3) carrying out nitric acid reflux treatment on the prepared graphitized mesoporous carbon.
3. A catalyst for preparing low-carbon alcohol from synthesis gas comprises a carrier and an active substance loaded on the carrier, and is characterized in that: which is prepared by the method for preparing the catalyst according to claim 1 or 2; the carrier is graphitized mesoporous carbon, resorcinol-formaldehyde resin is used as a carbon source, F127 is used as a template agent, and the graphitized mesoporous carbon is prepared, wherein the average pore diameter of the graphitized mesoporous carbon is 2-6 nm; the graphitized mesoporous carbon has a regularly arranged hexagonal mesoporous pore channel structure, and the specific surface area of the graphitized mesoporous carbon is 450-500m2Per g, pore volume of 0.25-0.5m3The saturated water absorption capacity of the graphitized mesoporous carbon is 0.4-0.9 mL/g; the active material is a metal, and the active material is a metal,
the molar ratio of the carrier to the active substance is (2.5-5): 1.
4. The catalyst of claim 3, wherein: the active substance is the combination of copper, cobalt and cerium.
5. The catalyst of claim 4, wherein: the molar ratio of the copper to the cobalt to the cerium is (3-5) to (1-3) to 1.
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