CN116116424A - Dual-functional sulfur-tolerant shift catalyst and preparation method thereof - Google Patents
Dual-functional sulfur-tolerant shift catalyst and preparation method thereof Download PDFInfo
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- CN116116424A CN116116424A CN202310388718.1A CN202310388718A CN116116424A CN 116116424 A CN116116424 A CN 116116424A CN 202310388718 A CN202310388718 A CN 202310388718A CN 116116424 A CN116116424 A CN 116116424A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000005507 spraying Methods 0.000 claims abstract description 33
- 238000004898 kneading Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229940094933 n-dodecane Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000009977 dual effect Effects 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 15
- 230000007246 mechanism Effects 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- -1 magnesium aluminate Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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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Abstract
The invention belongs to the technical field of catalysts, and in particular relates to a difunctional sulfur-tolerant shift catalyst and a preparation method thereof, wherein the catalyst comprises the following raw materials: 6-11 parts of molybdenum source; 1-5 parts of cobalt source; 0.2-0.5 part of rare earth metal; 0.2-0.8 part of metal auxiliary agent; 70.8-78.7 parts of pseudo-boehmite; 12.6-14 parts of magnesium material; 2.2-4.6 parts of binder; 1-2.7 parts of dispersing agent; 0.8-2.4 parts of pore-expanding agent; the preparation method comprises the following steps: the catalyst is prepared by adopting a kneading one-step molding method, spraying and conveying through a spraying production line, and directly entering a drying and roasting working section. The catalyst prepared by the invention has two functions of transformation and hydrolysis, and has the advantages of low cost, high catalyst strength and high catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a difunctional sulfur-tolerant shift catalyst and a preparation method thereof.
Background
The sulfur-tolerant shift catalyst is a catalyst which uses cobalt and molybdenum as active components and uses magnesium and aluminum as carriers, and is applied to a process for preparing ammonia synthesis gas, oxo synthesis gas, hydrogen or city gas by using coal, heavy oil or residual oil as raw materials.
The magnesia-alumina spinel as a composite oxide has the advantages of both magnesia and alumina, stable structure and high hydration resistance, and has the advantages not possessed by both oxides, so that the magnesia-alumina powder with magnesia-alumina spinel phase is an excellent carrier component, and is also applied to the field of sulfur-tolerant shift catalysts in view of the excellent properties of magnesia-alumina spinel.
The invention patent with publication number CN1219500A, named as "novel CO sulfur-tolerant shift catalyst and preparation method", is disclosed in Chinese patent office on 6/16 1999, and is prepared through mixing three kinds of powder material of magnesium, aluminum and titanium, adding molybdenum solution, kneading, drying, crushing, adding extrusion aid and peptizing agent, kneading, forming, drying, roasting, water treatment at room temperature, and roasting to obtain MgO and Al catalyst 2 O 3 The main existing form is magnesium aluminate spinel structure.
The invention patent with the publication number of CN102049262A, named as a preparation method of clean CO sulfur-tolerant shift catalyst, is disclosed in the Chinese patent office of 2011, 5 and 11, and is characterized in that a magnesium acetate aqueous solution is mixed with pseudo-boehmite aqueous slurry, a titanium-containing auxiliary agent is added, a magnesia-alumina spinel basic material is prepared after stirring, drying and roasting, then the basic material, aluminum powder, the auxiliary agent and a pore-expanding agent are mixed, a magnesium solution is poured into the mixture to knead and squeeze strips to prepare a carrier, and then cobalt-molybdenum complex solution is used for impregnation, and the catalyst is prepared after drying and roasting; or mixing the basic material, aluminum powder, magnesium powder, auxiliary agent and pore-enlarging agent, pouring into cobalt-molybdenum complex solution, kneading and extruding to obtain the catalyst.
The invention discloses a sulfur-tolerant shift catalyst and a preparation method thereof in China patent office, 3/13/2020, with publication number of CN110876940A, which uses decarbonized magnesia-alumina spinel material as main carrier component, pseudoboehmite as auxiliary agent, and Al as mass 2 O 3 Metering, removing carbon, magnesium aluminate spinel material and Al 2 O 3 The mass ratio is 6.2: 3.8 to 7.4: 2.6; cobalt nitrate and ammonium molybdate are used as active raw materials. The prepared catalyst has high activity and good stability.
The preparation methods of the sulfur-tolerant shift catalysts disclosed in the 3 patent documents all adopt an impregnation method, and have the following defects:
1) By adopting an impregnation method, after impregnation is finished, the impregnated product needs to be manually transported to a drying and roasting section, and the manpower transportation cost is high;
2) Before preparing the catalyst by the impregnation method, the carrier (magnesia-alumina spinel) needs to be prepared by baking, which consumes more energy.
Disclosure of Invention
The invention aims to provide a difunctional sulfur-tolerant shift catalyst and a preparation method thereof, which adopt a kneading one-step molding method, optimize the production process, cancel the dipping working section, discharge finished products once, spray and convey the finished products through a spraying production line, directly enter a drying and roasting working section, reduce one-time roasting and simultaneously reduce the cost of manual transportation of the dipping method.
The invention is realized by the following technical scheme:
namely a difunctional sulfur-tolerant shift catalyst which is characterized by comprising the following raw materials in parts by weight:
6-11 parts of molybdenum source;
1-5 parts of cobalt source;
0.2-0.5 part of rare earth metal;
0.2-0.8 part of metal auxiliary agent;
70.8-78.7 parts of pseudo-boehmite;
12.6-14 parts of magnesium material;
2.2-4.6 parts of binder;
1-2.7 parts of dispersing agent;
0.8-2.4 parts of pore-expanding agent;
the rare earth metal is one or the combination of two of cerium nitrate and lanthanum nitrate;
the metal auxiliary agent is one or the combination of two of sodium carbonate and nickel nitrate;
the magnesium material is one or the combination of more of magnesium oxide, magnesium carbonate, magnesium hydroxide and magnesium nitrate.
The introduction of the rare earth metal changes the surface charge of the active metal, reduces the aggregation phenomenon of the active metal, improves the dispersity of the active metal, weakens the acting force of the active metal and the magnesium-aluminum framework, and improves the activity of the catalyst.
The rare earth metal and the metal auxiliary agent are introduced, so that the catalyst has two functions of transformation and hydrolysis, the COS hydrolysis performance of the catalyst can be improved, the COS at the outlet of the transformation furnace is reduced to below 1ppm, the load of methanol washing in the subsequent working section is reduced, the generation of sulfur in the transformation side reaction and the like is reduced, and the reaction depth is improved.
Further, the molybdenum source of the present invention is one or a combination of any of molybdenum trioxide, ammonium heptamolybdate, ammonium tetramolybdate, ammonium molybdate, or molybdic acid.
Further, the cobalt source is one or a combination of more than one of cobalt nitrate, basic cobalt carbonate, cobalt acetate and cobalt oxalate.
Furthermore, the binder is one or a combination of any more of sesbania powder, sodium carboxymethyl cellulose, high alumina cement, bentonite and hydroxypropyl methyl cellulose.
Further, the dispersing agent is one or the combination of any more of ethylenediamine, polyethylene glycol, sodium dodecyl benzene sulfonate and EDTA.
The dispersing agent can improve the dispersibility of the solution, reduce agglomeration phenomenon and improve the dispersity of the supported metal so as to provide more active sites and improve the catalytic activity.
Further, the pore-expanding agent is one or a combination of any more of multi-wall carbon nano tubes, graphite, urea and n-dodecane.
The pore-enlarging agent can increase the pore volume and the pore diameter of the catalyst, avoid the aggregation of impurities to block pore channels, reduce the pressure drop in the later operation period, improve the strength of the catalyst, reduce the generation of catalyst powder and reduce the catalyst loss.
A preparation method of a difunctional sulfur-tolerant shift catalyst is characterized in that self-made magnesia-alumina spinel is adopted as a carrier, and required metals are all introduced in one step through kneading, and the preparation method comprises the following specific steps:
1) Mixing and kneading pseudo-boehmite powder and a magnesium material for 10 minutes; after the kneading is completed, adding a binder, a dispersing agent and a pore-enlarging agent, and continuing kneading for 10 minutes;
2) After the kneading materials in the step 1) are uniformly kneaded, preparing a molybdenum source, a cobalt source, rare earth metal, a metal auxiliary agent and deionized water into a clear solution, and then adding the clear solution into a kneader for kneading for 30 minutes;
3) Putting the materials kneaded in the step 2) into a strip extruder for extrusion, and then drying, wherein a mesh belt kiln is used for drying;
4) Spraying 3w% citric acid solution on the dried product obtained in the step 3) through a spraying production line, conveying to secondary drying equipment for secondary drying while spraying, and roasting after the secondary drying is finished to obtain the catalyst.
Further, in the step 3) of the invention, the temperature area of the mesh belt kiln is 80-90 ℃, 90-110 ℃, 110-130 ℃, 130-110 ℃, 110-80 ℃ and the drying time is more than or equal to 3 hours.
Furthermore, the spraying amount of the citric acid solution in the step 4) is 60-105kg of the solution required by each ton of the catalyst, and the conveying time of the product on a spraying production line is not less than 4.5 hours.
Further, in the step 4) of the invention, the secondary drying temperature is 90-135 ℃, the drying time is more than or equal to 3 hours, the roasting temperature is 550-610 ℃, the temperature is increased according to the speed of 40 ℃/h, and the roasting time is more than or equal to 3 hours.
The excessively long kneading time in the step 1) can cause the powder to adsorb water in the air, so that the subsequent kneading is influenced, and the uniform dispersion of the binder, the dispersing agent and the pore-expanding agent is ensured during the kneading.
In the step 2), the raw materials are ensured to be uniformly mixed during kneading, the hydrolysis of pseudo-boehmite is promoted, the viscosity is improved, the raw materials are unevenly mixed after too short time, the water content of the raw materials is reduced after too long time, and the forming is not facilitated;
the method comprises the step 2) of preparing a clear solution from a molybdenum source, a cobalt source, rare earth metal, a metal auxiliary agent and deionized water, and then adding the clear solution into a kneader for kneading, so that the supported metal is uniformly supported on a catalyst carrier, the metal agglomeration effect is reduced, and the catalytic activity is improved.
In the step 4), the phenomenon that the moisture in the catalyst volatilizes instantly to cause strip frying caused by the excessively high temperature rising rate during roasting is avoided.
The invention sprays 3w% citric acid solution as pretreatment means, which can further improve the strength and surface smoothness of the catalyst, reduce the actual loss of the catalyst, and the principle is that: citric acid belongs to weak acid solution, and spraying citric acid can promote catalyst hydration, and citric acid has cohesiveness, so that the surface can be ensured to be smooth.
The citric acid solution is quantitatively sprayed, and the same effect of equal volume impregnation can be achieved.
The traditional impregnation process is that the carrier is dried and roasted, then is sent to an impregnation device, is added with impregnation liquid, is discharged after being impregnated uniformly, and is dried and roasted again, and needs to be roasted twice. The invention cancels the dipping working section, once outputs finished products, then directly enters the drying and roasting working section through spraying and conveying by a spraying production line, reduces one-time roasting and simultaneously reduces the cost of manual transportation after dipping.
The utility model provides a spraying production line of difunctional sulfur-tolerant shift catalyst, its characterized in that includes conveying mechanism, is equipped with the collector on conveying mechanism's the conveying mechanism, along the direction of delivery, conveying mechanism's top is equipped with a plurality of sprinklers in proper order, every sprinkler department is equipped with the infrared sensor that points to conveying mechanism.
The conveying mechanism of the invention is a belt conveyor commonly used in the prior art, the collector is a hopper, and the sprinkler is connected with the citric acid storage tank through a pipeline and a conveying pump.
The spraying production line adopts a mode of spraying while conveying, and the principle is as follows:
and 4) after the dried product comes out of the kiln outlet, the product falls into a collector of a conveying mechanism, the collector is conveyed forward, when passing through an infrared detector at a sprinkler, the sprinkler receives signals of the infrared detector, 3wt% of citric acid is sprayed into the collector, and when the infrared detector does not detect the collector, the sprinkler at the position stops sprinkling water, so that the product is conveyed forward to a secondary drying section while spraying water.
The invention adopts the process of spraying while conveying, ensures uniform spraying and increases the reaction time. If the solution is sprayed in all at once, metal loss is caused.
The invention has the following technical effects:
1) The one-step forming method of kneading optimizes the production process, and saves the cost of impregnating equipment and carrier roasting in the traditional impregnating process by arranging a spraying production line;
2) The spraying production line can spray on line and transfer products to a drying section, so that the manpower transfer cost in the traditional dipping process is saved; the weak acid solution sprayed by the spraying production line can further improve the strength and the surface smoothness of the catalyst, and reduce the actual loss of the catalyst.
Drawings
FIG. 1 is a schematic view of a spray line according to the present invention.
As shown in the figure: 1. an infrared detector; 2. a sprinkler; 3. a collector; 4. and a conveying mechanism.
Detailed Description
Embodiments of the technical scheme of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and thus are merely examples, and are not intended to limit the scope of the present invention. It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
Example 1
The catalyst prepared in this example comprises the following raw materials in parts by weight:
78.7 parts of pseudo-boehmite, 12.6 parts of magnesium material (magnesium oxide), 6 parts of molybdenum source (ammonium heptamolybdate), 1 part of cobalt source (cobalt nitrate), 0.4 part of rare earth metal (cerium nitrate), 2.2 parts of adhesive (sesbania powder), 1 part of dispersing agent (EDTA), 0.2 part of metal auxiliary agent (sodium carbonate) and 2.4 parts of pore expanding agent (urea).
The preparation method comprises the following specific steps:
1) Mixing and kneading pseudo-boehmite powder and a magnesium material for 10 minutes; after the kneading is completed, adding a binder, a dispersing agent and a pore-enlarging agent, and continuing kneading for 10 minutes;
2) After the kneading materials in the step 1) are uniformly kneaded, preparing a molybdenum source, a cobalt source, rare earth metal, a metal auxiliary agent and deionized water into a clear solution, and then adding the clear solution into a kneader for kneading for 30 minutes;
3) Extruding the materials kneaded in the step 2) in a strip extruder, and then drying, wherein the drying time is more than or equal to 3 hours by using a mesh belt kiln with the temperature area of 80-90 ℃, 90-110 ℃, 110-130 ℃, 130-110 ℃ and 110-80 ℃;
4) Spraying 3w% citric acid solution to the product obtained in the step 3) through a spraying production line, wherein the spraying amount is 60-105kg of solution required by each ton of catalyst, the product is conveyed to secondary drying equipment for secondary drying while being sprayed, the conveying time is not less than 4.5 hours, the secondary drying temperature is 90-135 ℃, the drying time is not less than 3 hours, the catalyst is obtained after drying, the roasting temperature is 550-610 ℃, the heating rate is 40 ℃/h, and the roasting time is not less than 3 hours.
As shown in fig. 1: the total length of the spraying production line is preferably 62 meters, the total transfer time is 4.5 hours, the spraying production line comprises a conveying mechanism 4, a collector 3 is arranged on the conveying mechanism 4, a plurality of sprayers 2 are sequentially arranged above the conveying mechanism 4 along the conveying direction, and an infrared sensor 1 pointing to the conveying mechanism 4 is arranged at each sprayer.
The conveying mechanism 4 is a belt conveyor commonly used in the prior art, the collector 3 is a hopper, and the sprinkler 2 is connected with a citric acid storage tank through a pipeline and a conveying pump.
The spraying production line of this embodiment adopts the mode of spraying while carrying, when using: and 4) after the dried product comes out of the kiln outlet, the product falls into a collector 3 of a conveying mechanism 4, when the collector 3 passes through an infrared detector 1 at a sprinkler 2 in the forward conveying process, the sprinkler 2 receives a signal of the infrared detector 1-1, 3wt% of citric acid is sprayed into the collector 3, and when the infrared detector 1 cannot detect the collector 3, the sprinkler 2 at the position stops sprinkling water, so that the product is conveyed to a secondary drying section forward while spraying water.
Example 2
The catalyst prepared in this example comprises the following raw materials in parts by weight:
70.8 parts of pseudo-boehmite, 14 parts of magnesium (magnesium hydroxide), 11 parts of molybdenum source (ammonium tetramolybdate), 5 parts of cobalt source (cobalt oxalate), 0.5 part of rare earth metal (lanthanum nitrate), 4.6 parts of adhesive (sodium carboxymethyl cellulose), 2.7 parts of dispersing agent (sodium dodecyl benzene sulfonate), 0.8 part of metal auxiliary (nickel nitrate) and 0.8 part of pore expanding agent (n-dodecane).
The procedure for the preparation of this example was the same as in example 1.
Example 3
The catalyst prepared in this example comprises the following raw materials in parts by weight:
74 parts of pseudo-boehmite, 13 parts of magnesium material (magnesium nitrate), 9 parts of molybdenum source (molybdenum trioxide), 4 parts of cobalt source (cobalt acetate), 0.2 part of rare earth metal (cerium nitrate), 3.45 parts of adhesive (high alumina cement), 1.7 parts of dispersing agent (ethylenediamine), 0.5 part of metal auxiliary agent (sodium carbonate) and 1 part of pore-expanding agent (graphite).
The procedure for the preparation of this example was the same as in example 1.
Comparative example 1
The catalyst prepared in this comparative example comprises the following raw materials in parts by weight
11 parts of molybdenum source (ammonium heptamolybdate); 3 parts of a cobalt source (cobalt nitrate); 0.5 parts of rare earth metal (cerium nitrate); 78 parts of pseudo-boehmite; 14 parts of magnesium material (magnesium oxide); 3 parts of an adhesive (sesbania powder); 2 parts of a pore-expanding agent (urea);
the preparation method comprises the following steps: extruding and molding pseudo-boehmite and magnesium material, drying and roasting to obtain a carrier, preparing an impregnating solution containing active metal components, and impregnating the impregnating solution into the carrier; and then transferring the impregnated semi-finished product to a drying section for drying in a manual transfer mode, and roasting to obtain the finished catalyst.
The catalysts prepared in examples 1-3 were compared with the conventional catalyst prepared in comparative example 1 in the following experiments for CO conversion and organosulfur conversion:
raw material gas composition: CO:34%, CO 2 ：4%，H 2 ：13%；H 2 O：48%；H 2 S:1000ppm; COS:120ppm, the remainder being nitrogen.
Inlet temperature: 230 ℃;
pressure: 6MPa of
Airspeed 3000h -1
Catalyst loading: 50kg of
Vulcanization conditions
Raw material gas: 1wt% H 2 S/H 2
Temperature: 320 DEG C
Airspeed: 1000h -1
Comparison of the experimental results with the following Table
As can be seen from the table, compared with the traditional catalyst, the catalyst prepared by the invention can realize higher organic sulfur conversion rate, lighten the load of a subsequent low-A device, has higher CO conversion rate and meets industrial application indexes.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (10)
1. A difunctional sulfur-tolerant shift catalyst is characterized by comprising the following raw materials in parts by weight:
6-11 parts of molybdenum source;
1-5 parts of cobalt source;
0.2-0.5 part of rare earth metal;
0.2-0.8 part of metal auxiliary agent;
70.8-78.7 parts of pseudo-boehmite;
12.6-14 parts of magnesium material;
2.2-4.6 parts of binder;
1-2.7 parts of dispersing agent;
0.8-2.4 parts of pore-expanding agent;
the rare earth metal is one or the combination of two of cerium nitrate and lanthanum nitrate;
the metal auxiliary agent is one or the combination of two of sodium carbonate and nickel nitrate;
the magnesium material is one or the combination of more of magnesium oxide, magnesium carbonate, magnesium hydroxide and magnesium nitrate.
2. A dual function sulfur tolerant shift catalyst according to claim 1, characterized in that the molybdenum source is one or a combination of any of molybdenum trioxide, ammonium heptamolybdate, ammonium tetramolybdate, ammonium molybdate, molybdic acid.
3. A dual function sulfur tolerant shift catalyst according to claim 1, characterized in that the cobalt source is one or a combination of any of cobalt nitrate, basic cobalt carbonate, cobalt acetate, cobalt oxalate.
4. The dual-function sulfur tolerant shift catalyst of claim 1 wherein the binder is one or a combination of any of sesbania powder, sodium carboxymethyl cellulose, high alumina cement, bentonite, hydroxypropyl methylcellulose.
5. The dual-function sulfur tolerant shift catalyst of claim 1 wherein the dispersant is one or a combination of any of ethylenediamine, polyethylene glycol, sodium dodecylbenzene sulfonate, EDTA.
6. The dual-function sulfur tolerant shift catalyst of claim 1 wherein the pore-expanding agent is one or a combination of any of a plurality of multi-walled carbon nanotubes, graphite, urea, and n-dodecane.
7. A method for preparing the difunctional sulfur-tolerant shift catalyst according to claim 1, which is characterized in that self-made magnesia-alumina spinel is adopted as a carrier, and all required metals are introduced in one step by kneading, and the specific steps are as follows:
1) Mixing and kneading pseudo-boehmite powder and a magnesium material for 10 minutes; after the kneading is completed, adding a binder, a dispersing agent and a pore-enlarging agent, and continuing kneading for 10 minutes;
2) After the kneading materials in the step 1) are uniformly kneaded, preparing a molybdenum source, a cobalt source, rare earth metal, a metal auxiliary agent and deionized water into a clear solution, and then adding the clear solution into a kneader for kneading for 30 minutes;
3) Putting the materials kneaded in the step 2) into a strip extruder for extrusion, and then drying, wherein a mesh belt kiln is used for drying;
4) Spraying 3w% citric acid solution on the dried product obtained in the step 3) through a spraying production line, conveying to secondary drying equipment for secondary drying while spraying, and roasting after the secondary drying is finished to obtain the catalyst.
8. The method for preparing a bifunctional sulfur-tolerant shift catalyst according to claim 2, wherein the mesh belt kiln temperature zone in the drying in step 3) is 80-90 ℃, 90-110 ℃, 110-130 ℃, 130-110 ℃, 110-80 ℃ and the drying time is not less than 3 hours.
9. The method for preparing a dual-function sulfur tolerant shift catalyst according to claim 2, wherein the spraying amount of the citric acid solution in the step 4) is 60-105 kg/ton of the catalyst solution, and the conveying time of the product on the spraying production line is not less than 4.5 hours.
10. The method for preparing a bifunctional sulfur-tolerant shift catalyst according to claim 2, wherein the secondary drying temperature in step 4) is 90-135 ℃, the drying time is not less than 3 hours, the calcination temperature is 550-610 ℃, the temperature is raised at a rate of 40 ℃/h, and the calcination time is not less than 3 hours.
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| CN1154271A (en) * | 1996-01-11 | 1997-07-16 | 中国石化齐鲁石油化工公司 | Preparation method of novel CO sulfur-tolerant shift catalyst |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN104248961A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN106457224B (en) * | 2015-01-13 | 2019-03-19 | 福州大学 | A kind of sulfur-resistant CO conversion catalyst and preparation method thereof |
| WO2022089072A1 (en) * | 2020-10-27 | 2022-05-05 | 中国石油化工股份有限公司 | Catalyst and method for sulfur-tolerant shift catalytic reaction |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154271A (en) * | 1996-01-11 | 1997-07-16 | 中国石化齐鲁石油化工公司 | Preparation method of novel CO sulfur-tolerant shift catalyst |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN104248961A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN106457224B (en) * | 2015-01-13 | 2019-03-19 | 福州大学 | A kind of sulfur-resistant CO conversion catalyst and preparation method thereof |
| WO2022089072A1 (en) * | 2020-10-27 | 2022-05-05 | 中国石油化工股份有限公司 | Catalyst and method for sulfur-tolerant shift catalytic reaction |
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