CN114100622B - Sulfur-tolerant pre-shift catalyst and preparation and vulcanization methods thereof - Google Patents
Sulfur-tolerant pre-shift catalyst and preparation and vulcanization methods thereof Download PDFInfo
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- CN114100622B CN114100622B CN202010896542.7A CN202010896542A CN114100622B CN 114100622 B CN114100622 B CN 114100622B CN 202010896542 A CN202010896542 A CN 202010896542A CN 114100622 B CN114100622 B CN 114100622B
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- sepiolite
- sulfur
- cobalt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004073 vulcanization Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 30
- 239000004113 Sepiolite Substances 0.000 claims abstract description 55
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 55
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 55
- 238000004898 kneading Methods 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000011593 sulfur Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 claims description 2
- 230000000607 poisoning effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000003245 coal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 239000004552 water soluble powder Substances 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- B01J23/882—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/30—
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- B01J35/31—
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- B01J35/615—
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- B01J35/635—
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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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
Abstract
The invention belongs to the technical field of sulfur-tolerant shift, and particularly relates to a sulfur-tolerant pre-shift catalyst and a preparation and vulcanization method thereof. The catalyst is prepared by acid-TiO 2 The modified sepiolite is used as a carrier, loaded molybdenum and cobalt are used as active components, the composition comprises 3.0-8.0% of molybdenum oxide, 1.0-4.0% of titanium dioxide, 0.5-3.0% of cobalt oxide and the balance of sepiolite components by weight of oxide, and the sepiolite is prepared by a kneading method. The catalyst disclosed by the invention has the advantages of high strength, good structural stability, low initial activity and good activity stability, cobalt and molybdenum are reduced to a metal state and then vulcanized, so that 'deep' vulcanization can be realized, the activity stability is more outstanding, the catalyst is suitable for protecting sulfur-tolerant shift catalysts under severe conditions of high pressure, high airspeed and high water-gas ratio, the adopted raw materials are sepiolite which is wide in source and low in cost, the preparation process is simple, the preparation cost of the catalyst is greatly reduced, and good economic benefit and environmental protection benefit are realized.
Description
Technical Field
The invention belongs to the technical field of sulfur-tolerant shift, and particularly relates to a sulfur-tolerant pre-shift catalyst and a preparation and vulcanization method thereof.
Background
The cobalt-molybdenum sulfur-resistant wide temperature shift catalyst is mainly used for preparing raw gas from heavy raw materials such as heavy oil, residual oil, coal and the like, and is a core catalyst in the field of coal chemical industry. In recent years, along with the development of the coal chemical industry and the progress of the coal chemical technology, the gasification unit process as a coal chemical faucet is continuously promoted and new, and the CO content in the gasified synthetic gas is higher and higher, for example, the CO content of the synthetic gas in the Germany Siemens GSP gasification technology reaches more than 55%, and the CO content of the synthetic gas in the Shell gasification process reaches more than 60%. Meanwhile, the coal gasification scale is continuously enlarged, for example, the increase of the conversion partial gas quantity of the medium petrochemical 4 sets of chemical fertilizer reconstruction and expansion devices is over 50 percent, and the design conversion dry gas quantity in Shenhua coal oil production project reaches 17 ten thousand Nm 3 20 ten thousand Nm produced by China petrochemical Ministry of China 3 Coal hydrogen production device per hour, and single-furnace dry gas throughput reaches 26 ten thousand Nm 3 And/h. The increase in CO content in the synthesis gas and the increase in plant size lead to a dramatic increase in shift unit reactor exotherm. In order to reduce the influence of severe working conditions on the performance of the shift catalyst, the stable operation of the main shift reactor is ensured, a sulfur-resistant pre-shift reactor is generally added in the design unit before a purification section, and the process gas is pre-shifted, so that the burden of a subsequent shift system is reduced, the influence on the subsequent main shift catalyst caused by unstable process gas is reduced, and the service life of the shift catalyst is prolonged.
The sulfur-tolerant pre-conversion catalyst used in the industry at present has a plurality of defects, mainly characterized by short service cycle, poor activity stability, replacement even in 3 months, and relatively long service life of about 1 year; some manufacturers screen the waste sulfur-tolerant shift catalyst and then load the catalyst back into the pre-shift reactor, and although the catalyst can play a certain role in shift, the actual use effect is not ideal; meanwhile, the pre-conversion catalyst has poor activity stability, high conversion activity and much heat release in the initial use period, so that the subsequent main conversion catalyst starts to operate at high temperature, the CO conversion rate cannot be increased by increasing the reaction temperature in the final use period of the main conversion catalyst, and the actual service life is influenced. Instability of the activity of the pre-shift catalyst also causes the process parameters of the subsequent system operation to be continuously adjusted, and the operation is unlikely to cause water soaking or sintering of the subsequent main shift catalyst. Therefore, it is necessary to develop a sulfur tolerant pre-shift catalyst which is relatively stable in structure and activity, has a low initial activity and a long service life.
The hydrogenation catalysts used in chemical fertilizer plants, methanol plants, oil refinery hydrogen production devices and hydrodesulfurization devices which take natural gas, oil field gas, refinery gas and light oil as raw materials are similar to sulfur-tolerant shift catalysts, and most of the hydrogenation catalysts take cobalt and molybdenum as active components. The waste catalyst is mostly subjected to a series of treatments such as calcination, acid washing, alkali washing and the like to recover the metal components, and a certain environmental pollution is unavoidable in the method. In addition, part of the waste catalyst is used as raw material of fresh catalyst after being treated, so that the catalyst has good effect.
CN201711192201.6 utilizes waste Co-Mo-K/gamma-Al 2 O 3 Sulfur-tolerant shift catalyst is baked, naturally cooled, crushed and then subjected to hydrothermal reaction, gamma-Al 2 O 3 All the catalyst is converted into boehmite (AlOOH), and the existing technology for producing active alumina carrier by a quick-release method is utilized to prepare the high-stability fresh cobalt-molybdenum sulfur-tolerant shift catalyst, so that cobalt, molybdenum, potassium and alumina in the waste cobalt-molybdenum sulfur-tolerant shift catalyst are all utilized. This method requires high equipment requirements. CN201110255440.8 is prepared by reacting alkaline aqueous solution of potassium with waste cobalt-molybdenum sulfur-tolerant shift catalyst, converting molybdenum contained in the catalyst into water-soluble powder material, and directly using the water-soluble powder material as active component raw material for preparing the sulfur-tolerant shift catalyst. This method does not fully recover the carrier component of the catalyst.
Sepiolite is a magnesium-rich silicate clay mineral. Its theoretical chemical formula is Mg 8 [Si 2 O 30 ](OH) 4 ·12H 2 And 4 of the water molecules are crystal water: the balance of zeolite water. Sepiolite is a chain of S monoclinic or orthorhombic systemThe layered water-containing magnesium aluminosilicate or magnesium silicate mineral has a huge specific surface area and good adsorptivity, can adsorb various impurities, and is commonly used for sewage treatment. The sepiolite adsorptivity can be further increased by modifying and adjusting the pore size of the sepiolite. Sepiolite is widely used, but less research and report is being made on sulfur tolerant pre-shift catalyst supports.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, providing a sulfur-tolerant pre-shift catalyst and a preparation and vulcanization method thereof, fully utilizing the property of the waste catalyst, and 'renewing' a cobalt-molybdenum hydrogenation catalyst into a sulfur-tolerant pre-shift catalyst with moderate shift activity, stable activity and good adsorption performance, and finding a more effective and environment-friendly treatment and utilization way for waste catalyst treatment.
The sulfur-tolerant pre-shift catalyst of the invention adopts acid-TiO 2 The modified sepiolite is used as a carrier, loaded molybdenum and cobalt are used as active components, and the composition comprises 3.0-8.0% of molybdenum oxide, 1.0-4.0% of titanium dioxide, 0.5-3.0% of cobalt oxide and the balance of sepiolite components by weight of oxide.
Preferably, the composition comprises, by weight of oxide, 4.0 to 5.0% of molybdenum oxide, 1.5 to 2.5% of titanium dioxide and 1.5 to 2.0% of cobalt oxide.
The pore volume of the pre-conversion catalyst is 0.50-0.65 mL/g, and the specific surface area is 160-200 m 2 The bulk density per gram is 0.75-0.80 kg/L, and the side pressure strength is 180-250N/cm.
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
(1) Pulverizing sepiolite, soaking, removing scum, filtering, and drying;
(2) Dissolving alpha-titanic acid in a dilute inorganic acid solution to prepare a modified solution, adding the modified solution into sepiolite, kneading for 4-6 hours, standing for 4-12 hours, drying, roasting and crushing to obtain the required modified sepiolite;
(3) Selecting a waste cobalt-molybdenum hydrogenation catalyst, drying, sieving to remove broken catalyst powder, and crushing to be smaller than 160 meshes to prepare catalyst aggregate;
(4) Weighing a cobalt-containing metal element compound and a molybdenum-containing metal element compound, adding ammonia water and glycol amine mixed aqueous solution, and heating to dissolve the cobalt-containing metal element compound and the molybdenum-containing metal element compound to obtain a solution A; weighing one or more of a binder or a pore-expanding agent to prepare a mixed solution B;
(5) Uniformly mixing the modified sepiolite, the catalyst aggregate and the dry meta-titanic acid powder, adding the solution A, uniformly kneading, adding the solution B, uniformly kneading, and forming, drying and roasting to obtain the sulfur-tolerant pre-conversion catalyst finished product.
The sepiolite in the step (1) is fibrous sepiolite. The color is white or light gray, and light red, light yellow or brown and the like are avoided.
Preferably, the sepiolite is white sepiolite or gray sepiolite, and the mass percentage of the white sepiolite is as follows: siO (SiO) 2 ：66～68％，MgO：30～32％，Fe x O y Less than 0.2 percent, the balance of Al 2 O 3 CaO; the grey sepiolite comprises the following components in percentage by mass: siO (SiO) 2 ：65～67％，MgO：30～32％，Fe x O y Less than 1.0%, the balance of Al 2 O 3 、CaO。
The inorganic acid in the step (2) is nitric acid, the concentration is 0.2-0.4 mol/L, and the concentration of the modifying solution is 0.3-0.7 mol/L.
The drying temperature in the step (2) is 100-120 ℃ and the drying time is 8-24 h; the modification roasting temperature is 420-450 ℃ and the roasting time is 4-8 h.
The waste cobalt-molybdenum hydrogenation catalyst in the step (3) is a catalyst discharged at the end of normal operation, and has no abnormal working conditions such as poisoning, carbon formation, overtemperature and the like; the quality content of cobalt oxide in the waste cobalt-molybdenum hydrogenation catalyst is 1.0-2.3% and the quality content of molybdenum oxide is 6.5-12.0%.
The temperature of the active component solution A in the step (4) is more than 60 ℃, preferably 70-80 ℃, and the pH value is more than 10, preferably the pH value is 11-12.0.
The pore-expanding agent in the step (4) is one or more of polyvinyl alcohol, glucose, sesbania powder, citric acid, starch or sucrose, preferably sesbania powder. The binder is one or more of acetic acid, citric acid, oxalic acid or nitric acid, preferably citric acid and/or oxalic acid.
When the hole expanding agent adopts a soluble raw material, the hole expanding agent is prepared into a solution, and when the hole expanding agent is an insoluble raw material, the hole expanding agent is not required to be prepared into the solution, and the hole expanding agent is directly mixed with a carrier as a dry material during the molding in the step (5).
The mass ratio of the sepiolite modified in the step (5) to the catalyst aggregate is 1.2-1.5:1.
The roasting temperature of the catalyst in the step (5) is 380-500 ℃, preferably 430-460 ℃, and when the temperature is too low, the cobalt and molybdenum compounds are not thoroughly decomposed, and when the temperature is too high, the sepiolite layered structure is damaged.
The appearance of the sulfur-tolerant pre-conversion catalyst can be strip-shaped, clover-leaf, hollow strip-shaped or the like, and the hollow strip-shaped is preferred.
The method for vulcanizing the sulfur-tolerant pre-shift catalyst comprises the following steps:
the sulfur tolerant pre-shift catalyst needs to be vulcanized before use, and MoO in an oxidation state is obtained 3 And CoO to MoS 2 And Co 9 S 8 . The difference is that the pre-conversion catalyst of the invention needs to be partially reduced before being vulcanized compared with the common vulcanization process. The specific implementation is as follows:
and (3) loading the sulfur-tolerant pre-conversion catalyst into a reactor, heating to 275-300 ℃ under the nitrogen atmosphere, keeping the temperature for 2 hours, gradually introducing hydrogen, finally reaching the hydrogen atmosphere, keeping the temperature of the reactor to 275-300 ℃, avoiding over-temperature, and reducing for 4-6 hours. Then cooling to 250 ℃, and vulcanizing according to the conventional vulcanizing process.
The method has the advantages that cobalt and molybdenum are reduced to a metal state and then vulcanized, so that 'deep' vulcanization can be realized, sulfur and metal cobalt and molybdenum are combined more firmly, initial activity is reduced, and activity stability is more outstanding. The waste hydrogenation catalyst aggregate added in the catalyst is matched, so that the requirements of low initial activity and high activity stability of the pre-conversion process can be met to the greatest extent.
The invention fully utilizes the waste cobalt-molybdenum hydrogenation catalystThe catalyst itself is characterized by the growth of active component grains and the decrease of activity at the end of production, and by modulating the active component composition of the catalyst and adding new carrier components, the cobalt-molybdenum hydrogenation catalyst is renovated into a sulfur-tolerant pre-shift catalyst with moderate shift activity, stable activity and good adsorption performance. The pre-conversion catalyst takes a waste cobalt-molybdenum hydrogenation catalyst as a main component and takes TiO as a main component 2 The modified sepiolite is used as a carrier, a certain amount of cobalt and molybdenum are loaded to regulate the content of active components in the catalyst, and the catalyst is prepared by a kneading method. The sepiolite is introduced as a carrier, so that a higher-density cation active site can be formed in the inner hole of the catalyst, the water content in the pore canal is locally increased in the use process of the catalyst, further, methanation side reactions on the inner hole active site are inhibited, in addition, the pore structure of the catalyst can be regulated by adding the sepiolite, the adsorptivity of the catalyst is increased, meanwhile, the heat generated by the reaction is rapidly transferred, the hot spot temperature in the catalyst is reduced to a certain extent, methanation chain reaction is further inhibited, and the stability of the catalyst structure and the activity are ensured. In an industrial shift device, the catalyst can prevent the shift furnace from being overtemperated due to methanation side reaction caused by low water-gas ratio, stabilize shift temperature, reduce hydrogen consumption of methanation side reaction, improve the hydrogen production rate of the device, and have good economic benefit and environmental protection benefit.
Compared with the prior art, the invention has the following beneficial effects:
1. the sulfur-tolerant pre-shift catalyst has high strength, good structural stability, low initial activity and good activity stability, and is suitable for protecting the sulfur-tolerant shift catalyst under the severe conditions of high pressure, high airspeed and high water-gas ratio.
2. The sepiolite with wide sources and low cost is adopted as the raw material, the preparation process is simple, the preparation cost of the catalyst is greatly reduced, and the method has good economic benefit and environmental protection benefit.
3. According to the vulcanization method disclosed by the invention, cobalt and molybdenum are reduced to a metal state and then vulcanized, so that 'deep' vulcanization can be realized, sulfur and metal cobalt and molybdenum are combined more firmly, the activity stability is more outstanding, and the requirements of low initial activity and high activity stability required by a pre-conversion process can be met to the greatest extent by matching with waste hydrogenation catalyst aggregate added in the catalyst.
Drawings
FIG. 1 is a schematic view of a pressurization evaluation device of the present invention;
in the figure: 1. containing H 2 S, a raw material gas steel cylinder; 2. MFC (mass flow controller); 3. a vaporizer; 4. a mixer; 5. a reactor; 6. a reaction tube; 7. a thermocouple tube; 8. a condenser; 9. an alkaline washing tank; 10. a separator; 11. a water tank; 12. and (5) a nitrogen steel cylinder.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
1) 2.4g of alpha-titanic acid is dissolved in 60mL of dilute nitric acid solution to prepare a modified solution; adding the modified solution into 120g of sepiolite, kneading for 4 hours, standing for 4 hours, drying at 100 ℃ for 24 hours, roasting at 420 ℃ for 8 hours, and crushing to be smaller than 160 meshes to obtain modified sepiolite;
2) Weighing 8.5g of cobalt nitrate and 18.0g of ammonium molybdate, adding 60mL of ammonia water and 3mL of ethylenediamine, heating to 70 ℃ to obtain a transparent solution A1, measuring the pH value to be 12, and respectively adding 3g of oxalic acid and 2mL of acetic acid into 20mL of ionized water to obtain a solution B1;
3) Crushing the waste hydrogenation catalyst to 160 meshes, weighing 100g of the crushed waste hydrogenation catalyst as aggregate, uniformly mixing the crushed waste hydrogenation catalyst with modified sepiolite and 2.02g of meta-titanic acid, adding the solution A1, uniformly kneading, adding the solution B1, uniformly kneading, molding, naturally airing, and roasting at 430 ℃ for 8 hours to obtain the finished catalyst Cat-1.
Example 2
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
1) Dissolving 4.53 alpha-titanic acid in 80mL of dilute nitric acid solution to prepare a modified solution; adding the modified solution into 150g of sepiolite, kneading for 6 hours, standing for 8 hours, drying at 120 ℃ for 16 hours, roasting at 450 ℃ for 8 hours, and crushing to be smaller than 160 meshes to obtain modified sepiolite;
2) 15.08g of cobalt nitrate and 49.78g of ammonium molybdate are weighed, 100mL of ammonia water and 4mL of ethylenediamine are added, the temperature is heated to 75 ℃ to obtain a transparent solution A2, the pH value is measured to be 12, and 5g of citric acid is added into 40mL of deionized water to obtain a solution B2;
3) Crushing the waste hydrogenation catalyst to 160 meshes, weighing 100g of the crushed waste hydrogenation catalyst as aggregate, uniformly mixing the crushed waste hydrogenation catalyst with modified sepiolite and 2.83g of meta-titanic acid, adding the solution A2, uniformly kneading, adding the solution B2, uniformly kneading, molding, naturally airing, and roasting at 460 ℃ for 8 hours to obtain the finished catalyst Cat-2.
Example 3
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
1) Dissolving 7.25 alpha-titanic acid in 100mL of dilute nitric acid solution to prepare a modified solution; adding the modified solution into 140g of sepiolite, kneading for 6 hours, standing for 12 hours, drying at 100 ℃ for 24 hours, roasting at 420 ℃ for 6 hours, and crushing to be smaller than 160 meshes to obtain modified sepiolite;
2) Weighing 20.11g of cobalt nitrate and 68.66g of ammonium molybdate, adding 150mL of ammonia water and 6mL of ethylenediamine, heating to 70 ℃ to obtain a transparent solution A3, measuring the pH value to be 11.5, and respectively adding 6g of oxalic acid and 12mL of acetic acid into 30mL of deionized water to obtain a solution B3;
3) Crushing the waste hydrogenation catalyst to 160 meshes, weighing 100g of the crushed waste hydrogenation catalyst as aggregate, uniformly mixing the crushed waste hydrogenation catalyst with modified sepiolite, 6.5g of sesbania powder and 6.13g of meta-titanic acid, adding the solution A3, uniformly kneading, adding the solution B3, uniformly kneading, molding, naturally airing, and roasting at 450 ℃ for 4 hours to obtain the finished catalyst Cat-3.
Example 4
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
1) 1.81 alpha-titanic acid is dissolved in 30mL of dilute nitric acid solution to prepare a modified solution; adding the modified solution into 150g of sepiolite, kneading for 5 hours, standing for 4, drying at 120 ℃ for 8 hours, roasting at 420 ℃ for 8 hours, and crushing to be smaller than 160 meshes to obtain modified sepiolite;
2) Weighing 0.58g of cobalt nitrate and 6.87g of ammonium molybdate, adding 30mL of ammonia water and 3mL of ethylenediamine, heating to 70 ℃ to obtain transparent solution A4, measuring the pH value to be 11, and adding 3g of oxalic acid into 20mL of deionized water to obtain solution B4;
3) Crushing the waste hydrogenation catalyst to 160 meshes, weighing 100g of the crushed waste hydrogenation catalyst as aggregate, uniformly mixing the crushed waste hydrogenation catalyst with modified sepiolite and 1.34g of meta-titanic acid, adding the solution A4, uniformly kneading, adding the solution B4, uniformly kneading, molding, naturally airing, and roasting at 430 ℃ for 8 hours to obtain the finished catalyst Cat-4.
Example 5
The preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
1) Dissolving 3.33 alpha-titanic acid in 50mL of dilute nitric acid solution to prepare a modified solution; adding the modified solution into 130g of sepiolite, kneading for 5 hours, standing for 8 hours, drying at 110 ℃ for 16 hours, roasting at 440 ℃ for 6 hours, and crushing to be smaller than 160 meshes to obtain modified sepiolite;
2) Weighing 7.83g of cobalt nitrate and 20.17g of ammonium molybdate, adding 80mL of ammonia water and 5mL of ethylenediamine, heating to 75 ℃ to obtain a transparent solution A5, measuring the pH value to be 11.5, and respectively adding 3g of glucose and 3g of citric acid into 25mL of deionized water to obtain a solution B5;
3) Crushing the waste hydrogenation catalyst to 160 meshes, weighing 100g of the crushed waste hydrogenation catalyst as aggregate, uniformly mixing the crushed waste hydrogenation catalyst with modified sepiolite and 2.82g of meta-titanic acid, adding the solution A5, uniformly kneading, adding the solution B5, uniformly kneading, molding, naturally airing, and roasting at 450 ℃ for 6 hours to obtain the finished catalyst Cat-5.
Comparative example 1
The commercial sulfur shift resistant catalyst QYB-01 and the sulfur shift resistant catalyst QCS-03 were used as a comparative example to compare with the catalysts prepared in the examples.
Performance test 1
The strength and strength stability of the catalyst after normal pressure water boiling and high temperature high pressure water heating treatment are examined by water boiling and water heating treatment strengthening tests, and the results are shown in Table 1.
Water boiling test conditions: a certain amount of catalyst is taken and boiled in boiling water for 3 hours, and the change of the strength of the catalyst is measured after the catalyst is dried, so that the strength and the stability of the catalyst after the catalyst is soaked in hot water under normal pressure are examined.
High-temperature high-pressure hydrothermal treatment test conditions: pressurizing at original granularityOn the evaluation device, nitrogen and water vapor are used as media, and the dry gas airspeed is as follows: 4000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Pressure: 4.0MPa; inlet temperature was evaluated: 300 ℃; catalyst loading: 50.0mL; the catalyst was treated for 100 hours at a water-to-vapor ratio of 1.5 and the change in strength of the dried catalyst was measured to investigate the strength and stability of the catalyst after severe testing.
Table 1 comparison of catalyst strength and strength stability prepared by different preparation routes
As can be seen from Table 1, the strength and strength retention of the pre-shift catalysts prepared in examples 1-5 are superior to or equal to QCS-03, and can meet the strength and strength stability requirements of the pre-shift catalyst used with QCS-03, and the strength and strength retention of the pre-shift catalyst of the invention are significantly higher than those of the industrialized pre-shift catalyst QYB-01, so that the pre-shift catalyst has better strength and strength stability, and is more suitable for severe working conditions.
Performance test 2
The pre-shift catalyst prepared in examples 1 to 5 and the industrialized catalyst QYB-01 are put into a reactor, the temperature is raised to 280 ℃ under the nitrogen atmosphere, after the temperature is kept for 2 hours, hydrogen is gradually introduced, the hydrogen atmosphere is finally reached, the temperature of the reactor is kept at 280 ℃, the overtemperature is avoided, and the reaction is reduced for 6 hours. Then cooling to 250 ℃, and vulcanizing according to the conventional vulcanizing process.
Conventional vulcanization conditions:
temperature: 250 ℃; pressure: 2.0MPa; dry gas space velocity: 2000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Water/gas: 1.0; h 2 S content: 0.3%; time: 20h;
the catalyst after sulfiding according to the sulfiding method of the present invention is noted as: c-1, C-2, C-3, C-4, C-5, Q-1.
The catalysts after sulfiding according to the conventional methods are described as comparative examples: d-1, D-2, D-3, D-4, D-5, DQ-1.
Performance test 3
Evaluation of catalyst pressurization Activity
The pressurization activity evaluation apparatus and the flow chart are shown in fig. 1. The device is used for simulating industrial conditions, measuring the concentration and the change of carbon monoxide in tail gas of a catalyst with original granularity under different conditions under a certain pressure, comparing the conversion activity, stability and other performances of the catalyst, and comprehensively evaluating each performance of the catalyst. The reaction tube is a stainless steel tube with phi 45 multiplied by 5mm, and a thermocouple tube with phi 8 multiplied by 2mm is arranged in the center. Adopts the process gas before the conversion of a certain synthetic ammonia workshop as raw material gas, and adds a proper amount of H 2 S, adding a certain amount of water according to the requirements of different water-gas ratios, gasifying at high temperature, then feeding the water and gas into a reaction tube together with raw material gas for water-gas shift reaction, and carrying out chromatographic analysis on tail gas after reaction.
Raw material gas composition: CO content: 50.0% (V/V); CO 2 The content is as follows: 3.0% (V/V); h 2 S content: > 0.2% (V/V); the balance: h 2 The method comprises the steps of carrying out a first treatment on the surface of the Catalyst loading: 50mL;
sulfur shift catalyst pressurization evaluation conditions:
inlet temperature: 350 ℃; pressure: 4.0MPa; water/gas: 0.6; dry gas space velocity: 3000h -1 ；H 2 S content: 0.2 to 0.4 percent; time: 400h.
The evaluation results of the catalysts prepared according to the examples after vulcanization are shown in tables 2 and 3.
TABLE 2 comparison of 400h pressurized Activity of sulfur tolerant pre-shift catalyst
TABLE 3 comparison of 400h pressurized Activity of sulfur tolerant pre-shift catalyst
As can be seen from tables 2 and 3, the catalysts prepared by the sulfidation method of the present invention have generally lower initial activity than those prepared by the conventional sulfidation method; after a period of operation, the activity retention rate of the catalyst prepared by the vulcanization method is higher than that of the catalyst prepared by the conventional method, and the requirements of industrial devices on low initial activity and high activity stability of the pre-conversion catalyst can be met.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (8)
1. A sulfur tolerant pre-shift catalyst characterized by: with acid-TiO 2 The modified sepiolite is used as a carrier, loaded molybdenum and cobalt are used as active components, and the components comprise 3.0-8.0% of molybdenum oxide, 1.0-4.0% of titanium dioxide, 0.5-3.0% of cobalt oxide and the balance of sepiolite components by weight of oxide;
the preparation method of the sulfur-tolerant pre-shift catalyst comprises the following steps:
(1) Pulverizing sepiolite, soaking, removing scum, filtering, and drying;
(2) Dissolving alpha-titanic acid in a dilute inorganic acid solution to prepare a modified solution, adding the modified solution into sepiolite, kneading for 4-6 hours, standing for 4-12 hours, drying, roasting and crushing to obtain the required modified sepiolite;
(3) Selecting a waste cobalt-molybdenum hydrogenation catalyst, drying, sieving to remove broken catalyst powder, and crushing to be smaller than 160 meshes to prepare catalyst aggregate;
(4) Weighing a cobalt-containing metal element compound and a molybdenum-containing metal element compound, adding ammonia water and glycol amine mixed aqueous solution, and heating to dissolve the cobalt-containing metal element compound and the molybdenum-containing metal element compound to obtain a solution A; weighing at least one of a binder or a pore-expanding agent to prepare a mixed solution B;
(5) Uniformly mixing the modified sepiolite, the catalyst aggregate and the dry meta-titanic acid powder, adding the solution A, uniformly kneading, adding the solution B, uniformly kneading, and forming, drying and roasting to obtain a sulfur-resistant pre-conversion catalyst finished product; wherein the roasting temperature is 380-500 ℃;
the sulfur-tolerant pre-conversion catalyst is vulcanized before being used, the sulfur-tolerant pre-conversion catalyst is filled into a reactor, the temperature is raised to 275-300 ℃ under the nitrogen atmosphere, after the temperature is kept for 2 hours, hydrogen is introduced to reach the hydrogen atmosphere, the temperature of the reactor is kept at 275-300 ℃, the reaction is reduced for 4-6 hours, and then the temperature is reduced to 250 ℃ for vulcanization.
2. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the pore volume of the pre-conversion catalyst is 0.50-0.65 mL/g, and the specific surface area is 160-200 m 2 The bulk density per gram is 0.75-0.80 kg/L, and the side pressure strength is 180-250N/cm.
3. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the sepiolite in the step (1) is white sepiolite or gray sepiolite, and the mass percentage of the white sepiolite is as follows: siO (SiO) 2 ：66～68％，MgO：30～32％，Fe x O y Less than 0.2 percent, the balance of Al 2 O 3 CaO; the grey sepiolite comprises the following components in percentage by mass: siO (SiO) 2 ：65～67％，MgO：30～32％，Fe x O y Less than 1.0%, the balance of Al 2 O 3 、CaO。
4. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the inorganic acid in the step (2) is nitric acid, the concentration is 0.2-0.4 mol/L, and the concentration of the modifying solution is 0.3-0.7 mol/L.
5. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the drying temperature in the step (2) is 100-120 ℃ and the drying time is 8-24 h; the modification roasting temperature is 420-450 ℃ and the roasting time is 4-8 h.
6. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the waste cobalt-molybdenum hydrogenation catalyst in the step (3) is a catalyst which is discharged at the end of normal operation and has no poisoning, carbon formation and overtemperature, wherein the mass content of cobalt oxide in the waste cobalt-molybdenum hydrogenation catalyst is 1.0-2.3%, and the mass content of molybdenum oxide is 6.5-12.0%.
7. The sulfur tolerant pre-shift catalyst of claim 1 wherein: in the step (4), the temperature of the solution A is more than 60 ℃, and the pH value is more than 10.
8. The sulfur tolerant pre-shift catalyst of claim 1 wherein: the mass ratio of the sepiolite modified in the step (5) to the catalyst aggregate is 1.2-1.5:1.
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| WO2020103848A1 (en) * | 2018-11-21 | 2020-05-28 | 南京工业大学 | Environmentally-friendly high-temperature denitration catalyst and preparation method therefor |
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| CN108479754A (en) * | 2018-04-09 | 2018-09-04 | 天津大学 | A method of preparing the catalyst for methanation in presence of sulfur of zirconium oxide load |
| CN111054364A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Nickel series alkylation raw material selective hydrogenation catalyst and preparation method thereof |
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