CN110302795B - Reforming hydrogen production catalyst taking waste vanadium-titanium denitration catalyst as raw material and preparation method thereof - Google Patents
Reforming hydrogen production catalyst taking waste vanadium-titanium denitration catalyst as raw material and preparation method thereof Download PDFInfo
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- CN110302795B CN110302795B CN201910668738.8A CN201910668738A CN110302795B CN 110302795 B CN110302795 B CN 110302795B CN 201910668738 A CN201910668738 A CN 201910668738A CN 110302795 B CN110302795 B CN 110302795B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002699 waste material Substances 0.000 title claims abstract description 62
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 238000002407 reforming Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 93
- 239000012528 membrane Substances 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 65
- 238000001354 calcination Methods 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 36
- 238000000465 moulding Methods 0.000 abstract description 8
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000009616 inductively coupled plasma Methods 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004993 emission spectroscopy Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/888—Tungsten
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- 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
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
- C01B2203/1058—Nickel 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a reforming hydrogen production catalyst taking a waste vanadium-titanium denitration catalyst as a raw material and a preparation method thereof. The preparation method comprises the steps of preparing a porous ceramic membrane carrier by crushing, mixing, granulating, molding, calcining and other processes of the waste vanadium-titanium denitration catalyst, silicon source powder, aluminum source powder and molding agent solution, soaking the porous ceramic membrane carrier in an active component precursor solution, drying and roasting to obtain the reforming hydrogen production catalyst. The reforming hydrogen production catalyst can realize harmless treatment of the waste vanadium-titanium denitration catalyst, can also produce hydrogen by recycling the waste vanadium-titanium denitration catalyst with high added value, and can reform formaldehyde to produce hydrogen H2High selectivity, less active component load, low cost and wide market application prospect.
Description
Technical Field
The invention provides a reforming hydrogen production catalyst taking a waste vanadium-titanium denitration catalyst as a raw material and a preparation method thereof, belonging to the technical field of resource utilization of waste products and new energy.
Background
Nitrogen oxides are the main causes of pollution such as haze and acid rain, and denitration of industrial flue gas of thermal power plants becomes the key point of current atmospheric pollution control. When 2017 is reached, the in-service catalyst exceeds 120 million cubic meters, the average service life of the catalyst is calculated in 3-5 years according to the fact that the middle-heating power denitration project is integrated in 2013, and the vanadium-titanium denitration catalyst is about to be counted into the batch replacement period. On the other hand, the website of the ministry of environmental protection issues "a notification on the enhancement of the supervision work of the waste flue gas denitration catalyst", and the management, regeneration and utilization of the waste flue gas denitration catalyst are brought into the management of dangerous waste, and the improvement of the regeneration, utilization and disposal capabilities of the waste flue gas denitration catalyst is required. Therefore, the regeneration treatment or resource utilization of the waste vanadium-titanium denitration catalyst becomes an environmental protection problem to be solved urgently. The regeneration rate of the thermal power denitration catalyst is about 60%, and the conventional catalyst can be regenerated for 2-3 times generally and can only be completely scrapped. I.e. catalyst regeneration is not really the final treatment route. On the basis, the high-added-value resource utilization of the waste vanadium-titanium denitration catalyst is a feasible and economic conversion mode.
In the existing patents for treating waste vanadium-titanium denitration catalysts, patent CN201410623778.8 designs a continuous device for recovering vanadium, titanium and molybdenum elements in the waste vanadium-titanium denitration catalysts. In patent CN201510265236.2, the waste vanadium-titanium denitration catalyst is leached to obtain titanium-rich leaching residues and a leachate containing tungsten, molybdenum and vanadium, and the ratio of the content of each substance is adjusted after the valuable components in the leachate are purified synchronously to prepare a mixture of catalytic components, and further prepare the mixture into a new catalyst. Patent 201710717702.5 discloses a denitration catalyst, which is prepared by cleaning the surface of a waste denitration catalyst with a nitric acid solution, removing arsenic with a sodium hydroxide solution, removing mercury with sodium hydrosulfide to obtain denitration powder, and mixing portland cement, glass fiber, cerium dioxide and the waste denitration powder to prepare ceramic powder. The above patent not only uses various acids, alkalis and organic liquids for cleaning to cause secondary environmental pollution, but also does not fundamentally and effectively solve the harmlessness of the waste vanadium-titanium denitration catalyst, and has low market value. Patent CN201510852564.2 adopts raw materials such as silicon source powder, aluminum source powder, a burning promoter, a vanadium solid solvent and the like to be mixed with a waste denitration catalyst to prepare titanium-based ceramic. Although the catalyst can thoroughly solve the problem of harmlessness of the catalyst, the catalyst can only be used in the fields with low added value, such as textile porcelain, building and sanitary porcelain and the like.
Meanwhile, with the increasing global shortage of energy, the development and utilization of clean energy is in need. Hydrogen is a clean, efficient, renewable energy source that is receiving wide attention from global researchers. The commercial hydrogen production process mainly comprises three main types of hydrogen production by water electrolysis, hydrogen production by coal gasification and hydrogen production by catalytic reforming, wherein the hydrogen production by catalytic reforming is one of the hydrogen production processes with the most development potential. At present, hydrogen sources of a catalytic reforming hydrogen production process mainly comprise methane, ethanol, methanol and the like, the hydrogen sources have certain energy utilization, and the energy conversion way of the hydrogen sources does not have added value gain. Therefore, the development of the low-quality organic catalytic reforming hydrogen production technology has changesThe waste is valuable, has high added value and the like. The catalyst is the core of the catalytic reforming hydrogen production process. The patent CN20061013084.7 discloses a catalyst with a transition metal mixed oxide as an active component and alumina and magnesia as composite carriers, which has a high ethanol conversion rate and a hydrogen selectivity of 60%. Patent CN96100965.9A discloses a platinum palladium catalyst for converting gasoline into hydrogen-rich gas, which contains 17% hydrogen and 62% methane as active components, but has high cost and low hydrogen selectivity. Patent CN01138906.0A discloses RuO2The catalyst for hydrogen production by gasoline oxidation reforming, which is used as a catalytic active component and takes rare earth element oxide as a cocatalyst, has hydrogen selectivity of 1.5-1.7 mol (H) at 820 DEG C2+ CO)/mol C, the reaction temperature is relatively high, and the energy consumption is relatively high. Therefore, the design of the catalyst mainly aims at improving the selectivity of the catalyst, reducing the active loading of the catalyst and reducing the temperature of catalytic reaction.
In view of the problems that a large amount of waste vanadium-titanium denitration catalysts are lack of advanced safe disposal and resource utilization technology and the environmental pollution problem of organic pollutants, the invention innovatively provides a high-performance porous ceramic membrane reforming hydrogen production catalyst prepared by using the waste vanadium-titanium denitration catalysts, fundamentally solves the problem of large amount of waste vanadium-titanium denitration catalysts, and realizes high value-added resource utilization. The main basis is as follows: the titanium dioxide carrier in the denitration catalyst accounts for more than 90% of the catalyst powder, a proper amount of silicon source powder and aluminum source powder are added to be calcined to prepare the porous ceramic carrier, and after the active component nickel oxide is loaded, the high-performance porous ceramic membrane reforming hydrogen production catalyst can be prepared, and the reforming hydrogen production reaction of formaldehyde can be effectively catalyzed. The successful application of the invention can not only thoroughly solve the treatment problem of the waste vanadium-titanium denitration catalyst, but also greatly solve the problems of formaldehyde pollution and energy shortage when being used as a reforming hydrogen production catalyst, thereby bringing great economic, environmental and social benefits.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a porous ceramic membrane reforming hydrogen production catalyst using a waste vanadium-titanium catalyst as a raw material.
The purpose of the invention can be realized by the following technical scheme:
the technical scheme of the invention is as follows: according to the preparation method, aluminum source powder and silicon source powder are added into a vanadium-titanium denitration catalyst, so that a porous ceramic membrane carrier is prepared; on the other hand, titanium oxide, vanadium oxide and tungsten oxide in the vanadium-titanium denitration catalyst can be used as ceramic membrane carrier components, and can have strong interaction with active component nickel oxide, so that the catalytic activity of the active component nickel oxide is improved. The high-performance environment-friendly porous ceramic membrane reforming hydrogen production catalyst is developed by taking a waste vanadium-titanium denitration catalyst as a main raw material, adding a small amount of silicon source powder and aluminum source powder and loading active component nickel oxide, and aims to thoroughly and effectively solve the problems of treatment and high-added-value resource utilization of the waste vanadium-titanium denitration catalyst and the problems of formaldehyde pollution and development and utilization of clean energy.
The specific technical scheme of the invention is as follows: a reforming hydrogen production catalyst using a waste vanadium-titanium denitration catalyst as a raw material is characterized in that a porous ceramic membrane prepared from the waste vanadium-titanium denitration catalyst, silicon source powder, aluminum source powder and a forming agent solution is used as a carrier, and nickel oxide is used as a catalytic active component. Wherein: the waste vanadium-titanium denitration catalyst comprises, by weight, 80-90 parts of a waste vanadium-titanium denitration catalyst, 1-5 parts of a silicon source powder, 1-5 parts of an aluminum source powder, 8-10 parts of a forming agent solution and 1-10 parts of a catalytic active component nickel oxide.
The waste vanadium-titanium denitration catalyst is suitable for waste vanadium-titanium denitration catalysts of all manufacturers.
The invention also provides a preparation method of the porous ceramic membrane catalyst, which comprises the following specific steps:
(1) preparation of porous ceramic membrane carrier
Crushing and sieving a waste vanadium-titanium denitration catalyst, silicon source powder and aluminum source powder, uniformly mixing, adding a forming agent solution for granulation, adding granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and placing the ceramic blank in a kiln for primary calcination to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor solution
Adding nickel salt into deionized water, and stirring for reaction until the solution is clear and transparent to obtain a solution; wherein: the mass ratio of the nickel salt to the deionized water is 1: 1-6;
(3) catalyst preparation
And (3) soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor solution prepared in the step (2) for 1h, taking out the soaked porous ceramic membrane carrier, drying, and calcining for the second time to prepare the porous ceramic membrane reforming hydrogen production catalyst, wherein the loading capacity is 1-10%.
The invention also provides the porous ceramic membrane catalyst, and the preparation method of the catalyst comprises the following specific steps:
(1) preparation of porous ceramic membrane carrier
Crushing and sieving a waste vanadium-titanium denitration catalyst, silicon source powder and aluminum source powder, uniformly mixing, adding a forming agent solution for granulation, adding granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and placing the ceramic blank in a kiln for primary calcination to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor solution
Adding nickel salt into deionized water, and stirring for reaction until the solution is clear and transparent to obtain a solution; wherein: the mass ratio of the nickel salt to the deionized water is 1: 1-6;
(3) catalyst preparation
And (3) soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor solution prepared in the step (2) for 1h, taking out the soaked porous ceramic membrane carrier, drying, and calcining for the second time to prepare the porous ceramic membrane reforming hydrogen production catalyst, wherein the loading capacity is 1-10%.
Preferably: the silicon source powder is diatomite or silicon dioxide; the aluminum source powder is aluminum hydroxide or pseudo-boehmite; the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 1-15%; the active component precursor is soluble nickel salt.
Further preferably: the silicon source powder in the step (1) is diatomite with the granularity of less than 100 meshes, and the aluminum source powder is aluminum hydroxide with the granularity of less than 100 meshes; the forming agent solution in the step (1) is polyvinyl alcohol with the mass fraction of 7%.
Preferably: the pressurizing pressure in the step (1) is 10-15 MPa, and the pressure maintaining time is 1-3 min.
Further preferably: the precursor of the active component nickel oxide is nickel chloride or nickel nitrate.
Preferably, the following components: the primary calcination temperature is 1100-1300 ℃, the heat preservation time is 1.5-3 h, the secondary calcination temperature is 600-750 ℃, and the heat preservation time is 1.5-3 h.
The catalytic reaction conditions and results of the invention: and (3) loading a small sample (phi is 22mm, h is 10mm) of the porous ceramic membrane reforming hydrogen production catalyst cylinder into a catalyst performance evaluation reaction device, and introducing reaction gas for activity evaluation. The concentration of each gas is: n is a radical of hydrogen2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). Catalyst H at 400 deg.C2The selectivity can reach 74.5 percent, the CO selectivity is 52.3 percent, and the H content is higher than 450 DEG C2The selectivity was 100% and the CO selectivity was 86.25%.
Has the advantages that:
the leaching rate of the V element in the titanium-based ceramic product prepared by the porous ceramic membrane reforming hydrogen production catalyst prepared by the invention is far lower than the limit value requirement (less than or equal to 1ppm) of the V element content in GB26452-2011 discharge Standard of vanadium Industrial pollutants, and the secondary pollution and high value-added resource utilization of the waste toxic vanadium-titanium denitration catalyst are thoroughly and effectively solved. Meanwhile, the formaldehyde is used as a hydrogen source, and the hydrogen is prepared by reforming hydrogen production reaction under the action of a catalyst, so that the problems of energy shortage and formaldehyde environmental pollution can be solved. The catalyst for reforming the porous ceramic membrane to prepare the hydrogen has the advantages of environment-friendly components, simple preparation process, lower cost, high cost performance, stronger application and popularization value and wide market prospect.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
(1) Raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a standard sieve of 100 meshes for later use; ball-milling diatomite powder and aluminum hydroxide powder through a 100-mesh standard sieve respectively and homogenizing for later use;
(2) proportioning and granulating
Weighing 80g of waste denitration catalyst powder, 5g of diatomite powder and 5g of aluminum hydroxide powder, uniformly stirring, weighing 10g of polyvinyl alcohol forming agent solution, mixing with the powder, grinding and granulating;
(3) shaping and first calcination
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 10MPa, maintaining the pressure for 1min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a kiln for heat preservation for 1.5h at 1100 ℃ to calcine to obtain porous ceramic membrane carriers;
(4) preparation of active component precursor solution
3.18g of nickel chloride hexahydrate is weighed, and 15.90g of deionized water is added and stirred until the solution is clear and transparent, so that a solution is obtained.
(5) Catalyst preparation
And (3) soaking the prepared porous ceramic membrane carrier in the nickel chloride solution prepared in the step (4) for 1h, taking out the soaked porous ceramic membrane carrier, drying the porous ceramic membrane carrier in an oven at the temperature of 80 ℃, and then placing the porous ceramic membrane carrier in a kiln furnace for heat preservation at the temperature of 600 ℃ for 1.5h to prepare the 1% NiO-loaded porous ceramic membrane reforming hydrogen production catalyst.
(6) Catalyst Activity test
A small sample (phi is 22mm, h is 10mm) of 1 porous ceramic membrane catalyst cylinder is loaded into a catalyst performance evaluation reaction device, and reaction gas is introduced for activity evaluation. The concentration of each gas is: n is a radical of2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). Catalyst H at 400 deg.C2The selectivity can reach 74.5 percent, the CO selectivity is 52.3 percent, and the H content is higher than 450 DEG C2The selectivity was 100% and the CO selectivity was 86.2%.
(7) Catalyst element V leaching test
The leaching rate of V element of a sample detected by ICP (inductively coupled plasma emission spectrometry) is far lower than GB26452-2011 discharge Standard of pollutants for vanadium industry (less than or equal to 1 ppm).
(8) The application range is as follows: the reforming hydrogen production catalyst prepared by the method is suitable for catalyzing formaldehyde to reform and produce hydrogen.
Example 2:
(1) raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a 100-mesh standard sieve for later use; respectively ball-milling the silicon dioxide powder and the pseudo-boehmite powder through a standard sieve of 100 meshes and homogenizing for later use;
(2) proportioning and granulating
Weighing 90g of waste denitration catalyst powder, 1g of silicon dioxide powder and 1g of pseudo-boehmite powder, uniformly stirring, weighing 8g of polyvinyl alcohol forming agent solution, mixing with the powder, grinding and granulating;
(3) shaping and first calcination
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 15MPa, maintaining the pressure for 3min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a kiln for heat preservation for 3h at 1300 ℃ to obtain porous ceramic membrane carriers;
(4) preparation of active component precursor solution
31.81g of nickel chloride hexahydrate is weighed, 31.81g of deionized water is added, and stirring is carried out until the solution is clear and transparent, so as to obtain a solution.
(5) Catalyst preparation
And (3) soaking the prepared porous ceramic membrane carrier in the nickel chloride solution prepared in the step (4) for 1h, taking out the soaked porous ceramic membrane carrier, drying the porous ceramic membrane carrier in an oven at 80 ℃, and then placing the porous ceramic membrane carrier in a kiln furnace for heat preservation at 750 ℃ for 3h to prepare the 10% NiO-loaded porous ceramic membrane reforming hydrogen production catalyst.
(6) Catalyst Activity test
Taking 1 porous ceramic membrane catalyst cylinder sample (phi is 22mm, h is 10mm) and loading the sample into a catalyst performance evaluation reaction deviceAnd (4) neutralizing, and introducing reaction gas for activity evaluation. The concentration of each gas is: n is a radical of2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). Catalyst H at 400 deg.C2The selectivity can reach 80.1 percent, the CO selectivity is 58.3 percent, and the H content is at 450 DEG C2The selectivity was 100% and the CO selectivity was 96.4%.
(7) Catalyst V element leach test
The leaching rate of V element of a sample detected by ICP (inductively coupled plasma emission spectrometry) is far lower than GB26452-2011 discharge Standard of pollutants for vanadium industry (less than or equal to 1 ppm).
(8) The application range is as follows: the reforming hydrogen production catalyst prepared by the method is suitable for catalyzing formaldehyde to reform and produce hydrogen.
Example 3:
(1) raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a standard sieve of 100 meshes for later use; ball-milling diatomite powder and pseudo-boehmite powder respectively through a standard sieve of 100 meshes and homogenizing for later use;
(2) proportioning and granulating
Weighing 80g of waste denitration catalyst powder, 5g of diatomite powder and 5g of pseudo-boehmite powder, uniformly stirring, weighing 10g of polyvinyl alcohol forming agent solution, mixing with the powder, grinding and granulating;
(3) shaping and first calcination
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 10MPa, maintaining the pressure for 1min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a kiln for heat preservation for 1.5h at 1100 ℃ to calcine to obtain porous ceramic membrane carriers;
(4) preparation of active component precursor solution
5.89g of nickel sulfate hexahydrate is weighed, 19.45g of deionized water is added, and stirring is carried out until the solution is clear and transparent, so as to obtain a solution.
(5) Catalyst preparation
And (3) soaking the prepared porous ceramic membrane carrier in the nickel sulfate solution prepared in the step (4) for 1h, taking out the soaked porous ceramic membrane carrier, drying the porous ceramic membrane carrier in an oven at the temperature of 80 ℃, and then placing the porous ceramic membrane carrier in a kiln furnace for heat preservation at the temperature of 600 ℃ for 1.5h to prepare the 1.7% NiO-supported porous ceramic membrane reforming hydrogen production catalyst.
(6) Catalyst Activity test
A small sample (phi is 22mm, h is 10mm) of 1 porous ceramic membrane catalyst cylinder is loaded into a catalyst performance evaluation reaction device, and reaction gas is introduced for activity evaluation. The concentration of each gas is: n is a radical of2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). Catalyst H at 400 deg.C2The selectivity can reach 75.6 percent, the CO selectivity is 52.8 percent, and the H content is higher than 450 DEG C2The selectivity was 100% and the CO selectivity was 86.8%.
(7) Catalyst element V leaching test
The leaching rate of V element of a sample detected by ICP (inductively coupled plasma emission spectrometry) is far lower than GB26452-2011 discharge Standard of pollutants for vanadium industry (less than or equal to 1 ppm).
(8) The application range is as follows: the reforming hydrogen production catalyst prepared by the method is suitable for catalyzing formaldehyde to reform and produce hydrogen.
Example 4
(1) Raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a standard sieve of 100 meshes for later use; respectively ball-milling silicon dioxide powder and aluminum hydroxide powder through a standard sieve of 100 meshes and homogenizing for later use;
(2) proportioning and granulating
Weighing 90g of waste denitration catalyst powder, 1g of silicon dioxide powder and 1g of aluminum hydroxide powder, uniformly stirring, weighing 8g of polyvinyl alcohol forming agent solution, mixing with the powder, grinding and granulating;
(3) shaping and first calcination
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 15MPa, maintaining the pressure for 3min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, and placing the porous ceramic membrane blanks in a kiln for heat preservation for 3h at 1300 ℃ to obtain porous ceramic membrane carriers;
(4) preparation of active component precursor solution
7.85g of nickel acetate is weighed, 47.10g of deionized water is added, and stirring is carried out until the solution is clear and transparent, so as to obtain the solution.
(5) Catalyst preparation
And (3) soaking the prepared porous ceramic membrane carrier in the nickel acetate solution prepared in the step (4) for 1h, taking out the soaked porous ceramic membrane carrier, drying the porous ceramic membrane carrier in an oven at 80 ℃, and then placing the porous ceramic membrane carrier in a kiln furnace for heat preservation at 750 ℃ for 3h to prepare the 3.3% NiO-loaded porous ceramic membrane reforming hydrogen production catalyst.
(6) Catalyst Activity test
A small sample (phi is 22mm, h is 10mm) of 1 porous ceramic membrane catalyst cylinder is loaded into a catalyst performance evaluation reaction device, and reaction gas is introduced for activity evaluation. The concentration of each gas is: n is a radical of2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). Catalyst H at 400 deg.C2The selectivity can reach 84.1 percent, the CO selectivity is 63.5 percent, and the H content is at 450 DEG C2The selectivity was 100% and the CO selectivity was 95.7%.
(7) Catalyst element V leaching test
The leaching rate of V element of a sample detected by ICP (inductively coupled plasma emission spectrometry) is far lower than GB26452-2011 discharge Standard of pollutants for vanadium industry (less than or equal to 1 ppm).
(8) The application range is as follows: the reforming hydrogen production catalyst prepared by the method is suitable for catalyzing formaldehyde to reform and produce hydrogen.
Comparative example 1
(1) Raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a standard sieve of 100 meshes for later use; respectively ball-milling silicon source powder and aluminum source powder, passing through a standard sieve of 100 meshes, and homogenizing for later use;
(2) proportioning and granulating
Weighing 90g of waste denitration catalyst powder, 1g of diatomite powder and 1g of aluminum hydroxide powder, uniformly stirring, weighing 8g of polyvinyl alcohol forming agent solution, mixing with the powder, grinding and granulating;
(3) shaping and calcining
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 15MPa, maintaining the pressure for 3min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, placing the porous ceramic membrane blanks in a kiln, and keeping the temperature for 3h and calcining at 1300 ℃ to obtain the porous ceramic membrane catalyst;
(4) catalyst Activity test
A small sample (phi is 22mm, h is 10mm) of 1 porous ceramic membrane catalyst cylinder is loaded into a catalyst performance evaluation reaction device, and reaction gas is introduced for activity evaluation. The concentration of each gas is: n is a radical of2(90mL/min)；H2O (0.1 mL/min); HCHO (0.067 mL/min). H at 450 ℃ of2The selectivity was 5.6% and the CO selectivity was 0.7%.
(5) And (3) comparison effect: compared with examples 1-4, the catalyst for hydrogen production by porous ceramic membrane reforming has no nickel oxide which is a catalytic active component, has extremely low selectivity and basically has no catalytic reforming hydrogen production activity.
Comparative example 2
(1) Raw material crushing
Crushing the waste vanadium-titanium denitration catalyst by a crusher and a ball mill in sequence, and then homogenizing the waste vanadium-titanium denitration catalyst by a standard sieve of 100 meshes for later use;
(2) compounding and granulating
Weighing 92g of waste denitration catalyst powder, 8g of polyvinyl alcohol forming agent solution and mixing the powder for grinding and granulation;
(3) shaping and calcining
Weighing 10g of granulated pug, slowly adding the pug into a mold, pressurizing to 15MPa, maintaining the pressure for 3min, taking out a sample, repeating the blank molding for 10 times to obtain 10 porous ceramic membrane blanks, placing the porous ceramic membrane blanks in a kiln, and keeping the temperature for 3h and calcining at 1300 ℃ to obtain the porous ceramic membrane catalyst;
(4) the contrast effect is as follows: when the porous ceramic membrane reforming hydrogen production catalyst is prepared, and silicon source powder and aluminum source powder are not added, the catalyst is poor in wear resistance after being roasted, and cannot be prepared into a ceramic wafer.
Claims (10)
1. A reforming hydrogen production catalyst taking waste vanadium-titanium denitration catalyst as raw material is characterized in that: the catalyst takes a porous ceramic membrane prepared from a waste vanadium-titanium denitration catalyst, silicon source powder, aluminum source powder and a forming agent solution as a carrier, and takes nickel oxide as a catalytic active component; wherein: the weight parts of the waste vanadium-titanium denitration catalyst are 80-90 parts, the weight parts of the silicon source powder are 1-5 parts, the weight parts of the aluminum source powder are 1-5 parts, the weight parts of the forming agent solution are 8-10 parts, and the catalytic active component nickel oxide accounts for 1-10% of the mass percentage of the carrier.
2. A reforming hydrogen production catalyst according to claim 1, characterized in that: the silicon source powder is diatomite or silicon dioxide; the aluminum source powder is aluminum hydroxide or pseudo-boehmite; the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 1-15%; the precursor of the active component is soluble nickel salt.
3. A reforming hydrogen production catalyst according to claim 1, characterized in that: the catalyst is prepared by the following method:
(1) preparation of porous ceramic membrane carrier
Crushing and sieving a waste vanadium-titanium denitration catalyst, silicon source powder and aluminum source powder, uniformly mixing, adding a forming agent solution for granulation, adding granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and placing the ceramic blank in a kiln for primary calcination to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor solution
Adding nickel salt into deionized water, and stirring for reaction until the solution is clear and transparent to obtain a solution; wherein: the mass ratio of the nickel salt to the deionized water is 1: 1-6;
(3) catalyst preparation
And (3) soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor solution prepared in the step (2) for 1h, taking out the soaked porous ceramic membrane carrier, drying, and calcining for the second time to prepare the porous ceramic membrane reforming hydrogen production catalyst, wherein the loading capacity is 1-10%.
4. A reforming hydrogen production catalyst according to claim 3, characterized in that: the primary calcination temperature is 1100-1300 ℃, the heat preservation time is 1.5-3 h, the secondary calcination temperature is 600-750 ℃, and the heat preservation time is 1.5-3 h.
5. A reforming hydrogen production catalyst according to claim 3, characterized in that: the silicon source powder in the step (1) is diatomite with the granularity of less than 100 meshes, and the aluminum source powder is aluminum hydroxide with the granularity of less than 100 meshes.
6. A reforming hydrogen production catalyst according to claim 3, characterized in that: the pressurizing pressure in the step (1) is 10-15 MPa, and the pressure maintaining time is 1-3 min.
7. The preparation method of the reforming hydrogen production catalyst taking the waste vanadium-titanium denitration catalyst as the raw material as claimed in claim 1, is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of porous ceramic membrane carrier
Crushing and sieving a waste vanadium-titanium denitration catalyst, silicon source powder and aluminum source powder, uniformly mixing, adding a forming agent solution for granulation, adding granulated pug into a mold, pressurizing, maintaining pressure, preparing a ceramic blank, and placing the ceramic blank in a kiln for primary calcination to obtain a porous ceramic membrane carrier;
(2) preparation of active component precursor solution
Adding nickel salt into deionized water, and stirring for reaction until the solution is clear and transparent to obtain a solution; wherein: the mass ratio of the nickel salt to the deionized water is 1: 1-6;
(3) catalyst preparation
And (3) soaking the porous ceramic membrane carrier prepared in the step (1) in the active component precursor solution prepared in the step (2) for 1h, taking out the soaked porous ceramic membrane carrier, drying, and calcining for the second time to prepare the porous ceramic membrane reforming hydrogen production catalyst, wherein the loading capacity is 1-10%.
8. The method of claim 7, wherein: the primary calcination temperature is 1100-1300 ℃, the heat preservation time is 1.5-3 h, the secondary calcination temperature is 600-750 ℃, and the heat preservation time is 1.5-3 h.
9. The method of claim 7, wherein: the silicon source powder in the step (1) is diatomite with the granularity of less than 100 meshes, and the aluminum source powder is aluminum hydroxide with the granularity of less than 100 meshes.
10. The method for producing according to claim 7, characterized in that: the pressurizing pressure in the step (1) is 10-15 MPa, and the pressure maintaining time is 1-3 min.
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| CN109603849A (en) * | 2018-12-26 | 2019-04-12 | 南京工业大学 | Porous ceramic membrane catalyst taking waste rare earth-based denitration catalyst as raw material and preparation method and application thereof |
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| CN110302795A (en) | 2019-10-08 |
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