CN117531535A - For N 2 Cobalt-based composite oxide catalyst for O catalytic decomposition and preparation method and application thereof - Google Patents
For N 2 Cobalt-based composite oxide catalyst for O catalytic decomposition and preparation method and application thereof Download PDFInfo
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- CN117531535A CN117531535A CN202311517817.1A CN202311517817A CN117531535A CN 117531535 A CN117531535 A CN 117531535A CN 202311517817 A CN202311517817 A CN 202311517817A CN 117531535 A CN117531535 A CN 117531535A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 33
- 239000010941 cobalt Substances 0.000 title claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003421 catalytic decomposition reaction Methods 0.000 title claims description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000002808 molecular sieve Substances 0.000 claims description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 239000010457 zeolite Substances 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
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- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 29
- 238000000354 decomposition reaction Methods 0.000 abstract description 20
- 238000007598 dipping method Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 229910003289 NiMn Inorganic materials 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical class C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005173 quadrupole mass spectroscopy Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
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- 210000000987 immune system Anatomy 0.000 description 1
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- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 perovskite Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for N 2 The catalyst is composed of a carrier and an active component, wherein the active component takes cobalt oxide as a main active component and is modified by a second metal, the second metal is transition metal, and the mole ratio of Co to the second metal is (1-10): (1-3), the mass content of the active component is 2.5-50%. The supported cobalt-based composite oxide catalyst is prepared by dipping, drying and roasting an active component-organic complexing agent. Compared with the prior art, the catalyst of the invention has N 2 The O decomposition temperature is low, the activity is good, and the stability is realized at high temperature (900 ℃) for a long timeGood quality, simple preparation process, energy conservation, good consistency and the like, and has wide industrial application prospect.
Description
Technical Field
The invention relates to the field of chemical technology and environmental protection, in particular to a method for catalytically decomposing N 2 O cobalt-based composite oxide catalyst and preparation method and application thereof.
Background
N 2 O, commonly referred to as nitrous oxide or laughing gas, is one of 6 greenhouse gases specified by the kyoto protocol, the Global Warming Potential (GWP) of which is CO 2 The contribution rate to global warming is 6% (third greenhouse gas), can be stably stored in the atmosphere for more than 150 years, can cause ozone layer destruction, cause ozone cavities and cause damage to human skin, eyes and immune system.
N in atmosphere 2 O is largely discharged N in the processes of combustion (boiler flue gas), urban automobile exhaust, biological denitrification and denitrification of sewage, and chemical industry production such as nitric acid or adipic acid production, etc., except natural sources mainly from lightning and microbial life activities (about 11.0 Tg/year) 2 O, especially ammonia as a carbon-free fuel and hydrogen carrier has been widely used in recent years for ammonia combustion power generation and ammonia internal combustion engines, and N is expected 2 The amount of human activity production of O will increase drastically year by year, and thus, reduction of emissions and post-treatment purification thereof are urgent.
For N 2 O is purified by post-treatment mainly by N in the presence of a catalyst 2 O is directly decomposed into N 2 And O 2 And wherein a highly efficient, highly stable catalyst is critical. The main catalysts at present comprise supported simple oxide catalysts such as cobalt oxide, manganese oxide, copper oxide and the like, and composite oxide catalysts such as perovskite, spinel, hexaaluminate and the likeThe catalyst and ion exchange type molecular sieve catalysts such as Fe, cu and Co, especially the transition metal ion exchange type molecular sieve catalysts have high activity and are widely reported in literature and patents. Patent CN200910136205.1 discloses a molecular sieve catalyst for iron ion exchange with noble metal modification to decompose N at low temperature 2 O. Patent CN128132A discloses an iron ion exchanged magnesium base molecular sieve catalyst which can be used for low concentration N in waste gas of nitric acid production 2 And (3) decomposing O. Patent 202310326207.7 reports a method for N 2 O-decomposed metal-supported molecular sieve catalysts exhibiting excellent N 2 O decomposition activity and hydrothermal stability, is suitable for N in tail gas of mobile source and fixed source 2 And (3) decomposing and removing O. Patent 201310001090.1 discloses an N 2 Preparation method of O-decomposed bimetallic supported molecular sieve catalyst, and prepared catalyst is used for preparing high-concentration N 2 In the O decomposition reaction, the stability and the catalytic activity are good at a high temperature (about 800 ℃) for a long time, and the service life of the catalyst can reach 3000 hours at a high airspeed. Patent 201210260278.3 reports that Cu ion exchanged ZSM-11 catalyst is in N 2 The CuZSM-11 has better activity and stability when applied to O decomposition, N at 400 DEG C 2 The O decomposition rate reaches 100 percent. Patent CN101905162A discloses a method for producing a smoke or an industrial waste gas N 2 The molecular sieve loaded cobalt composite oxide catalyst with O being directly decomposed adopts the steps of excessive dipping, evaporating to dryness and the like to load cobalt, rare earth, alkaline earth and other modified components on the molecular sieve, N 2 The complete decomposition temperature of O is not higher than 650 ℃.
Due to N 2 The catalyst disclosed in the prior art can not cope with complex environments, and the development of a novel catalyst which shows high activity and high stability under complex working conditions is still a great challenge. In addition, the catalyst has low cost, and the preparation method is simple and environment-friendly, but the preparation method of the catalyst disclosed by the prior art is generally complex and has complex steps.
Disclosure of Invention
The invention is thatThe object of the present invention is to overcome the above-mentioned drawbacks of the prior art by providing a high thermal stability N 2 Cobalt-based composite oxide catalyst for O catalytic decomposition and preparation method and application thereof. The active component of the invention has high dispersion load and small amount, N 2 The decomposition activity of O is high, especially under the condition of high space velocity, and the catalyst still maintains higher catalytic activity and stability under the condition of oxygen, water vapor and the like, in addition, the catalyst has excellent high temperature resistance, even after aging for a long time at 900 ℃, the activity is still higher, and the catalyst can be applied to N in the nitric acid production process 2 Pyrolysis in O furnace, nitric acid or adipic acid production, ammonia combustion, waste gas in sewage biological denitrification and denitrification processes, traditional movable source tail gas and N in boiler flue gas 2 O low-temperature decomposition and other scenes, and has wide application prospect. The preparation method and the process of the catalyst are simple, the catalyst is suitable for industrial production, the catalyst has low cost, long service life and low use cost.
The aim of the invention can be achieved by the following technical scheme:
for N 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized by comprising a carrier and an active component, wherein the active component takes cobalt oxide as a main active component and is modified by a second metal, the second metal is transition metal, and the mole ratio of Co to the second metal is (1-10): (1-3), preferably (1-2): (1-3), the mass content of the active ingredient is 2.5-50%, preferably 5-15%.
Further, the second metal is Fe, ni, mn, cu or Zn;
the carrier is alumina, silica, titania, cerium-zirconium solid solution or zeolite molecular sieve with high surface area and high heat/water heat stability.
Further, the second metal is Ni and/or Mn, so that the activity and stability are further improved;
the molecular sieve is zeolite molecular sieve. Further, the zeolite molecular sieve is ZSM-5, beta, MOR, A, X, Y or SSZ-13.
Further, in order to improve the performance of the commercial zeolite molecular sieve, it may be subjected to a dealumination treatment to generate a rich active hydroxyl group to disperse and stabilize the metal oxide and to improve the catalyst activity, wherein the carrier is a dealuminated carrier, and the dealumination treatment comprises low-temperature dealumination in an acid solution and high-temperature steam dealumination. Dealumination by low-temperature acid solution is to reflux or hydrothermally treat in 0.5-15M acid solution such as nitric acid, hydrochloric acid, sulfuric acid, etc. at 25-150deg.C for 1-24h, dealumination by high-temperature vapor is to introduce 0.5-100% water vapor into molecular sieve carrier and treat at high temperature (generally 200-750deg.C) for 1-24h.
The invention also provides a method for N 2 The preparation method of the cobalt-based composite oxide catalyst for O catalytic decomposition selects commercial conventional zeolite molecular sieve or zeolite molecular sieve after dealumination, and metal precursors such as cobalt and the like are loaded on a zeolite molecular sieve carrier in a high-dispersion way through an organic complexing agent impregnation method to prepare the loaded cobalt-based composite oxide catalyst. The method specifically comprises the following steps:
s1, dissolving a metal precursor in deionized water;
s2, adding an organic complexing agent into the solution containing the metal precursor;
s3, slowly dripping or spraying the solution obtained in the step S2 onto a carrier, rapidly stirring, standing at room temperature for 0-24 hours, drying at 50-120 ℃, and roasting at 300-650 ℃ in air atmosphere or other atmospheres for 1-24 hours to obtain the catalyst.
Further, the metal precursor in step S1 is a soluble salt of Co and a second metal, including nitrate, sulfate, chloride, carbonate, acetate, or the like.
Further, the organic complexing agent in step S2 includes triethanolamine, nitrilotriacetic acid and salts, ethylenediamine tetraacetic acid, ascorbic acid, citric acid, tartaric acid, or gluconic acid and salts; the metal ions are stabilized through the complexation between the transition metal and the complexing agent, and the competitive adsorption ensures that the active components are uniformly and highly dispersed on the zeolite molecular sieve carrier.
The molar ratio of the organic complexing agent to the total metal is 0.01-1.5:1.
for N 2 Use of a cobalt-based composite oxide catalyst for O catalytic decomposition, said catalyst being used for N 2 In the O catalytic decomposition reaction, the reaction conditions are as follows: the reaction pressure is normal pressure, N in the reaction gas 2 The volume concentration of O is 0.01-50%, O 2 The volume concentration of (2) is 0-10%, H 2 The volume concentration of O is 0-15%, and the airspeed is 5000-200000h -1 The operating temperature is 200-1000 ℃. On-line analysis and monitoring of N in tail gas by adopting thermal conductance gas chromatography and quadrupole mass spectrometry 2 O concentration and N 2 And O 2 Is generated.
Can be applied to N in the nitric acid production process 2 Pyrolysis (two-stage catalyst) in O furnace, production of nitric acid/adipic acid and the like, ammonia combustion (ammonia power plant and ammonia engine), waste gas in sewage biological denitrification and denitrification processes, traditional movable source tail gas and N in boiler flue gas 2 O is decomposed and eliminated at low temperature.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst of the invention adopts zeolite molecular sieve with high surface area and high thermal/hydrothermal stability and the like as a carrier, takes high-activity cobalt as a main active component and is assisted with transition metal modification to adjust the structure and valence of the main active component, adopts an isovolumetric impregnation method with stable organic complexing agent to load the active component on the carrier, and has high dispersion load and small amount of active component and N 2 The decomposition activity of O is high, especially under the condition of high space velocity, and the catalyst still maintains high catalytic activity and stability under the condition of oxygen, water vapor and the like.
In addition, dealumination treatment of carriers such as zeolite molecular sieve generates abundant active hydroxyl groups to further disperse and stabilize metal oxide, and improves the activity and stability of the catalyst, so that the prepared catalyst has N 2 The O has the advantages of low decomposition temperature, good activity, good stability at high temperature (900 ℃) for a long time, simple preparation process, energy saving, good consistency and the like. The preparation process is simple, and the uniform and high dispersion of the active components can be ensured.
Is suitable for N in the nitric acid production process 2 Pyrolysis (two-stage catalyst) in O furnace, nitric acid/adipic acid and the likeProduction, ammonia combustion (ammonia power plant, ammonia engine), waste gas from biological denitrification and denitrification process of sewage, traditional mobile source tail gas, and N in boiler flue gas 2 O is decomposed and eliminated at low temperature, and has wide industrial application prospect.
Drawings
FIG. 1 is N before and after high temperature aging of the catalyst prepared in example 8 2 O decomposition activity diagram.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are not intended to limit the scope of the invention.
The experiments of examples 1 to 8 were performed using the following experimental apparatus, analytical methods and devices.
N 2 The test of the catalytic decomposition activity of O adopts a miniature reaction device to react N in the mixed gas 2 The O content was 1500ppm, the oxygen content was 4%, and nitrogen or argon (when mass spectrometry was used) was the balance gas. The gas flow rate is controlled by a mass flowmeter, the total flow rate is 100ml/min, the micro quartz reaction tube is directly 3mm, and the airspeed is 30000 ml/g.h. The catalyst loading was 100mg,40-60 mesh. The reaction was carried out at normal pressure with a programmed heating rate of 5 ℃/min and a temperature rise from 150 ℃ to 850 ℃. Reactants and products are analyzed or monitored on line using thermal conductivity gas chromatography or quadrupole mass spectrometry.
Example 1
0.592g of Co (NO) 3 ) 2 ·6H 2 O and 1.172g Mn (NO) 3 ) 2 (50% solution) was dissolved in 0.5g deionized water, after complete dissolution, then slowly dropped onto 2g ZSM-5 (silica-alumina ratio: 250) and stirred uniformly, left at room temperature for 4 hours after impregnation, dried at 60 ℃, and then calcined in an air atmosphere at 550 ℃ for 4 hours to prepare a zeolite molecular sieve-supported cobalt-based composite oxide catalyst (labeled Mn 9 Co 6 /ZSM-5-N). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 650 ℃, N 2 The conversion of O was 99%.
Example 2
0.592g of Co (NO) 3 ) 2 ·6H 2 O and 1.172g Mn (NO) 3 ) 2 Dissolving (50% solution) in 0.5g deionized water, adding 0.35g ascorbic acid organic complexing agent after complete dissolution, stirring for dissolving, slowly dripping onto 2g ZSM-5 (with silicon-aluminum ratio of 250) and stirring uniformly, standing at room temperature for 4h after soaking, drying at 110deg.C, and roasting at 550deg.C in air atmosphere for 4h to obtain zeolite molecular sieve-loaded cobalt-based composite oxide catalyst (marked as Mn) 9 Co 6 /ZSM-5). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 575 ℃, N 2 The conversion of O was 99%.
Mn obtained in this example 2 9 Co 6 ZSM-5 and Mn in example 1 9 Co 6 The difference of ZSM-5-N is only that an ascorbic acid complexing agent is added, so that the activity of the catalyst is improved.
Example 3
0.592g of Co (NO) 3 ) 2 ·6H 2 O and 1.172g Mn (NO) 3 ) 2 (50% solution) was dissolved in 2.5g of deionized water, after complete dissolution, 0.35g of an ascorbic acid organic complexing agent was added, stirred for dissolution, then slowly dropped onto 2g of alumina and stirred uniformly, left at room temperature for 4 hours after impregnation, dried at 110 ℃, and then calcined in an air atmosphere at 550 ℃ for 4 hours to prepare an alumina carrier-supported cobalt-based composite oxide catalyst (labeled as Mn 9 Co 6 /Al 2 O 3 ). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 600 ℃, N 2 The conversion of O was 99%.
Mn obtained in this example 3 9 Co 6 /Al 2 O 3 Mn as in example 2 9 Co 6 The ZSM-5 is different only in carrier, and the result shows that the carrier has obvious influence on the performance of the cobalt-based composite oxide catalyst and the zeolite is separatedThe subscreen has a higher N 2 O-decomposition activity.
Example 4
1.00g of Co (NO) was weighed out 3 ) 2 ·6H 2 O and 0.62g Mn (NO) 3 ) 2 Dissolving (50% solution) in 1.0g deionized water, adding 0.35g ascorbic acid organic complexing agent after complete dissolution, stirring for dissolving, slowly dripping onto 2g ZSM-5 (with silicon-aluminum ratio of 250) and stirring uniformly, standing at room temperature for 4h after soaking, drying at 110deg.C, and roasting at 550deg.C in air atmosphere for 4h to obtain zeolite molecular sieve-loaded cobalt-based composite oxide catalyst (marked as Mn) 1 Co 2 /ZSM-5). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 525 ℃, N 2 The conversion of O was 99%.
Mn obtained in this example 4 1 Co 2 ZSM-5 and Mn of example 2 9 Co 6 The ZSM-5 differs only in the ratio of Mn to Co, and the result shows that the Mn/Co ratio can optimize the catalyst performance, and the improvement of the cobalt content further increases N 2 O-decomposition activity.
Example 5
0.592g of Co (NO) 3 ) 2 ·6H 2 O and 0.89g Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 1.7g deionized water, adding 0.35g ascorbic acid organic complexing agent after complete dissolution, stirring for dissolution, then slowly dripping onto 2g ZSM-5 (silicon-aluminum ratio is 250) and stirring uniformly, standing for 4h at room temperature after impregnation, drying at 110 ℃, and roasting for 4h in air atmosphere at 550 ℃ to obtain the zeolite molecular sieve-loaded cobalt-based composite oxide catalyst (marked as Mn) 9 Ni 6 /ZSM-5). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 525 ℃, N 2 The conversion of O was 99%.
Mn obtained in this example 5 9 Ni 6 ZSM-5 and Mn of example 2 9 Co 6 The ZSM-5 differs only in that the second metal Mn is replaced by Ni, and the result shows that the modification effect of Ni is better than that of Mn, N 2 The O-decomposition activity is further enhanced.
Example 6
0.835g of Co (NO) was weighed out 3 ) 2 ·6H 2 O、0.139g Ni(NO 3 ) 2 ·6H 2 O and 0.343g Mn (NO) 3 ) 2 (50% solution) was dissolved in 1.4g of deionized water, after complete dissolution, 0.35g of an ascorbic acid organic complexing agent was added, stirred and dissolved, then slowly dropped onto 2g of ZSM-5 (silica-alumina ratio 250) and stirred uniformly, left at room temperature for 4 hours after impregnation, dried at 60℃and then calcined in an air atmosphere at 550℃for 4 hours to prepare a zeolite molecular sieve-supported cobalt-based composite oxide catalyst (labeled (NiMn 2 )Co 2 /ZSM-5). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 500 ℃, N 2 The conversion of O was 99%.
The catalyst obtained in this example 6 (NiMn 2 )Co 2 ZSM-5 and Mn of example 4 1 Co 2 ZSM-5 differs in that the third metal Ni is adopted for further modification, and the introduction of Ni improves N 2 The O decomposition activity, the result shows that multicomponent modification such as Ni and Mn bimetallic modification can optimize catalyst structure and performance to a greater extent.
Example 7
2.505g Co (NO) 3 ) 2 ·6H 2 O、0.417g Ni(NO 3 ) 2 ·6H 2 O and 1.029g Mn (NO) 3 ) 2 (50% solution) was dissolved in 2.376g of deionized water, after complete dissolution, 0.501g of an ascorbic acid organic complexing agent was added, stirred and dissolved, then slowly dropped onto 6g of ZSM-5 (silica alumina ratio 25) and stirred uniformly, left at room temperature for 4 hours after impregnation, dried at 60℃and then calcined in an air atmosphere at 550℃for 2 hours to prepare a zeolite molecular sieve-supported cobalt-based composite oxide catalyst (labeled (NiMn 2 )Co 2 /ZSM-5-25). Tabletting, sieving, collecting 100mg of granule with particle diameter of 40-60 meshes, and loading into continuous flow micro-deviceIn a reactor of the type N is carried out according to the reaction conditions mentioned above 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 475 ℃, N 2 The conversion of O was 99%.
The catalyst obtained in example 7 (NiMn 2 )Co 2 ZSM-5-25 was the same as in example 6 (NiMn 2 )Co 2 The difference of ZSM-5 is that the zeolite molecular sieves have different silicon to aluminum ratios, and the results prove that ZSM-5 with low silicon to aluminum ratio shows higher N due to more acid sites and transition metal anchor sites 2 O-decomposition activity.
Example 8
First 18.4g HNO were weighed out 3 (68%) was diluted in 200ml deionized water, 10g of ZSM-5 (silica alumina ratio 25) was dispersed therein, heated to 100℃and refluxed for 6 hours, then washed and suction filtered and dried at 110℃to obtain the dealuminated ZSM-5. Then 0.835g of Co (NO) 3 ) 2 ·6H 2 O、0.139g Ni(NO 3 ) 2 ·6H 2 O and 0.343gMn (NO 3 ) 2 (50% solution) was dissolved in 0.792g of deionized water, after complete dissolution, 0.167g of an ascorbic acid organic complexing agent was added, stirred and dissolved, then slowly dropped onto 2g of the above dealuminized ZSM-5 and stirred uniformly, left at room temperature for 4 hours after impregnation, dried at 60℃and then calcined in an air atmosphere at 550℃for 2 hours to prepare a zeolite molecular sieve-supported cobalt-based composite oxide catalyst (labeled (NiMn 2 )Co 2 /deAlZSM-5-25). Tabletting, sieving, collecting 100mg of 40-60 mesh granule, loading into continuous flow microreactor, and performing N according to the above reaction conditions 2 And (5) evaluating the catalytic decomposition performance of O. At a reaction temperature of 425 ℃, N 2 The conversion of O was 99%.
Obtained in this example 8 (NiMn 2 )Co 2 DeAlZSM-5-25 was carried out in accordance with the method of example 7 (NiMn 2 )Co 2 The difference of ZSM-5 is that the zeolite molecular sieve is subjected to dealumination treatment, and the result proves that ZSM-5 with low silicon-aluminum ratio shows higher N after dealumination treatment due to the fact that more silicon nest hydroxyl groups are generated and are beneficial to high dispersion load of transition metal 2 O-decomposition activity.
The catalysts prepared in examples 7 and 8 were subjected to an air atmosphere at 900 ℃Roasting for 100h and 200h, and then N-roasting 2 O decomposition activity test. The test conditions were: n in the reaction mixture 2 The O content was 1500ppm, the oxygen content was 4%, and nitrogen was the balance gas. The gas flow rate is controlled by a mass flowmeter, the total flow rate is 100ml/min, the micro quartz reaction tube is directly 3mm, and the airspeed is 60000 ml/g.h. The catalyst loading was 50mg,40-60 mesh. The reaction was carried out at normal pressure with a programmed heating rate of 5 ℃/min and a temperature rise from 150 ℃ to 850 ℃. As shown in fig. 1, the result is: fresh catalyst at 500 ℃ N 2 The conversion rate of O is 99%, and when the reaction temperature of the catalyst after aging for 100h is 625 ℃, N is 2 The conversion rate of O exceeds 99%, and when the reaction temperature of the catalyst after aging for 200 hours is 650 ℃, N 2 The conversion of O was 99%. Whereas example 7 without dealumination had 99% N on the catalyst 2 The temperatures of O decomposition were 650 ℃ (after 100h of aging) and 750 ℃ (200 h of aging), respectively.
From the above results, it can be seen that: the catalyst can make N in the range of 450-650 deg.C under the condition of high space velocity and high oxygen concentration 2 O is completely decomposed, the catalyst activity is good, N 2 The lower the O decomposition temperature is, the better the activity is, the smaller the catalyst activity decline after aging (900 ℃) at high temperature for a long time is, the smaller the reaction temperature increase is, the better the high temperature resistance and the service life of the catalyst are, and the zeolite molecular sieve after dealumination treatment shows better high temperature resistance, because of the stabilization of the silicon nest hydroxyl group on the transition metal.
Claims (10)
1. For N 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized by comprising a carrier and an active component, wherein the active component takes cobalt oxide as a main active component and is modified by a second metal, the second metal is transition metal, and the mole ratio of Co to the second metal is (1-10): (1-3), the mass content of the active component is 2.5-50%.
2. For N according to claim 1 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in thatIs Fe, ni, mn, cu, or Zn;
the carrier is alumina, silica, titania, cerium-zirconium solid solution or zeolite molecular sieve.
3. The method for N according to claim 2 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the second metal is Ni and/or Mn;
the molecular sieve is zeolite molecular sieve.
4. A method according to claim 3 for N 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the zeolite molecular sieve is ZSM-5, beta, MOR, A, X, Y or SSZ-13.
5. A method according to claim 3 for N 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the mass content of the active component is 5-15%;
the molar ratio of Co to the second metal is (1-2): (1-3).
6. For N according to claim 1 2 The cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the carrier is a carrier subjected to dealumination treatment, and the dealumination treatment comprises low-temperature dealumination in an acid solution and high-temperature steam dealumination.
7. A method for N as claimed in any one of claims 1 to 6 2 The preparation method of the cobalt-based composite oxide catalyst for O catalytic decomposition is characterized by comprising the following steps:
s1, dissolving a metal precursor in deionized water;
s2, adding an organic complexing agent into the solution containing the metal precursor;
s3, slowly dripping or spraying the solution obtained in the step S2 onto a carrier, rapidly stirring, standing at room temperature for 0-24 hours, drying at 50-120 ℃, and roasting at 300-650 ℃ in air atmosphere or other atmospheres for 1-24 hours to obtain the catalyst.
8. The method for N according to claim 7 2 The preparation method of the cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the metal precursor in the step S1 is soluble salt of Co and a second metal, and the soluble salt comprises nitrate, sulfate, chloride, carbonate or acetate.
9. The method for N according to claim 7 2 The preparation method of the cobalt-based composite oxide catalyst for O catalytic decomposition is characterized in that the organic complexing agent in the step S2 comprises triethanolamine, nitrilotriacetic acid and salts, ethylenediamine tetraacetic acid, ascorbic acid, citric acid, tartaric acid or gluconic acid and salts;
the molar ratio of the organic complexing agent to the total metal is 0.01-1.5:1.
10. a method for N as claimed in any one of claims 1 to 6 2 The use of a cobalt-based composite oxide catalyst for O catalytic decomposition, characterized in that the catalyst is used for N 2 In the O catalytic decomposition reaction, the reaction conditions are as follows: the reaction pressure is normal pressure, N in the reaction gas 2 The volume concentration of O is 0.01-50%, O 2 The volume concentration of (2) is 0-10%, H 2 The volume concentration of O is 0-15%, and the airspeed is 5000-200000h -1 The operating temperature is 200-1000 ℃.
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