CN117443398A - Mesoporous iron-based composite oxide catalyst and preparation method and application thereof - Google Patents
Mesoporous iron-based composite oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN117443398A CN117443398A CN202311412284.0A CN202311412284A CN117443398A CN 117443398 A CN117443398 A CN 117443398A CN 202311412284 A CN202311412284 A CN 202311412284A CN 117443398 A CN117443398 A CN 117443398A
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- Prior art keywords
- based composite
- composite oxide
- oxide catalyst
- toluene
- iron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 174
- 238000000034 method Methods 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 230000002195 synergetic effect Effects 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000002184 metal Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 7
- 150000003657 tungsten Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000012855 volatile organic compound Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009841 combustion method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- CQWVAHMJJPEGQE-UHFFFAOYSA-N CC=C.C(Cl)Cl Chemical compound CC=C.C(Cl)Cl CQWVAHMJJPEGQE-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- -1 automobile repair Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2065—Cerium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/00—Catalysts
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- B01D2255/20746—Cobalt
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- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
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- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
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- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a mesoporous iron-based composite oxide catalyst and a preparation method and application thereof, and belongs to the technical field of environmental catalytic purification. The chemical formula of the iron-based composite oxide catalyst is Fe a M b W (a+b)/4 O y . The catalyst is prepared by adopting a simple urea precipitation method, other complex operations are not needed, the method is simple and quick, the conditions are easy to control, and the repeatability is high. The mesoporous iron-based composite prepared by the inventionOxide catalysts can be used for NO x The method has the advantages of synergistic purification treatment with toluene waste gas, good denitration performance and good toluene oxidation capability, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of environmental catalytic purification, in particular to a mesoporous iron-based composite oxide catalyst and a preparation method and application thereof.
Background
The second major economy of China is world, however, energy consumption is inevitably caused while economy is developed, the energy consumption structure of China can be divided into coal, petroleum, natural gas, primary power and other energy, but due to the fact that the energy consumption of China is large, the supply of new energy such as solar energy, wind energy and hydrogen energy in a short time can not meet the requirement of economy development, and therefore, traditional fossil energy is still the core in the energy consumption structure for a relatively long time. Along with the combustion of fossil fuel, various elements in the fuel can be converted into atmospheric pollutants, the emission of smoke causes serious environmental pollution, and the environment is increasingly and directly threatening the survival of organisms. Common smoke pollutants are NO x VOCs, hg, etc. Wherein NO is x Is discharged into the atmosphere and reacts with light, a series of chemical reactions can occur, and secondary pollutants such as secondary organic aerosol, nitrate, sulfate and the like are formed. The generation of secondary pollutants can further cause environmental pollution problems, and serious environmental problems such as haze, photochemical smog, acid rain and the like are formed. In addition, NO x The existence of the medicine can directly damage the respiratory system of a human body and cause damage to respiratory organs.
NO x And VOCs are important co-precursors of PM2.5 and ozone. At present, SO in the atmospheric environment of China 2 、NO x The method has the advantages that the pollution control effects of PM2.5 and PM10 are remarkable, but the reduction of VOCs is not remarkable, so that the ozone concentration is not reduced and the ozone concentration is reversely increased, and the pollution control effects of the VOCs and NO are realized x The cooperative control of the pollutants effectively reduces the pollutant emission, thereby promoting the continuous improvement and improvement of the environmental air quality. Thus, the key to the synergistic remediation of PM2.5 and ozone is NO x And the synergistic emission reduction of VOCs.
Thus, development of efficient synergistic removal of toluene and NO x The purification materials and techniques are of great significance.
Currently, NO x The control techniques of (a) can be divided into: (1) Denitration before combustion refers to removing nitrogen-containing compounds in fuel to realize source decrement; (2) Denitration in combustion (denitration in furnace) by adjustment andcontrolling combustion process, reducing NO x Is generated; (3) Denitration after combustion (flue gas denitration), NO generated in the furnace is reacted chemically x And (5) removing. The denitration technology in the furnace mainly comprises the following steps: low nitrogen burner, fuel staged combustion, air staged combustion, flue gas recirculation, etc. have low denitration efficiency, generally not higher than 50%. The selective non-catalytic reduction (SNCR) technology is to spray reducing agent into the furnace chamber at 850-1100 deg.c to reduce NO in the fume into N 2 Is also generally classified as in-furnace denitration. The common reducing agent comprises ammonia and urea, and the removal efficiency is about 30-50%. The SNCR technology is widely applied because of simple equipment and small transformation of a power plant, but when the injection amount of the reducing agent is excessive, ammonia escape phenomenon can occur, so that the flue is corroded.
NO which is not removed from flue gas after application of in-furnace denitration technology x And the requirements of emission standards cannot be met, so that the flue gas is further removed by means of flue gas denitration technology. Common flue gas denitration techniques are Selective Catalytic Reduction (SCR) and oxidative absorption. The oxidative absorption technique is to add an oxidizing substance, e.g. NaClO, to the flue gas or wet spray tower x 、H 2 O 2 、KMnO 4 、O 3 EDTA, etc., to oxidize NO to higher valence state NO x And finally, wet absorption. SCR technology is the most widely used technology in large coal-fired power plants at present, and is to reduce NO into N by using a reducing agent under the action of a catalyst 2 . Compared with SNCR technology, the removal efficiency is high and can reach 90%. SCR is NH 3 As a reducing agent, by means of a catalyst, to make NO x And NH 3 The neutralization reaction is carried out at the temperature of 150-450 ℃ to convert N 2 And H 2 O(4NH 3 +4NO+O 2 →4N 2 +6H 2 O) with by-product N 2 O(4NH 3 +4NO+3O 2 →4N 2 O+6H 2 O) and NH easily occurs at higher reaction temperature 3 And (5) oxidizing.
The industrial VOCs are various and complex in composition. Sources of VOCs can be divided into natural sources and artificial sources. Wherein the natural source comprises plant release and volcanic explosionEmissions of VOCs are caused by natural factors such as hair. The artificial sources in turn include mobile sources and stationary sources. The movable source refers to VOCs discharged through transportation, and the fixed source refers to the discharge of VOCs caused by factors such as industrial and agricultural production, wherein the industrial production mainly comprises production activities of industries such as furniture boards, petroleum processing, oil refining, chemical industry, paint, automobile repair, rubber, package printing, decoration and the like. Agricultural production activities mainly include the production and use of a large number of pesticides and fertilizers. Benzene series, represented by toluene, are major pollutants emitted by chemical enterprises. Most VOCs have toxicity and can cause different injuries to human bodies. Studies have shown that exposure of humans to high concentrations of toluene can affect the central nervous system, causing neurological disorders. In addition to affecting human health, it is discharged into the atmosphere and NO in the atmosphere x Photochemical pollution and near-ground ozone pollution generated by the reaction cause damage to the ecological environment, which is difficult to repair.
At present, the treatment technology for VOCs can be divided into two main types, namely source control and terminal treatment. The source control is a preventive measure, the production cost and the operation mode are high in production equipment requirement, the effective removal is difficult to achieve at the current technical level, the terminal treatment technology mainly comprises a combustion method, an adsorption method, a biological method, a membrane separation method and a plasma method, the treatment capacity of the adsorption method and the catalytic combustion method is large, the removal efficiency is high, and the method is two feasible methods for treating large-gas-volume flue gas such as coal-fired flue gas and industrial waste gas.
(1) The adsorption control technology mainly carries out physical adsorption on VOCs in the waste gas through an adsorbent, so that the effect of purifying the flue gas is achieved, and the adsorption control technology is a VOCs treatment technology widely applied at present. Among them, the activated carbon has a great deal of attention because of its advantages of large specific surface area, abundant pore structure and surface functional groups. Li Liqing et al studied the influence of acid (nitric acid, sulfuric acid, hydrochloric acid) modified activated carbon on the adsorption performance of toluene and methanol, and found HNO 3 The specific surface area and pore volume of the treated activated carbon are increased, the oxygen-containing functional groups on the surface are increased, and the adsorption performance is improved; jie Li equal preparation of waste-based ActivityThe adsorption performance of the toluene is researched, and the waste-based activated carbon is found to have a preferential isotherm equilibrium curve, so that the carbon has good adsorption performance and realizes waste recycling.
(2) The treatment of VOCs waste gas by combustion method is divided into three types: the direct combustion method is suitable for the waste gas of the VOCs with higher concentration, and is difficult to eradicate the VOCs with low concentration; the VOCs are ignited by other combustion improver, so that the cost is high and secondary pollution is caused; catalytic combustion, by means of the catalyst, reduces the activation energy of chemical reaction, and directly degrades VOCs into CO in an oxidizing atmosphere 2 And H 2 And the O has small secondary pollution and thorough reaction. Compared with the direct combustion method and the combustion-supporting method, the catalytic combustion does not generate NO x 、SO 2 Secondary pollution and the like, and has corresponding application in the emission reduction of VOCs.
Hu Yun et al contrast commercial NH 3 SCR catalyst studied the pair NO of the bifunctional Cu-VWTi catalyst by impregnation method x Performance study on co-treatment with toluene, propylene dichloromethane, naphthalene and the like, the conversion rate of the catalyst to 50ppm toluene reaches more than 99% at the temperature of more than 350 ℃ and simultaneously NO is maintained x The conversion is greater than 90% (environ. Sci. Technology.2022, 56, 3719-3728); shogaofet et al prepared V using the commercial catalyst preparation method 2 O 5 -WO 3 /TiO 2 V (V) 2 O 5 -MoO 3 /TiO 2 The catalyst reached 90% conversion of 50ppm toluene at 350 ℃ (Chemical Engineering Journal,2022,435,134914); in addition, for NO x In conjunction with toluene removal, researchers have also investigated Mo/Ni impregnated VWTiO x Catalyst for 100ppm toluene and 500ppm NO x The reaction mechanism of the synergistic control between the two catalysts reaches that the toluene conversion rate of the two catalysts after being immersed reaches 99 percent at the temperature of more than 260 ℃, and NO x The conversion of (2) reaches 70% (Applied Surface Science 599 (2022) 153986) at 420 ℃; mnO with different morphologies was studied in Chenglong et al x Catalyst pair NO of (c) x Synergistic catalytic performance and mechanism with toluene, mnO x Simultaneous removal of NO with nanorod catalysts x And toluene activity superior to MnO x Nanocube catalyst (Journal ofEnvironmental Chemic)al Engineering 10 (2022) 108646); zhang Shigong preparing Cu-SAPO-34 by hydrothermal method, soaking MnO in excess x Loaded on a carrier prepared by a hydrothermal method, thereby MnO x Cu-SAPO-34 catalyst, and research on synergistic catalytic performance and reaction mechanism of the catalyst on 50ppm toluene and 500ppm NO, and under the condition of 300-380 ℃, the optimal synchronous removal performance of nitrogen oxides and toluene is more than or equal to 80%, and meanwhile, the catalyst has higher CO 2 Selectivity (. About.100%) and N 2 Selectivity of>80%) of the model molecules of toluene vs. NO by numerous researchers x Synergistic removal with aromatic compounds has been explored primarily in terms of both performance and mechanism. Most of the catalysts adopt metal vanadium with high toxicity, the preparation steps are complicated, and the use of a large amount of toxic chemical reagents causes serious harm to human bodies and the environment.
Disclosure of Invention
The invention aims to provide a mesoporous iron-based composite oxide catalyst, and a preparation method and application thereof, which are used for solving the problems that the catalyst has high toxicity, complex preparation process and can not efficiently remove NO in a synergic manner x And toluene.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a mesoporous iron-based composite oxide catalyst, wherein the chemical formula of the iron-based composite oxide catalyst is Fe a M b W (a+b)/4 O y Wherein M is one or more of Ce, cu, co and Ga, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 9.
The invention also provides a preparation method of the mesoporous iron-based composite oxide catalyst, which comprises the following steps:
(1) Sequentially adding ferric salt, metal salt and tungsten salt into urea solution for reaction to obtain precursor solution;
(2) Standing the precursor solution for a certain time, pouring out supernatant, and sequentially centrifuging, drying and roasting residues to obtain the iron-based composite oxide catalyst;
the metal salt is nitrate or sulfate.
Further, in the step (1), the reaction temperature is 80-100 ℃, and the reaction time is 12-36 h.
Further, in the step (1), the mass fraction of the urea solution is 2-5%, and the ferric salt is as follows: metal salt: the mass ratio of the tungsten salt is 1-3: 0.5 to 2:0.4 to 1;
the mass ratio of urea to ferric salt in the urea solution is 5-13: 1 to 3.
Further, in the step (2), the rotational speed of the centrifugation is 4000-6000 rpm; the drying temperature is 80-100 ℃, and the drying time is 20-48 h; the temperature of the roasting treatment is 400-600 ℃, the time of the roasting treatment is 4-6 h, and the temperature rising rate is 3-8 ℃/min.
The invention also provides application of the mesoporous iron-based composite oxide catalyst in the cooperative treatment of toluene and nitrogen oxides, and the mesoporous iron-based composite oxide catalyst and mixed raw material gas are mixed and reacted.
Further, the mixed raw material gas contains 400 to 1000ppm NH 3 、400～1000ppmNO、3～20％O 2 And 100 to 700ppm toluene.
Further, the total flow of the mixed raw material gas is 100-400 mL/min, and the dosage of the mesoporous iron-based composite oxide catalyst is 0.1-0.7 g.
Further, the temperature of the reaction is 150-500 ℃.
Further, the airspeed of the mixed raw material gas is 10000-70000 h -1 。
The invention has the beneficial effects that:
(1) The catalyst can keep better denitration performance and good toluene oxidation capability in the cooperative reaction, and has good industrial application prospect;
(2) The catalyst is prepared by adopting a simple urea precipitation method, other complex operations are not needed, the method is simple and rapid, the conditions are easy to control, the repeatability is high, the sources of the catalyst materials used by the method are wide, the price is relatively low, and the catalyst cost is low.
Drawings
FIG. 1 is a graph showing the activity of toluene catalytic removal of the catalyst prepared in example 1;
FIG. 2 is a graph of NO for the catalyst prepared in example 1 x Catalytic removal activity diagram;
FIG. 3 is a graph showing the activity of toluene catalytic removal of the catalyst prepared in example 2;
FIG. 4 is a graph of NO for the catalyst prepared in example 2 x Catalytic removal activity diagram;
FIG. 5 is a graph showing the catalytic toluene removal activity of the catalyst prepared in example 2 at various toluene concentrations;
FIG. 6 shows NO at various toluene concentrations for the catalyst prepared in example 2 x A synergistic catalytic removal activity diagram;
FIG. 7 is a graph showing the catalytic toluene removal activity of the catalyst prepared in example 2 at various oxygen concentrations;
FIG. 8 is a graph of NO at various oxygen concentrations for the catalyst prepared in example 2 x Catalytic removal activity profile.
Detailed Description
The invention provides a mesoporous iron-based composite oxide catalyst, wherein the chemical formula of the iron-based composite oxide catalyst is Fe a M b W (a+b)/4 O y Wherein M is one or more of Ce, cu, co and Ga, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 9.
In the present invention, M is preferably one or more of Ce, co, and Ga, and more preferably Ce.
The invention also provides a preparation method of the mesoporous iron-based composite oxide catalyst, which comprises the following steps:
(1) Sequentially adding ferric salt, metal salt and tungsten salt into urea solution for reaction to obtain precursor solution;
(2) Standing the precursor solution for a certain time, pouring out supernatant, and sequentially centrifuging, drying and roasting residues to obtain the iron-based composite oxide catalyst;
the metal salt is nitrate or sulfate.
In the present invention, the metal salt is preferably nitrate.
In the present invention, in the step (1), the temperature of the reaction is 80 to 100 ℃, preferably 85 to 95 ℃, and more preferably 90 ℃; the reaction time is 12 to 36 hours, preferably 18 to 28 hours, more preferably 24 hours.
In the present invention, in the step (1), the mass fraction of the urea solution is 2 to 5%, preferably 2.3 to 4.8%, and more preferably 2.5 to 4%; the iron salt: metal salt: the mass ratio of the tungsten salt is 1-3: 0.5 to 2:0.4 to 1, preferably 1.4 to 2.8:0.7 to 1.8:0.5 to 0.9, more preferably 1.6 to 2.5:0.8 to 1.5:0.6 to 0.8.
In the invention, the mass ratio of urea to ferric salt in the urea solution is 5-13: 1 to 3, preferably 6 to 11:1.5 to 2.9, more preferably 7 to 10:1.8 to 2.8.
In the present invention, in the step (2), the rotational speed of the centrifugation is 4000 to 6000rpm, preferably 4200 to 5700rpm, and more preferably 4500 to 5500rpm; the drying temperature is 80-100 ℃, preferably 85-95 ℃, and more preferably 90 ℃; the drying time is 20 to 48 hours, preferably 23 to 40 hours, and more preferably 27 to 35 hours.
In the invention, the temperature of the roasting treatment is 400-600 ℃, the time of the roasting treatment is 4-6 hours, and the temperature rising rate is 3-8 ℃/min; preferably, the temperature of the roasting treatment is 450-550 ℃, the time of the roasting treatment is 4.5-5.5 hours, and the temperature rising rate is 4-6 ℃/min; further preferably, the temperature of the calcination treatment is 500 ℃, the time of the calcination treatment is 5 hours, and the temperature rising rate is 5 ℃/min.
In the present invention, the time for standing is 10 to 24 hours, preferably 12 to 20 hours, more preferably 14 to 18 hours.
The invention also provides application of the mesoporous iron-based composite oxide catalyst in the cooperative treatment of toluene and nitrogen oxides, and the mesoporous iron-based composite oxide catalyst and mixed raw material gas are mixed and reacted.
In the present invention, the mixed raw material gas contains 400 to 1000ppm NH 3 、400～1000ppmNO、3～20％O 2 And 100 to 700ppm toluene, preferably 450 to 800ppm NH 3 、460～850ppmNO、7～18％O 2 And 200 to 600ppm toluene, more preferably 500 to 600ppm NH 3 、500～600ppm NO、10～15％O 2 And 300 to 500ppm toluene.
In the present invention, the total flow rate of the mixed raw material gas is 100 to 400mL/min, preferably 150 to 350mL/min, and more preferably 200 to 300mL/min; the amount of the mesoporous iron-based composite oxide catalyst is 0.1 to 0.7g, preferably 0.2 to 0.5g, and more preferably 0.3 to 0.4g.
In the present invention, the temperature of the reaction is 150 to 500 ℃, preferably 200 to 480 ℃, and more preferably 250 to 450 ℃.
In the invention, the airspeed of the mixed raw material gas is 10000-70000 h -1 Preferably 15000 to 65000h -1 Further preferably 20000 to 60000h -1 。
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Dissolving 7.2g of urea in 250mL of water to prepare urea solution, sequentially adding 2.9088g of ferric nitrate nonahydrate, 1.0421g of cerium nitrate hexahydrate and 0.5912g of ammonium metatungstate, and reacting at 90 ℃ for 24 hours;
(2) Standing at room temperature for 12h, pouring out supernatant, centrifuging, drying and roasting at 5000rpm for 6min at 90 ℃ for 24h, and roasting in a muffle furnace for 5h from room temperature to 500 ℃ at a heating rate of 5 ℃/min;
(3) Tabletting the catalyst prepared in the step (2) into 40-mesh granules to obtain FeCeWO, wherein the molar ratio of Fe, ce and W is 3:1:1, catalyst a.
Examples 2 to 5
The catalyst prepared according to the procedure of example 1, except that cerium nitrate was replaced with different metal nitrates, copper nitrate, cobalt nitrate, gallium nitrate and no cerium nitrate, in the same molar ratios as cerium nitrate, was prepared to FeCuWO, feCoWO, feGaWO, feWO, in which the molar ratio of Fe, cu and W was 3:1:1, the molar ratio of Fe, co and W is 3:1:1, molar ratio of Fe, ga to W is 3:1:1, molar ratio of Fe to W is 4:1, catalyst B, C, D, E.
Test example 1
Reacting 0.4g mesoporous iron-based composite oxide catalyst A, B, C, D and E with mixed raw material gas respectively, reacting in micro fixed bed continuous flow microreactor, and NO after the reaction is finished x And toluene synergistic catalytic removal activity test, wherein the test instrument is an online gas chromatograph provided with an FID detector, and the test conditions are as follows: HP-1 capillary column; carrier gas: high purity N 2 The method comprises the steps of carrying out a first treatment on the surface of the Sample inlet temperature: 150 ℃; column temperature: 110 ℃; FID detector temperature: 270 ℃; the specific conditions for the test are: introducing 500ppm toluene and 500ppm NH into the mixed raw material gas 3 500ppm NO and 3% oxygen by volume concentration, argon is used as balance gas, the total flow of the mixed raw material gas is 250mL/min, and the airspeed of the mixed raw material gas is 36000h -1 . Toluene and NO at different temperatures for each catalyst x The conversion results of toluene and NO are shown in tables 1 and 2 x The synergistic reactivity is shown in FIGS. 1 and 2.
TABLE 1 toluene conversion for catalysts of different nitrates
TABLE 2 conversion of catalyst nitrogen oxides for different nitrates
As can be seen from tables 1 and 2 and FIGS. 1 and 2, toluene T of catalyst A 90％ (the conversion reached 90% of the temperature) was 325℃and catalyst B was T 90％ T of catalyst C at 300 DEG C 90％ T of catalyst D at 375℃ 90％ T of catalyst E at 400 DEG C 90％ 375 deg.c; in addition, the nitrogen oxides T of catalyst A 90％ (the conversion rate reaches 90% of the temperature) is 325 ℃, the temperature window is wider, and the T of the catalyst B is 90％ Not up to 90%, as does catalyst C, D, E, wherein catalyst A exhibits the best catalytic oxidation activity of toluene and NO x The removal rate; when the temperature is 450 ℃, the conversion rate of toluene of the catalyst A, B, C, D and the catalyst E reaches 100 percent, and the conversion rate of nitrogen oxides is higher.
Example 6
The catalyst prepared by the procedure of example 1, with other parameters unchanged, was prepared by replacing the starting materials with 7.2g urea, 1.4396g ferric sulfate, 0.6821g cerium sulfate and 0.5912g ammonium metatungstate to give Fe 3 CeWO 9 I.e. catalyst F. Toluene and NO of catalyst F x The conversion and the test results of the synergistic reaction activity were similar to those of catalyst a.
Example 7
The amounts of iron nitrate and cerium nitrate used in catalyst a of example 1 were varied so that the total fe+ce mole was not changed to 4. The catalysts are divided into a, b, c, d, e, f, g, h, i according to the different Fe/Ce molar ratios, wherein a is Fe: ce: w=3: 1:1. b is Fe: ce: w=3.5: 0.5: 1. c is Fe: ce: w=2.5: 1.5: 1. d is Ce: w=4: 1. and e is Fe: w=4: 1. f is Fe: ce: w=2: 2: 1. g is Fe: ce: w=1.5: 2.5:1. h is Fe: ce: w=1: 3: 1. i is Fe: ce: w=0.5: 3.5:1.
test example 2
The specific conditions for the test are: 200ppm toluene, 500ppm NH 3 500ppm NO and 3% oxygen by volume concentration, argon as balance gas, the reaction gas flow rate of 250mL/min, and the reaction gas space velocity of 36000h -1 。
Toluene and NO at different temperatures for each catalyst x The conversion results of each catalyst are shown in tables 3 and 4, toluene and NO as a function of temperature x The reactivity curves of (2) are shown in FIGS. 3 and 4.
TABLE 3 toluene conversion of Fe/Ce catalysts in different molar ratios
TABLE 4 Nitrogen oxide conversion of Fe/Ce catalysts in different molar ratios
Test example 3
The toluene concentration in the test conditions was varied using catalyst A of example 1, the remaining conditions remained unchanged, and toluene and NO at different temperature points for catalyst A under different toluene concentrations x The conversion results of (2) are shown in tables 5 and 6, and the reaction activity curves with temperature are shown in FIGS. 5 and 6.
TABLE 5 toluene conversion tested for different toluene concentrations
Table 6 nitrogen oxide conversion tested for different toluene concentrations
Test example 4
The oxygen concentration in the test conditions was varied using catalyst A of example 1, the remaining conditions remaining unchanged, catalyst A being different under different oxygen concentrationsToluene and NO at temperature point x The conversion results of (2) are shown in tables 7 and 8, and the reaction activity curves with temperature are shown in FIGS. 7 and 8.
TABLE 7 toluene conversion for different oxygen concentration tests
Table 8 nitrogen oxide conversion tested for different oxygen concentrations
According to the embodiment, the mesoporous iron-based composite oxide catalyst, the preparation method and the application thereof are provided, and in the synergistic reaction, the catalyst can keep good denitration performance and good toluene oxidation capability, and has good industrial application prospect; meanwhile, the catalyst is prepared by adopting a simple urea precipitation method, other complex operations are not needed, the method is simple and rapid, the conditions are easy to control, the repeatability is high, the sources of the catalyst materials used in the method are wide, the price is relatively low, and the catalyst cost is low.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A mesoporous iron-based composite oxide catalyst is characterized in that the chemical formula of the iron-based composite oxide catalyst is Fe a M b W (a+b)/4 O y Wherein M is one or more of Ce, cu, co and Ga, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 9.
2. The method for preparing the mesoporous iron-based composite oxide catalyst according to claim 1, comprising the steps of:
(1) Sequentially adding ferric salt, metal salt and tungsten salt into urea solution for reaction to obtain precursor solution;
(2) Standing the precursor solution for a certain time, pouring out supernatant, and sequentially centrifuging, drying and roasting residues to obtain the iron-based composite oxide catalyst;
the metal salt includes nitrate or sulfate.
3. The method according to claim 2, wherein in the step (1), the reaction is carried out at a temperature of 80 to 100℃for a period of 12 to 36 hours.
4. A method according to claim 2 or 3, wherein in step (1), the urea solution has a mass fraction of 2 to 5%, and the iron salt is: metal salt: the mass ratio of the tungsten salt is 1-3: 0.5 to 2:0.4 to 1;
the mass ratio of urea to ferric salt in the urea solution is 5-13: 1 to 3.
5. The method according to claim 4, wherein in the step (2), the rotational speed of the centrifugation is 4000 to 6000rpm; the drying temperature is 80-100 ℃, and the drying time is 20-48 h; the temperature of the roasting treatment is 400-600 ℃, the time of the roasting treatment is 4-6 h, and the temperature rising rate is 3-8 ℃/min.
6. The application of the mesoporous iron-based composite oxide catalyst in the cooperative treatment of toluene and nitrogen oxides, which is characterized in that the mesoporous iron-based composite oxide catalyst and mixed raw material gas are mixed and reacted.
7. The use of the mesoporous iron-based composite oxide catalyst according to claim 6, wherein said mixed feed gas comprises 400 to 1000ppm NH 3 、400～1000ppmNO、3～20％O 2 And 100 to 700ppm toluene.
8. The application of the mesoporous iron-based composite oxide catalyst according to claim 7 in the cooperative treatment of toluene and nitrogen oxides, wherein the total flow of the mixed raw material gas is 100-400 mL/min, and the dosage of the mesoporous iron-based composite oxide catalyst is 0.1-0.7 g.
9. The use of the mesoporous iron-based composite oxide catalyst according to claim 7 or 8 in the synergistic treatment of toluene and nitrogen oxides, wherein the temperature of the reaction is 150-500 ℃.
10. The application of the mesoporous iron-based composite oxide catalyst in the cooperative treatment of toluene and nitrogen oxides according to claim 9, wherein the airspeed of the mixed raw material gas is 10000-70000 h -1 。
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