CN115193447A - Catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants as well as preparation method and application of catalyst - Google Patents
Catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants as well as preparation method and application of catalyst Download PDFInfo
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- CN115193447A CN115193447A CN202110397579.XA CN202110397579A CN115193447A CN 115193447 A CN115193447 A CN 115193447A CN 202110397579 A CN202110397579 A CN 202110397579A CN 115193447 A CN115193447 A CN 115193447A
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- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 107
- 239000011593 sulfur Substances 0.000 title claims abstract description 107
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 102
- 238000000746 purification Methods 0.000 title claims abstract description 99
- 230000003647 oxidation Effects 0.000 title claims abstract description 96
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 96
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 94
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 94
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 86
- 230000002829 reductive effect Effects 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000012876 carrier material Substances 0.000 claims abstract description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 83
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 72
- 239000000047 product Substances 0.000 claims description 45
- 238000005470 impregnation Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 36
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 235000006408 oxalic acid Nutrition 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000012695 Ce precursor Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 75
- 239000007789 gas Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 28
- 239000002105 nanoparticle Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 9
- 239000002671 adjuvant Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000005261 decarburization Methods 0.000 description 7
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
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- 230000008021 deposition Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 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 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000010942 self-nucleation Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
Abstract
The invention provides a catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants, and a preparation method and application thereof, and belongs to the field of catalyst preparation. Comprises an inner layer and an outer layer, wherein the inner layer comprises a first carrier material, a first active component, a first cocatalyst and a second cocatalyst, and the outer layer comprises a second carrier material and a second active component; the first carrier material is CeO 2 ‑ZrO 2 A mesoporous support, the first promoter comprising Mn oxide and/or Co oxide, the second promoter comprising MoO 3 And/or WO 3 The first active component comprises Pt; the second carrier material is TiO 2 The second active component is V 2 O 5 . The first active component in the invention is used as an inner layerThe catalytic oxidation VOCs can be realized, the second active component can catalyze and oxidize reductive sulfur pollutants as an outer layer, and the synergistic purification of the VOCs and the reductive sulfur pollutants is realized.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants, and a preparation method and application thereof.
Background
Currently, the synthesis gas required for ammonia, methanol and other monocarbon industries is mainly derived from coal-based gas. But the synthesis gas (CO + H) obtained in the process of making gas from coal 2 ) Often still has a large amount of CO 2 Furthermore, the synthesis gas obtained by direct gas production generally requires partial conversion or full conversion (CO + H) for subsequent industrial production 2 O→CO 2 +H 2 ) To adjust the hydrocarbon ratio. Therefore, the coal gas after the shift reaction contains more CO 2 In order to avoid the influence on the subsequent synthesis reaction, decarburization treatment is required. At present, more decarburization technologies are adopted, and different solutions are mainly used for treating CO 2 The difference in solubility with coal gas will be CO 2 Separating with coal gas, decarbonizing, and separating to obtain high-concentration CO 2 The waste gas is decarbonized tail gas (CO) 2 Volume concentration greater than 75%). It is well known that coal contains sulfides, which are mainly malodorous reducing sulfides (H) and are transferred to coal gas through gasification 2 S, COS and CS 2 ) And a trace amount of reducing sulfide inevitably enters decarburization tail gas in the decarburization process. In addition, the coal gasification process often has trace amount of VOCs which can not be deeply gasified into CO and H 2 And part of the VOCs is easily absorbed, concentrated and released in a decarburization link to enter decarburization tail gas, and a small amount of volatile organic solvent enters the decarburization tail gas in the use process. Therefore, the decarbonized tail gas contains a certain amount of VOCs besides a small amount of reducing sulfides.
At present, most of decarbonized tail gas is directly discharged, and malodorous reducing sulfides and VOCs need to be purified. Catalytic combustion of VOCs alone is numerous but the need to treat reducing sulfur is not met only with VOCs, but with very few catalysts or sorbents for reducing sulfur purification and no ability to treat VOCs. Namely, the problem that the reductive sulfides and the VOCs cannot be treated simultaneously exists in the prior art.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for the catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants, and a preparation method and an application thereof. The catalyst provided by the invention can be used for simultaneously carrying out catalytic oxidation and synergistic purification on VOCs and reducing sulfur pollutants.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a catalyst for catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants, which comprises an inner layer and an outer layer, wherein the inner layer comprises a first carrier material, a first active component, a first cocatalyst and a second cocatalyst, and the outer layer comprises a second carrier material and a second active component;
the first carrier material is CeO 2 -ZrO 2 A mesoporous support, the first promoter comprising Mn oxide and/or Co oxide, the second promoter comprising MoO 3 And/or WO 3 The first active component comprises Pt and the CeO 2 -ZrO 2 The first active component, the first cocatalyst and the second cocatalyst are loaded on the mesoporous pores and the surface of the mesoporous carrier;
the second carrier material is TiO 2 And the second active component is V 2 O 5 And the second active component is loaded on the surface of the second carrier material.
Preferably, the CeO 2 -ZrO 2 CeO in mesoporous carrier 2 And ZrO 2 The total content of the catalyst is 70-93 wt% of the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants.
Preferably, the CeO 2 -ZrO 2 CeO in mesoporous carrier 2 The content of (b) is 45-50 wt%, zrO 2 The content of (A) is 50-55%.
Preferably, the total content of the first active component and the second active component in the catalytic oxidation synergistic purification catalysis of the VOCs and the reduced sulfur pollutants is 7-26 wt% calculated by metal simple substances.
Preferably, the content of the first active component in the catalytic oxidation synergistic purification catalysis of the VOCs and the reducing sulfur pollutants is 0.1-1 wt%, and the content of the first active component in the catalytic oxidation synergistic purification catalysis of the VOCs and the reducing sulfur pollutants is V 2 O 5 The content of (b) is 1-8 wt%, and the VOCs and the reductive sulfur pollutants are subjected to catalytic oxidation and synergistic purification catalysis to obtain TiO 2 The content of (B) is 6-20 wt%.
Preferably, the Mn oxide is MnO 2 And/or Mn 3 O 4 。
Preferably, the content of the first promoter in the catalyst for the synergistic purification of the catalytic oxidation of the VOCs and the reducing sulfur pollutants is 1 to 5wt%, and the content of the second promoter in the catalyst for the synergistic purification of the catalytic oxidation of the VOCs and the reducing sulfur pollutants is 4 to 10wt%.
The invention also provides a preparation method of the catalyst for the catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants, which comprises the following steps:
mixing a first cocatalyst precursor, a Ce precursor, a Zr precursor, a pore-forming agent and oxalic acid, and carrying out a first hydrothermal reaction to obtain CeO 2 -ZrO 2 A mesoporous support;
mixing a first active component metal salt, a second cocatalyst precursor and water to obtain an impregnation liquid;
subjecting the CeO to 2 -ZrO 2 Immersing the mesoporous carrier into the impregnation liquid, and sequentially performing first drying and first roasting to obtain a first target product;
mixing the first target product, ethanol, a thickening agent and a titanium precursor, carrying out hydrolysis reaction on the obtained suspension, carrying out second hydrothermal reaction, and sequentially carrying out second drying and second roasting on the obtained precipitate to obtain a second target product;
mixing the second active component metal salt with water to obtain second active component metal salt impregnation liquid;
immersing the second target product into the second active component metal salt impregnation liquid, and then sequentially carrying out third drying and third roasting to obtain the catalyst for catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants
Preferably, the pore-forming agent is polyethylene glycol or polyvinylpyrrolidone.
The invention also provides an application of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants in the technical scheme or the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants prepared by the preparation method in the technical scheme in the treatment of decarbonized tail gas.
The invention provides a catalyst for catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants, which comprises an inner layer and an outer layer, wherein the inner layer comprises a first carrier material, a first active component, a first cocatalyst and a second cocatalyst, and the outer layer comprises a second carrier material and a second active component; the first carrier material is CeO 2 -ZrO 2 A mesoporous support, the first promoter comprising Mn oxide and/or Co oxide, the second promoter comprising MoO 3 And/or WO 3 The first active component comprises Pt and the CeO 2 -ZrO 2 The first active component, the first cocatalyst and the second cocatalyst are loaded on the mesopores and the surface of the mesoporous carrier; the second carrier material is TiO 2 And the second active component is V 2 O 5 And the second active component is loaded on the surface of the second carrier material.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst provided by the invention can be used for reducing sulfide (H) 2 S, COS and CS 2 ) Catalytic oxidation to SO 2 Detoxication and deodorization are carried out, VOCs are catalytically oxidized into CO 2 And H 2 The invention realizes the synergistic purification of the VOCs and the reducing sulfur pollutants, and has the advantages of low cost, good selectivity, wide active window, difficult carbon deposition, stable catalytic activity and capability of realizing the low-temperature catalytic purification at low temperatureHigh-efficiency catalytic oxidation is realized at the temperature (320 ℃).
The invention also provides a preparation method of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants, which is simple and convenient to operate.
Detailed Description
The invention provides a catalyst for catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants, which comprises an inner layer and an outer layer, wherein the inner layer comprises a first carrier material, a first active component, a first cocatalyst and a second cocatalyst, and the outer layer comprises a second carrier material and a second active component;
the first carrier material is CeO 2 -ZrO 2 A mesoporous support, the first promoter comprising Mn oxide and/or Co oxide, the second promoter comprising MoO 3 And/or WO 3 The first active component comprises Pt and the CeO 2 -ZrO 2 The first active component, the first cocatalyst and the second cocatalyst are loaded on the mesopores and the surface of the mesoporous carrier;
the second carrier material is TiO 2 And the second active component is V 2 O 5 And the second active component is loaded on the surface of the second carrier material.
In the present invention, the CeO 2 -ZrO 2 CeO in mesoporous carrier 2 And ZrO 2 Preferably the total content of (a) is 70 to 93wt%, more preferably 72 to 78wt%, even more preferably 73 to 76wt%, most preferably 75.5 wt% of the VOCs and reduced sulfur contaminant catalytic oxidation co-purification catalyst.
In the present invention, the CeO 2 -ZrO 2 CeO in mesoporous carrier 2 The content of (b) is preferably 45 to 50wt%, zrO 2 The content of (B) is preferably 50 to 55%.
In the present invention, the CeO 2 -ZrO 2 The mass content of the Mn oxide in the mesoporous carrier is preferably 3-10%, and the mass content of the Co oxide is preferably 3-8%. In the present invention, the Mn oxide preferably includes MnO 2 And/or Mn 3 O 4 。
In the present invention, the CeO 2 -ZrO 2 The average pore diameter of the mesoporous support is preferably 20 to 30nm.
In the present invention, the content of the first promoter in the catalyst for the catalytic oxidation of the synergistic purification of VOCs and reduced sulfur pollutants is preferably 1 to 5wt%, more preferably 2 to 4wt%, and most preferably 3wt%, and the content of the second promoter in the catalyst for the catalytic oxidation of the synergistic purification of VOCs and reduced sulfur pollutants is preferably 4 to 10wt%, more preferably 5 to 7wt%, and most preferably 6wt%.
In the invention, the sum of the contents of the first active component and the second active component in the catalytic oxidation synergistic purification catalysis of the VOCs and the reduced sulfur pollutants is preferably 7 to 26wt%, more preferably 12 to 22wt%, further preferably 14 to 20wt%, and most preferably 16 to 17wt% calculated by metal simple substance.
In the present invention, the content of the first active component in the catalytic oxidation synergistic purification catalyst for the VOCs and the reduced sulfur pollutants is preferably 0.1 to 1wt%, more preferably 0.2 to 0.8wt%, and most preferably 0.5wt%.
In the present invention, the first active component preferably further includes Ru, and when the first active component preferably further includes Ru, the present invention is not particularly limited to the mass ratio of Pt to Ru.
In the invention, the VOCs and the reductive sulfur pollutants are subjected to catalytic oxidation to cooperatively purify V in catalysis 2 O 5 Preferably in an amount of 1 to 5 wt.%, more preferably 2 to 4.2 wt.%, most preferably 3 to 3.2 wt.%, said VOCs and reduced sulfur contaminants are catalytically oxidized to co-purify the TiO in the catalysis 2 The content of (B) is preferably 6 to 20% by weight, more preferably 8 to 15% by weight, still more preferably 9 to 13% by weight, most preferably 10% by weight.
The invention also provides a preparation method of the catalyst for the catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants, which comprises the following steps:
mixing a first cocatalyst precursor, a Ce precursor, a Zr precursor, a pore-forming agent and oxalic acid to perform a first hydrothermal reactionTo obtain CeO 2 -ZrO 2 A mesoporous support;
mixing a first active component metal salt, a second cocatalyst precursor and water to obtain an impregnation liquid;
subjecting the CeO to 2 -ZrO 2 Immersing the mesoporous carrier into the impregnation liquid, and sequentially performing first drying and first roasting to obtain a first target product;
mixing the first target product, ethanol, a thickening agent and a titanium precursor, carrying out hydrolysis reaction on the obtained suspension, carrying out a second hydrothermal reaction, and sequentially carrying out second drying and second roasting on the obtained precipitate to obtain a second target product;
mixing the second active component metal salt with water to obtain second active component metal salt impregnation liquid;
and immersing the second target product into the second active component metal salt impregnation liquid, and then sequentially carrying out third drying and third roasting to obtain the catalytic oxidation synergistic purification catalyst for the VOCs and the reducing sulfur pollutants.
The method comprises the steps of mixing a first cocatalyst precursor, a Ce precursor, a Zr precursor, a pore-forming agent and oxalic acid, and carrying out a first hydrothermal reaction to obtain CeO 2 -ZrO 2 A mesoporous support.
In the invention, the first promoter precursor is preferably one or more of manganese nitrate, cobalt nitrate, manganese acetate and cobalt acetate.
In the present invention, the Ce precursor is preferably cerium nitrate or cerium acetate, and the Zr precursor is preferably zirconium nitrate or zirconium acetate.
In the present invention, the pore-forming agent is preferably polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP). In the invention, the mass of the pore-forming agent is preferably 10-20% of the mass of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants.
In the present invention, the oxalic acid is preferably added in the form of an oxalic acid aqueous solution, the mass concentration of the oxalic acid aqueous solution is preferably 15%, the volume ratio of the sum of the volume of the part of the promoter precursor, the Ce precursor, the Zr precursor and the pore former to the oxalic acid aqueous solution is preferably 1.2.
In the present invention, the temperature of the first hydrothermal reaction is preferably 150 to 170 ℃ and the time is preferably 2 to 4 hours.
After the hydrothermal reaction, the method preferably further comprises washing, drying and roasting the obtained first hydrothermal reaction product in sequence to obtain the CeO 2 -ZrO 2 A mesoporous support.
In the present invention, the drying temperature is preferably 120 to 130 ℃ and the drying time is preferably 6 to 8 hours.
In the invention, the roasting temperature is preferably 450-550 ℃, and the time is preferably 3-5 h.
According to the invention, a first active component metal salt, a second cocatalyst precursor and water are mixed to obtain an impregnation liquid.
In the present invention, the second co-catalyst precursor is preferably Mo (NO) 3 ) 4 And (NH) 4 ) 6 H 2 W 12 O 40 ·6H 2 O。
In the present invention, the first active component metal salt is preferably H 2 PtCl 6 Or RuCl 3 。
To obtain CeO 2 -ZrO 2 After the mesoporous carrier and the impregnation liquid are used, the CeO is mixed 2 -ZrO 2 And immersing the mesoporous carrier into the impregnation liquid, and sequentially performing first drying and first roasting to obtain a first target product.
In the present invention, the first drying preferably includes a low-temperature stirring drying treatment and a thermal drying treatment which are sequentially performed, the temperature of the low-temperature stirring drying treatment is preferably 40 to 60 ℃, and the time is preferably 6 to 7 hours, and the stirring speed of the low-temperature stirring drying treatment is not particularly limited in the present invention; the temperature of the thermal drying treatment is preferably 110-120 ℃, and the time is preferably 4-6 h.
In the present invention, the temperature of the first calcination is preferably 600 to 700 ℃, and the time is preferably 5 to 7 hours.
After the first firing is completed, the present invention preferably ball-mills more first firing products for 30min to obtain uniform nanoparticle powder, i.e., the first target product.
After the first target product is obtained, the first target product, ethanol, a thickening agent and a titanium precursor are mixed, the obtained suspension is subjected to hydrolysis reaction, a second hydrothermal reaction is carried out, and the obtained precipitate is subjected to second drying and second roasting in sequence to obtain a second target product.
In the present invention, the thickening agent is preferably polyethylene glycol (PEG) or polyvinyl alcohol (PVA).
In the invention, the titanium precursor is preferably butyl titanate, tetraisopropyl titanate or titanium tetrachloride, the butyl titanate, tetraisopropyl titanate or titanium tetrachloride is hydrolyzed in a hydrolysis reaction, and CeO is loaded on a first active component (noble metal Pt) 2 -ZrO 2 Surface control uniform deposition of TiO on mesoporous inner layer catalyst 2 。
In the invention, the hydrolysis reaction may have dead angles, namely the second active component (outer layer catalyst) coats and protects the first active component (noble metal Pt, inner layer catalyst), the incomplete coating obviously weakens the protection effect, the hydrolysis reaction deposition has the advantages of high coverage and the defect of easy self-nucleation (namely forming particles and growing by itself to cause ineffective TiO) 2 Particle presence), multiple depositions again can lead to ineffective TiO 2 More particles are added, the effect of adding the second active component metal salt containing titanium salt again in the invention is to make up the possible incomplete coating problem in the previous step and better disperse the active vanadium substance V 2 O 5 。
In the present invention, the hydrolysis reaction is preferably an airborne steam hydrolysis method.
In the present invention, the temperature of the second hydrothermal reaction is preferably 150 to 170 ℃ and the time is preferably 2 to 4 hours.
In the present invention, the temperature of the second drying is preferably 120 to 130 ℃, and the time is preferably 6 to 8 hours.
In the present invention, the temperature of the second roasting is preferably 450 to 550 ℃, and the time is preferably 3 to 5 hours.
According to the invention, the second active component metal salt and water are mixed to obtain the second active component metal salt impregnation liquid.
In the present invention, the second active component metal salt is preferably NH 4 VO 3 And TiOSO 4 ·2H 2 And O. In the invention, the TiO obtained by the third roasting of the second active component metal salt 2 Sequentially carrying out hydrolysis reaction, second hydrothermal reaction, second drying and second roasting on the precursor of titanium to obtain TiO 2 The total mass of the catalyst is that the VOCs and the reductive sulfur pollutants are subjected to catalytic oxidation and synergistic purification of TiO in the catalyst 2 The quality of (c).
After a second active component metal salt impregnation liquid and a second target product are obtained, the second target product is immersed into the second active component metal salt impregnation liquid, and then third drying and third roasting are sequentially carried out, so that the VOCs and the reductive sulfur pollutant catalytic oxidation synergistic purification catalyst are obtained.
The definition of the third drying and the third firing of the present invention is preferably identical to that of the first drying and the first firing, and will not be described herein.
After the third roasting is completed, the obtained third roasting product is preferably subjected to drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of the VOCs and the reducing sulfur pollutants. The present invention is not particularly limited with respect to the specific manner in which the drum is formed.
The invention also provides an application of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants in the technical scheme or the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants prepared by the preparation method in the technical scheme in the treatment of decarbonized tail gas.
The source of the decarbonized tail gas is not particularly limited in the present invention, and any source known to those skilled in the art can be used.
In the invention, VOCs in the decarbonized tail gas preferably comprise CO and H 2 、CH 4 And CH 3 One or more of OH, the reduced sulfur contaminant in the decarbonated tail gas preferably comprising H 2 S, COS and CS 2 One or more of (a).
In the present invention, the decarbonized tail gas preferably has a VOCs content of 1000ppm and a reduced sulfur contaminant of preferably 40ppm, wherein H is 2 The S content is preferably 20ppm, the COS content is preferably 10ppm 2 The content of (B) is preferably 10ppm.
In the present invention, the application preferably includes: and (3) carrying out combustion reaction on the decarbonized tail gas through the catalytic oxidation synergistic purification catalyst of the VOCs and the reductive sulfur pollutants.
In the invention, the flow rate of the decarbonized tail gas passing through the VOCs and the reductive sulfur pollutant catalytic oxidation synergistic purification catalyst is preferably 5000-8000 m 3 /h。
In the present invention, the temperature of the combustion reaction is preferably 320 ℃.
In order to further illustrate the present invention, the following examples are provided to describe the catalyst for the catalytic oxidation of co-purification of VOCs and reduced sulfur contaminants and the preparation and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
5g of VOCs and reductive sulfur pollutant are prepared together to be used as a catalyst for catalytic oxidation and synergistic purification. In which CeO is present 2 、ZrO 2 The total content of the components is 73.5wt%, and the total content of the active components is 16.5wt% (wherein, the content of Pt is 0.25wt%, the content of Ru is 0.25wt%, and V 2 O 5 3wt% of TiO 2 Content 13 wt%), the first promoter content in the adjuvant was 3%, and the second promoter content was 7%.
Weigh 0.2720g of Co (NO) 3 ) 2 ·6H 2 O and 0.1544g Mn (NO) 3 ) 2 、6.6999g Zr(NO 3 ) 4 ·5H 2 O、4.4026g Ce(NO 3 ) 3 ·6H 2 Mixing O and a pore-forming agent polyethylene glycol (which is 10% of the mass of the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants), adding 15% (mass concentration) oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2Filtering and washing the precipitate, drying at 130 deg.C for 6h, calcining at 600 deg.C for 5h to obtain CeO 2 -ZrO 2 A mesoporous support;
the above CeO 2 -ZrO 2 The mesoporous carrier is immersed in a solution containing 0.0263g H 2 PtCl 6 1.7102mL of RuCl with a concentration of 15mg/mL 3 Solution, 0.4181g Mo (NO) 3 ) 4 、0.1927g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Stirring and drying the soaking solution of O at the low temperature of 60 ℃ for 6h, then drying the soaking solution at the temperature of 110 ℃ for 6h, roasting the soaking solution at the temperature of 600 ℃ for 7h after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolytic precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 170 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 130 ℃ for 6 hours, and roasting at 600 ℃ for 5 hours to obtain a second target product;
weigh 0.1928gNH 4 VO 3 、1.7157g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 60 ℃ for 6 hours, then drying at a temperature of 110 ℃ for 6 hours, roasting at a temperature of 600 ℃ for 7 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants is obtained, the gas to be treated (decarbonized tail gas) is kept at 5000-8000 m 3 The activity of the catalyst for the catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants by combustion reaction is measured by passing the prepared catalyst at a flow rate of/h.
Example 2
5g of VOCs and reductive sulfur pollutant are prepared together, and the catalyst is used for catalytic oxidation and synergistic purification. In which CeO is present 2 、ZrO 2 The content of the active component accounts for 72wt% in total, and the content of the active component accounts for 20wt% in total (wherein the content of Pt is 1wt%, V 2 O 5 5wt% of TiO 2 Content 14 wt%), the first promoter content in the adjuvant is 2%, and the second promoter content is 6%.
Weigh 3.534g of Co (NO) 3 ) 2 ·6H 2 O and 4.536g Zr (NO) 3 ) 4 ·5H 2 O and a pore-forming agent polyethylene glycol (10 percent of the mass of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants) are mixed to prepare a solution, and 0.118g of Mn (NO) is added 3 ) 2 ·4H 2 O、0.131g Co(NO 3 ) 2 ·6H 2 And O is continuously stirred and mixed, then 15 percent (mass concentration) oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2 2 -ZrO 2 A mesoporous support;
0.104g of H 2 PtCl 6 、0.344g Mo(NO 3 ) 4 、0.112g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Mixing O with water to obtain a soaking solution, and mixing the above-mentioned CeO 2 -ZrO 2 Immersing the mesoporous carrier into the impregnation liquid, stirring and drying at a low temperature of 40 ℃ for 7h, then drying at a temperature of 120 ℃ for 4h, roasting at a temperature of 700 ℃ for 5h after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8 hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.154g NH 4 VO 3 、1.41g TiOSO 4 ·2H 2 Mixing O and dissolving in water to obtain a steeping liquor, immersing the second target product in the steeping liquor, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, drying and then cooling at a temperature of 700 DEG CRoasting for 5h, and then molding in a rotary drum to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After obtaining the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants, the gas to be treated (decarbonized tail gas) is controlled at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 3
10g of VOCs and reductive sulfur pollutant are prepared together to be used as the catalyst for catalytic oxidation and synergistic purification. In which CeO is present 2 、ZrO 2 The content of the active component accounts for 80wt% in total, and the content of the active component accounts for 12wt% in total (wherein the content of Pt is 0.8wt%, V 2 O 5 3.2wt% of TiO 2 Content 8 wt%), the first promoter content in the adjuvant is 3%, and the second promoter content is 5%.
Weigh 0.917g Co (NO) 3 ) 2 ·6H 2 O and 0.188g Mn (NO) 3 ) 2 、11.770g Zr(NO 3 ) 4 ·5H 2 O、11.9076g Ce(NO 3 ) 3 ·6H 2 O and a pore-forming agent polyethylene glycol (10 percent of the mass of the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants) are mixed to prepare a solution, and 0.118g of Mn (NO) is added 3 ) 2 ·4H 2 O、0.131g Co(NO 3 ) 2 ·6H 2 And O is continuously stirred and mixed, then 15 percent (mass concentration) oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2 2 -ZrO 2 A mesoporous support;
0.145g of H 2 PtCl 6 、0.3584g Mo(NO 3 ) 4 、0.441g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Mixing O with water to obtain a solution, and mixing the above CeO 2 -ZrO 2 Immersing the mesoporous carrier in the impregnating solution, stirring and drying at 40 deg.C for 7 hr, drying at 120 deg.C for 4 hr, drying, and drying at 700 deg.CRoasting at the temperature of 5 hours, and performing ball milling for 30min to obtain uniform nano-particle powder, namely a first target product;
dispersing the obtained nano-particle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and titanium tetrachloride, mixing to prepare a solution, stirring, performing hydrolytic precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.525g NH 4 VO 3 、1.098g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants is obtained, the gas to be treated (decarbonized tail gas) is kept at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 4
10g of VOCs and reductive sulfur pollutant are prepared in total and are used as a catalyst for catalytic oxidation and synergistic purification. Wherein CeO 2 、ZrO 2 The content is 80wt%, the content of active components is 12wt% (wherein, the content of Pt is 0.5wt%, the content of Ru is 0.5wt%, V) 2 O 5 2wt% of TiO 2 Content 9 wt%), the first promoter content in the adjuvant is 3%, and the second promoter content is 5%.
Weigh 0.932g Co (NO) 3 ) 2 ·6H 2 O and 0.191gMn (NO) 3 ) 2 、12.819g Zr(NO 3 ) 4 ·5H 2 O、11.7512g Ce(NO 3 ) 3 ·6H 2 O and pore-forming agent polyethylene glycol (10 percent of the mass of the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants) are mixed to prepare a solution, and then 15 percent (mass concentration) is added) Oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2 2 -ZrO 2 A mesoporous support;
the above-mentioned CeO 2 -ZrO 2 Immersing the mesoporous carrier into a solution containing 0.183g of H 2 PtCl 6 4.9267mL RuCl with a concentration of 15mg/mL 3 Solution, 0.613g Mo (NO) 3 ) 4 、5.416g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Stirring and drying the O-containing impregnation liquid at a low temperature of 50 ℃ for 6 hours, then drying the O-containing impregnation liquid at a temperature of 125 ℃ for 5 hours, roasting the O-containing impregnation liquid at a temperature of 650 ℃ for 6 hours after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nano-particle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, performing hydrothermal reaction at 160 ℃ for 5 hours to obtain a precipitate, filtering and washing the precipitate, drying at 125 ℃ for 8 hours, and roasting at 650 ℃ for 4 hours to obtain a second target product;
weigh 0.333gNH 4 VO 3 、1.255g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 50 ℃ for 6 hours, then drying at a temperature of 125 ℃ for 5 hours, roasting at a temperature of 650 ℃ for 6 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants is obtained, the gas to be treated (decarbonized tail gas) is kept at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 5
10g of VOCs and reductive sulfur pollutant are prepared in total and are used as a catalyst for catalytic oxidation and synergistic purification. Wherein CeO 2 、ZrO 2 The content of the active component accounts for 76wt% in total, and the content of the active component accounts for 16wt% in total (wherein the content of Pt is 1wt%, V 2 O 5 Content 5wt%, tiO 2 Content 10 wt%), the first promoter content in the adjuvant is 4%, and the second promoter content is 4%.
Weigh 0.7252g Co (NO) 3 ) 2 ·6H 2 O and 0.4117g of Mn (NO) 3 ) 2 、13.3998g Zr(NO 3 ) 4 ·5H 2 O、9.5846g Ce(NO 3 ) 3 ·6H 2 O and a pore-forming agent polyethylene glycol (which is 10 percent of the mass of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants) are mixed to prepare a solution, 15 percent (mass concentration) of oxalic acid solution is added (the volume ratio of the oxalic acid solution to the solution is 1.2) 2 -ZrO 2 A mesoporous support;
the above-mentioned CeO 2 -ZrO 2 The mesoporous carrier is immersed in a solution containing 0.1051g of H 2 PtCl 6 6.8408mL of RuCl with a concentration of 15mg/mL 3 Solution, 0.4779g Mo (NO) 3 ) 4 、0.2203g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Stirring and drying the soaking solution of O at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder into absolute ethyl alcohol, adding a polyvinyl alcohol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8 hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.6428gNH 4 VO 3 、2.6395g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After obtaining the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants, the gas to be treated (decarbonized tail gas) is controlled at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 6
5g of VOCs and reductive sulfur pollutant are prepared together, and the catalyst is used for catalytic oxidation and synergistic purification. Wherein CeO 2 、ZrO 2 70wt% in total, and 22wt% in total of active components (wherein the Pt content is 0.4wt%, the Ru content is 0.6wt%, V) 2 O 5 6wt% of TiO 2 Content 15 wt%), the first promoter content in the adjuvant is 3%, and the second promoter content is 5%.
Weigh 3.422g Ce (NO) 3 ) 3 ·6H 2 O、4.667g Zr(NO 3 ) 4 ·5H 2 O and pore-forming agent polyethylene glycol (10% of the mass of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants) are mixed to prepare a solution, and 0.126g of Mn (NO) is added 3 ) 2 、0.197g Co(NO 3 ) 2 ·6H 2 And O is continuously stirred and mixed, 15 percent (mass concentration) oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2) 2 -ZrO 2 A mesoporous support;
0.0521g of H 2 PtCl 6 1.794mL of RuCl at a concentration of 15mg/mL 3 Solution, 0.286gMo (NO) 3 ) 4 、0.093g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Mixing O with water to obtain a soaking solution, and mixing the above-mentioned CeO 2 -ZrO 2 Immersing the mesoporous carrier into the impregnation liquid, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing ball milling for 30 minutes to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8 hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.185gNH 4 VO 3 、1.510g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants is obtained, the gas to be treated (decarbonized tail gas) is kept at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 7
10g of VOCs and reductive sulfur pollutant are prepared together to be used as the catalyst for catalytic oxidation and synergistic purification. In which CeO is present 2 、ZrO 2 The content of the active components accounts for 73wt% in total and 17wt% in total (wherein the content of Pt is 0.5wt%, the content of Ru is 0.5wt%, and V is 2 O 5 3wt% of TiO 2 Content 13 wt%), the first promoter content in the adjuvant was 3%, and the second promoter content was 7%.
Weigh 0.920g Co (NO) 3 ) 2 ·6H 2 O and 0.188g Mn (NO) 3 ) 2 、11.450g Zr(NO 3 ) 4 ·5H 2 O、10.6641g Ce(NO 3 ) 3 ·6H 2 O and pore-forming agentMixing polyethylene glycol (accounting for 10% of the mass of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants) to prepare a solution, adding 15% (mass concentration) oxalic acid solution (the volume ratio of the oxalic acid solution to the solution is 1.2) 2 -ZrO 2 A mesoporous support;
the above-mentioned CeO 2 -ZrO 2 The mesoporous support is immersed in a solution containing 0.182g of H 2 PtCl 6 4.9267ml RuCl with a concentration of 15mg/ml 3 Solution, 0.846g Mo (NO) 3 ) 4 、7.576g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Stirring and drying the soaking solution of O at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8 hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.493gNH 4 VO 3 、1.787g TiOSO 4 ·2H 2 And mixing O, dissolving in water to obtain an impregnation solution, immersing the second target product into the impregnation solution, performing low-temperature stirring and drying treatment at 40 ℃ for 7 hours, then performing drying treatment at 120 ℃ for 4 hours, roasting at 700 ℃ for 5 hours after drying, and performing drum forming to obtain the VOCs and the reductive sulfur pollutant catalytic oxidation synergistic purification catalyst.
After obtaining the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants, the gas to be treated (decarbonized tail gas) is controlled at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
Example 8
10g of VOCs and reductive sulfur pollutant are prepared together to be used as a catalyst for catalytic oxidation and synergistic purification. In which CeO is present 2 、ZrO 2 78wt% in total, and 14wt% in total of active component (wherein the Pt content is 0.8wt%, V) 2 O 5 Content 4.2wt%, tiO 2 Content 9 wt%), the first promoter content in the adjuvant is 3%, and the second promoter content is 5%.
Weigh 0.899g Co (NO) 3 ) 2 ·6H 2 O and 0.184g Mn (NO) 3 ) 2 、11.506g Zr(NO 3 ) 4 ·5H 2 O、11.6352g Ce(NO 3 ) 3 ·6H 2 O (which is 10 percent of the mass of the catalyst for catalyzing, oxidizing and synergistically purifying the VOCs and the reductive sulfur pollutants) is mixed to prepare a solution, 15 percent (mass concentration) of oxalic acid solution is added, the volume ratio of the oxalic acid solution to the solution is 1.2 2 -ZrO 2 A mesoporous support;
the above-mentioned CeO 2 -ZrO 2 The mesoporous support was immersed in a solution containing 0.142g of H 2 PtCl 6 、0.0571g RuCl 3 ，0.3584gMo(NO 3 ) 4 、0.442g(NH 4 ) 6 H 2 W 12 O 40 ·6H 2 Stirring and drying the soaking solution of O at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing ball milling for 30min to obtain uniform nanoparticle powder, namely a first target product;
dispersing the obtained nanoparticle powder in absolute ethyl alcohol, adding a polyethylene glycol thickening agent and butyl titanate, mixing to prepare a solution, stirring, performing hydrolysis precipitation by adopting an air-borne steam hydrolysis method, performing hydrothermal reaction on the obtained suspension at 150 ℃ for 4 hours to obtain a precipitate, filtering and washing the precipitate, drying at 120 ℃ for 8 hours, and roasting at 700 ℃ for 4 hours to obtain a second target product;
weigh 0.675gNH 4 VO 3 、1.211g TiOSO 4 ·2H 2 And mixing O and dissolving in water to obtain an impregnation solution, immersing a second target product into the impregnation solution, stirring and drying at a low temperature of 40 ℃ for 7 hours, then drying at a temperature of 120 ℃ for 4 hours, roasting at a temperature of 700 ℃ for 5 hours after drying, and performing rotary drum forming to obtain the catalyst for catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants.
After obtaining the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants, the gas to be treated (decarbonized tail gas) is controlled at 5000-8000 m 3 The activity of the catalyst for catalytic oxidation and synergistic purification of VOCs and reducing sulfur pollutants is determined by combustion reaction through the prepared catalyst at a flow rate of/h.
The activity of the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants prepared in the examples 1 to 8 was tested, and the reaction gas composition was simulated: VOCs at 1000ppm, reduced sulfur contaminants at 40ppm (where H) 2 S is 20ppm, COS is 10ppm, CS is 2 10 ppm), the space velocity of the reaction is 10000h -1 The results are shown in Table 1. Therefore, the invention realizes the synergistic purification of VOCs and reductive sulfur pollutants, has low cost and good selectivity, and can realize high-efficiency catalytic oxidation at a lower temperature (320 ℃).
Table 1 results of activity test of catalysts obtained in examples 1 to 8
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The catalyst for the catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants is characterized by comprising an inner layer and an outer layer, wherein the inner layer comprises a first carrier material, a first active component, a first cocatalyst and a second cocatalyst, and the outer layer comprises a second carrier material and a second active component;
the first carrier material is CeO 2 -ZrO 2 A mesoporous support, the first promoter comprising Mn oxide and/or Co oxide, the second promoter comprising MoO 3 And/or WO 3 The first active component comprises Pt and the CeO 2 -ZrO 2 The first active component, the first cocatalyst and the second cocatalyst are loaded on the mesopores and the surface of the mesoporous carrier;
the second carrier material is TiO 2 And the second active component is V 2 O 5 And the second active component is loaded on the surface of the second carrier material.
2. The catalyst of claim 1 wherein the CeO is a co-catalyst for the catalytic oxidation of VOCs and reduced sulfur contaminants 2 -ZrO 2 CeO in mesoporous carrier 2 And ZrO 2 The total content of the catalyst is 70-93 wt% of the catalytic oxidation synergistic purification catalyst for the VOCs and the reductive sulfur pollutants.
3. The catalyst for the catalytic oxidation-synergistic purification of VOCs and reduced sulfur contaminants according to claim 1 or 2, wherein the CeO 2 -ZrO 2 CeO in mesoporous carrier 2 The content of (a) is 45-50 wt%, zrO 2 The content of (A) is 50-55%.
4. The catalyst for catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants as claimed in claim 1, wherein the sum of the contents of the first active component and the second active component in the catalytic oxidation and synergistic purification of VOCs and reduced sulfur pollutants is 7-26 wt% calculated on the basis of the metal simple substance.
5. The catalyst for catalytic oxidation-synergistic purification of VOCs and reductive sulfur pollutants as claimed in claim 1 or 4, wherein the catalytic oxidation-synergistic purification of VOCs and reductive sulfur pollutants is performed with the first active componentThe content is 0.1-1 wt%, and the VOCs and the reductive sulfur pollutants are subjected to catalytic oxidation and synergistic purification and catalysis to obtain V 2 O 5 The content of (b) is 1-8 wt%, and the VOCs and the reductive sulfur pollutants are subjected to catalytic oxidation and synergistic purification catalysis to obtain TiO 2 The content of (B) is 6-20 wt%.
6. The catalyst for the catalytic oxidation-synergistic purification of VOCs and reduced sulfur contaminants of claim 1, wherein the Mn oxide is MnO 2 And/or Mn 3 O 4 。
7. The catalyst for catalytic oxidation and cooperative purification of VOCs and reducing sulfur pollutants as claimed in claim 1, wherein the content of the first promoter in the catalyst for catalytic oxidation and cooperative purification of VOCs and reducing sulfur pollutants is 1-5 wt%, and the content of the second promoter in the catalyst for catalytic oxidation and cooperative purification of VOCs and reducing sulfur pollutants is 4-10 wt%.
8. The method for preparing the catalyst for the catalytic oxidation and synergistic purification of VOCs and reductive sulfur pollutants as claimed in any one of claims 1 to 7, comprising the steps of:
mixing a first cocatalyst precursor, a Ce precursor, a Zr precursor, a pore-forming agent and oxalic acid, and carrying out a first hydrothermal reaction to obtain CeO 2 -ZrO 2 A mesoporous support;
mixing a first active component metal salt, a second cocatalyst precursor and water to obtain an impregnation liquid;
subjecting the CeO 2 -ZrO 2 Immersing the mesoporous carrier into the impregnation liquid, and sequentially performing first drying and first roasting to obtain a first target product;
mixing the first target product, ethanol, a thickening agent and a titanium precursor, carrying out hydrolysis reaction on the obtained suspension, carrying out second hydrothermal reaction, and sequentially carrying out second drying and second roasting on the obtained precipitate to obtain a second target product;
mixing the second active component metal salt and water to obtain a second active component metal salt impregnation liquid;
and immersing the second target product into the second active component metal salt impregnation liquid, and then sequentially performing third drying and third roasting to obtain the catalyst for the catalytic oxidation and synergistic purification of the VOCs and the reductive sulfur pollutants.
9. The preparation method of claim 8, wherein the pore-forming agent is polyethylene glycol or polyvinylpyrrolidone.
10. Use of the co-purification catalyst for catalytic oxidation of VOCs and reduced sulfur contaminants as claimed in any one of claims 1 to 7 or the co-purification catalyst for catalytic oxidation of VOCs and reduced sulfur contaminants as prepared by the method of claim 8 or 9 for treating decarbonized tail gas.
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| US20050081443A1 (en) * | 1999-02-08 | 2005-04-21 | Rita Aiello | Catalyst composition |
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| DE2845362A1 (en) * | 1978-10-16 | 1980-04-24 | Union Oil Co | Catalytic oxidn. of hydrogen sulphide - mixed with sec. oxidisable component, using vanadium oxide or sulphide on non-alkaline support |
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