CN118142566A - CuO-CeO2HZSM-5 composite catalyst, preparation method and application thereof - Google Patents
CuO-CeO2HZSM-5 composite catalyst, preparation method and application thereof Download PDFInfo
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- CN118142566A CN118142566A CN202211559745.2A CN202211559745A CN118142566A CN 118142566 A CN118142566 A CN 118142566A CN 202211559745 A CN202211559745 A CN 202211559745A CN 118142566 A CN118142566 A CN 118142566A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 26
- 238000006731 degradation reaction Methods 0.000 claims abstract description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- -1 anhydride compound Chemical class 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 229940014800 succinic anhydride Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 241001120493 Arene Species 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229920013822 aminosilicone Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000002468 redox effect Effects 0.000 abstract 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a CuO-CeO 2/HZSM-5 composite catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts. Firstly preparing a carboxyl modified carrier HZSM-5, then growing a Ce-based MOF on the carrier HZSM-5 with the carboxyl modified carrier, finally adsorbing copper salt solution by using the Ce-based MOF, and calcining to prepare the composite catalyst; enriched in HZSM-5The acidic sites enhance the adsorption process to CVOCs while taking advantage of the high redox properties of the metals Ce and Cu to carry out deep oxidation of the contaminants. The preparation method disclosed by the invention is mild in preparation condition, convenient to operate, environment-friendly and simple in process, and the prepared catalyst has higher catalytic activity and stability in low-temperature catalytic degradation CVOCs of organic pollutants, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a CuO-CeO 2/HZSM-5 composite catalyst, a preparation method and application thereof in low-temperature catalytic degradation CVOCs.
Background
Chlorinated volatile organic compounds (Chlorinated Volatile Organic Compounds, CVOCs) are a relatively common class of VOCs, including chlorinated alkanes, chlorinated alkenes, chlorinated arenes, and the like. Wherein, the chlorinated aromatic hydrocarbon has better chemical stability and is difficult to degrade. CVOCs is mainly used for industrial process, including petrochemical industry, fine chemical industry, medicine and pesticide manufacture, and has the characteristics of large discharge amount, strong migration capability, high toxicity, serious pollution hazard, etc. Therefore, how to eliminate CVOCs has become one of the important problems in the current environmental pollution control.
Among the numerous degradation CVOCs methods, the catalytic combustion method is an effective means for treating CVOCs, and has the characteristics of low operation temperature, low cost, high efficiency, small secondary pollution and the like. The key to this technology is the development of catalysts that are highly active at low temperatures, highly stable and do not produce more toxic by-products.
Disclosure of Invention
In view of the above, the invention aims to provide a CuO-CeO 2/HZSM-5 composite catalyst, a preparation method and application thereof in degradation CVOCs, and the CuO-CeO 2/HZSM-5 composite catalyst can catalyze and degrade CVOCs pollutants under a low temperature condition, and has the advantages of simple process, high degradation rate and low energy consumption.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A preparation method of a CuO-CeO 2/HZSM-5 composite catalyst comprises the steps of adding HZSM-5 into a solvent in which aminosilicone and an anhydride compound are dissolved, stirring for reaction, filtering, drying to obtain carboxyl modified HZSM-5, adding the carboxyl modified HZSM-5 into an aqueous solution in which Ce salt and a carboxylic acid ligand are dissolved, stirring, filtering, drying to obtain HZSM-5 carrying Ce-based MOF, adsorbing copper salt solution by the HZSM-5 carrying Ce-based MOF, and calcining to obtain the CuO-CeO 2/HZSM-5 composite catalyst.
Based on the technical scheme, the preparation method mainly comprises the following steps:
(1) Dissolving aminosiloxane and anhydride compounds in a solvent to prepare a mixed solution, adding HZSM, stirring at room temperature for reaction for 10-48 h, filtering, washing and drying to obtain carboxyl modified HZSM-5; the molar ratio of the aminosiloxane to the anhydride compound is 0.5-2.0; the solvent is one or the combination of two of N, N-dimethylformamide and N, N-dimethylacetamide; the mass ratio of the HZSM-5 to the anhydride compound is 0.02-0.50;
(2) Dissolving Ce salt and a carboxylic acid ligand in deionized water to prepare a mixed solution, adding the carboxyl modified HZSM-5 obtained in the step (1), stirring for 12-36 h at room temperature, filtering, washing and drying to obtain the Ce-based MOF-loaded HZSM-5; ce accounts for 0.05 to 0.25 of the mass of the carboxyl modified HZSM-5 carrier in the Ce-based MOF;
(3) Adding the HZSM-5 loaded with Ce-based MOF obtained in the step (2) into an ethanol-water solution dissolved with Cu salt, and stirring until the mixture is dry, wherein copper accounts for 0.01-0.05 of the mass of the HZSM-5 loaded with Ce-based MOF; calcining for 1-8 h at 300-800 ℃ in air atmosphere to obtain the CuO-CeO 2/HZSM-5 composite catalyst.
Based on the technical scheme, in the step (1), the HZSM-5 is calcined HZSM-5 zeolite with a silicon-aluminum molar ratio of 10-400; the aminosiloxane is one or the combination of more than two of 3-aminopropyl triethoxysilane or a silane coupling agent; the anhydride compound is any one or the combination of more than two of phthalic anhydride, maleic anhydride, succinic anhydride or glutaric anhydride; the concentration of the anhydride compound in the mixed solution is 0.1-2 mol/L.
Based on the technical scheme, further, the Ce salt in the step (2) is one or the combination of more than two of cerium nitrate, cerium acetate and ammonium cerium nitrate; the carboxylic acid ligand is terephthalic acid, trimesic acid or biphenyl dicarboxylic acid, and the molar ratio of Ce salt to the carboxylic acid ligand is 0.5-2.0; the concentration of Ce salt in the mixed solution is 0.01-1 mol/L; the volume of the ethanol and the water in the ethanol-water solution is 1:10-10:1.
Based on the technical scheme, further, the Cu salt in the step (3) is one or two of copper nitrate and copper acetate; the concentration of Cu salt in the ethanol-water solution is 0.01-1 mol/L.
The invention also provides the CuO-CeO 2/HZSM-5 composite catalyst prepared by the preparation method.
The invention also provides an application of the CuO-CeO 2/HZSM-5 composite catalyst in degradation CVOCs.
Based on the above technical scheme, CVOCs further comprises one or a mixture of more than two of chloralkane, chloralkene and chlorarene.
Based on the technical scheme, further, the catalyst is mixed with chlorinated aromatic hydrocarbon-containing organic pollutants after being ground or is processed and molded and then is placed in an environment containing CVOCs pollutants, and catalytic degradation is achieved through heating.
Based on the technical scheme, further, the reaction temperature is 150-400 ℃, preferably 250-350 ℃.
The invention has the following beneficial effects:
(1) The preparation condition of the CuO-CeO 2/HZSM-5 composite catalyst is mild, the preparation method is simple and feasible, the operation is convenient, and the environment is friendly.
(2) The CuO-CeO 2/HZSM-5 composite catalyst has high stability, strong poisoning resistance and simple regeneration method, and the catalyst can be reused after roasting, so that secondary pollution is avoided.
(3) The CuO-CeO 2/HZSM-5 composite catalyst disclosed by the invention realizes activation and adsorption of reactants by utilizing rich pore channels and specific acid sites of a molecular sieve material, realizes selectivity of products, and improves the dispersity of active elements by utilizing the large specific surface area of an MOF material, so that the activity of the catalyst is improved, and the prepared catalyst has higher catalytic activity and stability in the reaction of catalytically degrading chlorinated aromatic hydrocarbon organic pollutants at a low temperature and has a good application prospect.
Drawings
For a further understanding of the present invention, reference will now be made in detail to the following examples, examples of which are illustrated in the accompanying drawings, in which:
FIG. 1 is an SEM image of a CuO-CeO 2/HZSM-5 composite metal catalyst prepared in example 1;
FIG. 2 is an XRD pattern of the CuO-CeO 2/HZSM-5 composite metal catalyst prepared in example 1;
FIG. 3 is an N 2 adsorption/desorption isotherm of the CuO-CeO 2/HZSM-5 composite metal catalyst prepared in example 1.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The degradation efficiency in the following examples was calculated as follows:
R＝(C0-C)/C0*100％
R: degradation efficiency;
C 0: CVOCs initial concentrations;
c: CVOCs post-reaction concentration.
Example 1
The preparation method of the CuO-CeO 2/HZSM-5 composite catalyst mainly comprises the following steps:
(1) Dissolving 3-aminopropyl triethoxysilane and succinic anhydride in a molar ratio of 0.9 in 100mL of N, N-dimethylformamide, wherein the concentration of the succinic anhydride is 0.8mol/L, adding 1gHZSM-5 (silicon-aluminum ratio of 25), stirring at room temperature for 20h, filtering, washing, and drying the obtained powder to obtain a carboxyl modified HZSM-5 carrier;
(2) Weighing a certain amount of ceric ammonium nitrate, dissolving in water (the concentration of ceric ammonium nitrate is 0.15 mol/L), adding 1g of carboxyl modified HZSM-5, stirring, adding terephthalic acid (the molar ratio of ceric ammonium nitrate to terephthalic acid is 1.5), stirring at room temperature for 24 hours, filtering, washing, and drying to obtain a product of the product, namely the HZSM-5 loaded with Ce-based MOF, wherein Ce accounts for 0.21 of the mass of the carboxyl modified HZSM-5 carrier;
(3) A certain amount of copper nitrate is weighed and dissolved in a water-ethanol mixed solution (the volume ratio of water to ethanol is 1:5), 1g of HZSM-5 loaded with Ce-based MOF is added, wherein copper accounts for 0.027 of the mass of the Ce-based MOF loaded by the HZSM, the mixture is stirred at 50 ℃ until the mixture is completely dried, and the mixture is put into a muffle furnace for calcination at 600 ℃ for 2 hours, so that CuO-CeO 2/HZSM-5 is obtained.
The SEM, XRD and BET spectra of the obtained sample CuO-CeO 2/HZSM-5 are shown in FIGS. 1 to 3.
Example 2
The degradation effect of the catalyst was evaluated by using a fixed bed, specifically, 0.05g of the catalyst obtained in example 1 was mixed with 0.15g of SiO 2 and then packed in a fixed bed as a reaction zone, the temperature was set to 150 ℃,200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃,0.2 uL of 1, 2-dichlorobenzene was injected, and steam formed by evaporation upon heating was fed to the reaction zone by carrier gas (10% O 2+90％N2) having a flow rate of 4mL/min, and passed through the reaction zone and then entered into an adsorption zone packed with 0.60g of Florisil adsorbent, and the temperature of the adsorption zone was maintained at 30 ℃ or lower. After the reaction, the reaction medium and the adsorbent are subjected to ultrasonic extraction by adopting a normal hexane solvent, and the obtained extracting solution is subjected to filtration and volume fixing and then is analyzed by adopting GC-ECD. The degradation efficiency was calculated. Analysis and calculation show that the degradation efficiency is 77.6%,78.6%,83.7%,92.8%,99.9% and 100.0% at 150 ℃,200 ℃, 250 ℃, 300 ℃, 350 ℃ and 400 ℃.
Example 3
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: the mass ratio of HZSM-5 to succinic anhydride is 0.02. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 300 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 91.6% through analysis and calculation.
Example 4
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: the mass ratio of HZSM-5 to succinic anhydride is 0.5. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 250 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 88.9% through analysis and calculation.
Example 5
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: 1g of carboxyl modified HZSM-5 is added, ce accounts for 0.05 of the mass of the carboxyl modified HZSM-5 carrier, and the concentration of ammonium cerium nitrate is 0.04mol/L. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 250 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 85.2% through analysis and calculation.
Example 6
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: 1g of carboxyl modified HZSM-5 is added, ce accounts for 0.25 of the mass of the carboxyl modified HZSM-5 carrier, and the concentration of ammonium cerium nitrate is 0.18mol/L. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 250 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 92.1% through analysis and calculation.
Example 7
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: 1g of HZSM-5 supporting Ce-based MOF was added, wherein copper accounted for 0.01 mass of HZSM-5 supporting Ce-based MOF. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 250 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 75.0% through analysis and calculation.
Example 8
The procedure for preparing the composite metal oxide CuO-CeO 2/HZSM-5 according to example 1 was the same, except that: 1g of HZSM-5 supporting Ce-based MOF was added, wherein copper accounted for 0.05 mass of HZSM-5 supporting Ce-based MOF. The catalyst obtained was ground, 0.05g of the catalyst was mixed with 0.15g of SiO 2 and packed in a fixed bed as a reaction zone, and 0.2uL of 1, 2-dichlorobenzene was injected for reaction at 250 ℃. The residue after the reaction is extracted by normal hexane in an ultrasonic way, and the obtained extracting solution is detected and analyzed by GC-ECD, so as to calculate the degradation efficiency. The degradation efficiency is 91.0% through analysis and calculation.
Claims (10)
1. A preparation method of a CuO-CeO 2/HZSM-5 composite catalyst is characterized in that HZSM-5 is added into a solvent in which aminosilicone and an anhydride compound are dissolved, after stirring reaction, the mixture is filtered and dried to obtain carboxyl modified HZSM-5, then the carboxyl modified HZSM-5 is added into an aqueous solution in which Ce salt and a carboxylic acid ligand are dissolved, stirring, filtering and drying are carried out to obtain HZSM-5 carrying Ce-based MOF, finally the HZSM-5 carrying Ce-based MOF is subjected to copper salt adsorption solution, and calcination is carried out to obtain the CuO-CeO 2/HZSM-5 composite catalyst.
2. The preparation method according to claim 1, characterized in that the preparation method mainly comprises the following steps:
(1) Dissolving aminosiloxane and anhydride compounds in a solvent to prepare a mixed solution, adding HZSM, stirring at room temperature for reaction for 10-48 h, filtering, washing and drying to obtain carboxyl modified HZSM-5; the molar ratio of the aminosiloxane to the anhydride compound is 0.5-2.0; the solvent is one or the combination of two of N, N-dimethylformamide and N, N-dimethylacetamide; the mass ratio of the HZSM-5 to the anhydride compound is 0.02-0.50;
(2) Dissolving Ce salt and a carboxylic acid ligand in deionized water to prepare a mixed solution, adding the carboxyl modified HZSM-5 obtained in the step (1), stirring at room temperature, filtering, washing and drying to obtain Ce-based MOF-loaded HZSM-5; ce accounts for 0.05 to 0.25 of the mass of the carboxyl modified HZSM-5 carrier in the Ce-based MOF;
(3) Adding the HZSM-5 loaded with Ce-based MOF obtained in the step (2) into an ethanol-water solution dissolved with Cu salt, and stirring until the mixture is dry, wherein copper accounts for 0.01-0.05 of the mass of the HZSM-5 loaded with Ce-based MOF; calcining for 1-8 h at 300-800 ℃ in air atmosphere to obtain the CuO-CeO 2/HZSM-5 composite catalyst.
3. The process according to claim 1, wherein the HZSM-5 in step (1) is calcined HZSM-5 zeolite having a molar ratio of silica to alumina of 10 to 400; the aminosiloxane is one or the combination of more than two of 3-aminopropyl triethoxysilane or a silane coupling agent; the anhydride compound is any one or the combination of more than two of phthalic anhydride, maleic anhydride, succinic anhydride or glutaric anhydride; the concentration of the anhydride compound in the mixed solution is 0.1-2 mol/L.
4. The preparation method according to claim 1, wherein the Ce salt in the step (2) is one or a combination of two or more of cerium nitrate, cerium acetate and ammonium cerium nitrate; the carboxylic acid ligand is terephthalic acid, trimesic acid or biphenyl dicarboxylic acid, and the molar ratio of Ce salt to the carboxylic acid ligand is 0.5-2.0; the concentration of Ce salt in the mixed solution is 0.01-1 mol/L; the volume of the ethanol and the water in the ethanol-water solution is 1:10-10:1.
5. The method according to claim 1, wherein the Cu salt in the step (3) is one or both of copper nitrate and copper acetate; the concentration of Cu salt in the ethanol-water solution is 0.01-1 mol/L.
6. The CuO-CeO 2/HZSM-5 composite catalyst prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the CuO-CeO 2/HZSM-5 composite catalyst according to claim 6 for degradation CVOCs.
8. The use according to claim 7, wherein CVOCs comprises one or a mixture of two or more of chlorinated alkanes, chlorinated alkenes, chlorinated arenes.
9. The method according to claim 7, wherein the catalyst is ground, mixed with organic pollutant containing chlorinated aromatic hydrocarbon or processed and formed, and then placed in environment containing CVOCs pollutant, and heated to realize catalytic degradation.
10. Use according to claim 7, characterized in that the reaction temperature is 150-400 ℃, preferably 250-350 ℃.
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