CN111135816A - Catalyst for catalytic combustion of chlorine-containing volatile organic gas and preparation method thereof - Google Patents
Catalyst for catalytic combustion of chlorine-containing volatile organic gas and preparation method thereof Download PDFInfo
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- CN111135816A CN111135816A CN201911373051.8A CN201911373051A CN111135816A CN 111135816 A CN111135816 A CN 111135816A CN 201911373051 A CN201911373051 A CN 201911373051A CN 111135816 A CN111135816 A CN 111135816A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000000460 chlorine Substances 0.000 title claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 28
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 27
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 80
- 238000001035 drying Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000012065 filter cake Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 150000001804 chlorine Chemical class 0.000 abstract description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 33
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
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Abstract
The invention discloses a catalyst for catalytic combustion of chlorine-containing volatile organic gases, which comprises composite oxide TiO2‑SiO2The carrier is a composite metal oxide M-Ce-O as an active component, wherein M is one of La, Zr and Ca. First of all by means of TiO2‑SiO2As a composite support, TiO2Can provide a certain surface acidity site, and SiO2Can promote TiO on the surface of the catalyst2The catalyst has higher structural strength and is reduced from mechanical damage such as abrasion, vibration and the likeThe possibility. Secondly, M can form a solid solution with Ce, enabling the enlargement of CeO2Thereby increasing the degree of lattice defect of CeO2The oxygen vacancy provides more active oxygen species in the reaction process, reduces the ignition temperature of catalytic combustion, further is beneficial to improving the activity of the catalyst, and can reduce the generation possibility of dioxin. Furthermore, M can also play a role in protecting Ce and avoid CeO which is a main active component2And the chlorine is lost when producing chlorine salt with chlorine element. Moreover, the preparation method is simple and suitable for large-scale production.
Description
Technical Field
The invention relates to the field of air pollution prevention and control, in particular to a catalyst for catalytic combustion of chlorine-containing volatile organic gases and a preparation method thereof, which aims at purifying industrial waste gas containing volatile organic compounds.
Background
The emission of industrial Organic waste gas has become an important source of composite air pollution in China, and the main pollution components of the industrial Organic waste gas are Volatile Organic Compounds (VOCs) including benzene series, aldehydes, ketones, halogenated hydrocarbons and the like. These substances can be produced in various production steps of printing and dyeing, agriculture, agricultural chemicals, medicines, organic synthesis and other industries. Among all VOCs, chlorine-containing volatile organic compounds (Cl-VOCs) have stable structures, are difficult to biodegrade, are easy to accumulate in organisms, have strong carcinogenic, teratogenic and mutagenic 'triple-causing' effects, and have attracted close attention of the whole society for purification.
The catalytic combustion method can efficiently purify Cl-VOCs at a lower temperature than the direct combustion of the Cl-VOCs by the activation effect of the catalyst, and becomes a mainstream technology in the field of Cl-VOCs treatment. At the same time, however, the active components of these catalysts are generally composed of noble metals and metal oxides. For example, chinese patent application No. 201810094573.3 discloses a catalyst in which an iron source, a manganese source, and a cerium source are mainly used as raw materials for preparing an active material. For another example, application No. 201410209004.0 discloses a catalyst, whose main active components are cerium oxide and ruthenium metal, which can convert chlorine-containing volatile organic gases into CO2And treated inorganic gases such as HCl.
Although the two catalysts can effectively purify chlorine-containing volatile organic gases, in the combustion process of chlorine-containing volatile organic gases, chlorine easily reacts with active components such as iron element, manganese element, cerium element, ruthenium element and the like in the catalysts, so that the problems of catalyst Cl poisoning and even active component loss are caused, and the activity and the service life of the catalysts are seriously influenced. Therefore, it is necessary to develop a catalytic combustion catalyst with less loss of active substances and strong poisoning resistance.
Disclosure of Invention
The invention aims to provide a catalyst for catalytic combustion of chlorine-containing volatile organic gases, which has strong poisoning resistance and capability of reducing loss of active components and is beneficial to prolonging the service life of the catalyst.
The above object of the present invention is achieved by the following technical solutions: a catalyst for catalytic combustion of the volatile organic gas containing Cl is prepared fromOxide TiO2-SiO2The carrier is a composite metal oxide M-Ce-O as an active component, wherein M is one of La, Zr and Ca.
By adopting the technical scheme, firstly, the composite oxide TiO is utilized2-SiO2As the carrier, the carrier can ensure that the carrier has higher structural strength while providing a certain surface acid site, thereby being beneficial to improving the mechanical property of the catalyst and reducing the possibility of mechanical damage to the catalyst.
Second, at Ce02In which M is added to increase CeO2To cause CeO2The oxygen vacancy is increased, so that the temperature of catalytic combustion can be obviously reduced, and the activity of the catalyst is favorably improved. Moreover, as the temperature of catalytic combustion decreases, it also decreases the probability of chlorine reacting with metal elements. Moreover, M metal can play a role in protecting Ce, and the loss caused by the production of chloride by main active components of CeO and chlorine is avoided.
Preferably, the M-Ce-O accounts for 25-45% of the total mass of the catalyst.
By adopting the technical scheme, when the M-Ce-O accounts for 25-45% of the total mass of the catalyst, the catalyst surface is distributed in a monoatomic layer, so that the acid sites and the reaction sites on the catalyst surface can be in full contact with Cl-VOCs molecules in the waste gas, and the improvement of the purification treatment of the gas containing Cl-VOCs is facilitated.
Preferably; SiO 22Accounting for 45-55% of the total mass of the carrier.
Preferably, the active component also comprises 5 wt% of CoO.
By adopting the technical scheme, the grain size of CoO generated in the reaction process can be gradually reduced, so that the CoO is uniformly released to the surface of the carrier and is highly dispersed, and the CeO can be filled up2The space without oxygen vacancy further increases the number of oxygen vacancies on the catalyst, and enhances the catalytic combustion effect.
A preparation method of a catalyst for catalytic combustion of chlorine-containing volatile organic gases comprises the following steps:
the method comprises the following steps: dissolving a certain amount of Ti (SO) in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving a certain amount of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration of the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: weighing a certain amount of Ce (NO) according to the mass ratio3)3·6H2O，M(NO3)x·nH2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step one into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: putting the gel F into a drying oven, drying for 24 hours at 110 ℃, and then putting into a muffle furnace for burning; roasting at 500 ℃ for 5h to prepare the catalyst M-Ce-O/TiO2-SiO2；
Step six: weighing Co (NO) with corresponding mass according to requirements3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G;
step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Aging the mixture for 12 hours in an inert gas environment, drying the mixture at 110 ℃ overnight, and roasting the dried mixture for 3 hours at 500 ℃ to prepare the catalyst Co/M-Ce-O/TiO2-SiO2。
By adopting the technical scheme, the heating is carried out by utilizing the oil bath, so that the raw materials are favorably and uniformly heated, and the normal operation of the reaction is further ensured.
Preferably, in the step seven, the aging process is performed by ultraviolet irradiation, and the intensity of the ultraviolet is controlled to be 100-200 uW/cm2。
By adopting the technical scheme, the ultraviolet irradiation aging is utilized, on one hand, the degradation of the organic solvent can be facilitated, the influence on the forming of the catalyst due to the volatilization of the organic solvent in the roasting process is reduced, on the other hand, the ultraviolet irradiation also facilitates the precuring of the catalyst, and the probability of the fragmentation in the catalyst carrying process is reduced.
Preferably, in the fifth step, before the gel F is roasted, the gel F is placed in a vacuum-pumping environment for 30min, and the absolute pressure is-0.1 MPa.
Through adopting above-mentioned technical scheme, place gel F in the evacuation environment, can detach air and surface water in the gel F like this to be favorable to guaranteeing that the final catalyst that becomes can be homogeneous stable, avoid local appear the thickness too thin and take place the breakage.
Preferably, the roasting temperature in the fifth step is firstly increased from the normal temperature to 200 ℃ at the speed of 2 ℃/min, the temperature is kept for 30min, then is increased to 320 ℃ at the speed of 2 ℃/min, the temperature is kept for 30min, and then is increased to 500 ℃ at the speed of 10 ℃/min to be roasted for 5 hours.
Through adopting above-mentioned technical scheme, rise to 200 ℃ earlier the temperature, be favorable to like this that the bound water in the gel G can distribute out from the raw materials with the mode of steam to avoid catalyst raw materials in 500 ℃ of solidification process, steam distributes out from inside again, and destroys the crystal structure of final catalyst, and then influences the structural strength and the catalytic efficiency of catalyst.
In the calcining process, the temperature is increased from normal temperature to 200 ℃ at the speed of 2 ℃/min, so that the citric acid in the catalyst synthesis raw material can be fully combusted within the range of 170-200 ℃, and the phenomenon that the citric acid is carbonized due to too fast heating to generate carbon deposition attached to the catalyst and influence the physical characteristics, such as the specific surface area, the pore structure and the like, the catalytic efficiency and the service life of the calcined catalyst is avoided. Meanwhile, the temperature is raised to 320 ℃ for heat preservation, which is to effectively remove nitrate ions, so that the final catalyst can meet the requirement of environmental protection.
Preferably, the heating is carried out by microwave in the roasting process, and the frequency of the microwave is controlled between 10GHz and 20 GHz.
By adopting the technical scheme, the microwave heating is utilized to ensure that the inside and the outside of the raw material can be synchronously and slowly heated, so that the condition that the catalyst module structure is uneven and even has deformation, cracks and other adverse sites caused by overlarge inside and outside temperature difference and different expansion type variables in the external curing process, and the structural strength of the final forming of the catalyst is influenced is avoided.
In conclusion, the beneficial technical effects of the invention are as follows:
1. in CeO2Doping with M element, which is effective in increasing CeO2The oxygen vacancy on the surface is favorable for improving the treatment efficiency of the chlorine-containing gas, the temperature of catalytic combustion can be reduced, the probability of generating chlorine salt by chlorine element and metal element is reduced, and the loss of the metal element is reduced;
2. with compound oxide TiO2-SiO2As a carrier, the catalyst can ensure that the carrier has higher structural strength while providing a certain surface acid site, thereby being beneficial to improving the mechanical property of the catalyst and reducing the possibility of mechanical damage to the catalyst;
3. co is added into the catalyst, and the grain size of the Co is gradually reduced in the reaction process, so that the Co is uniformly released to the surface of the carrier and is highly dispersed, and the Co can be used for filling CeO2There is no space for oxygen vacancy to improve the purification effect of chlorine-containing gas.
Detailed Description
Example A1
The method comprises the following steps: 101.37g of Ti (SO) were dissolved in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving 143.04g of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration in the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to formForming a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: 32.79g of Ce (NO) are weighed3)3·6H2O, 15.95g of La (NO)3)3·6H2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step two into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: placing the gel in a vacuum environment for 30min under the absolute pressure of-0.1 Mpa, placing the gel F in a drying oven, drying at 110 ℃ for 24h, placing in a muffle furnace, heating the muffle furnace by 10-20 GHz microwave, heating to 200 ℃/min at 2 ℃/min from normal temperature, keeping the temperature for 30min, heating to 320 ℃ at 2 ℃/min, keeping the temperature for 30min, heating to 500 ℃ at 10 ℃/min, and roasting at 500 ℃ for 5h to prepare the catalyst La-Ce-O/TiO2-SiO2。
Example A2
This example differs from example A1 in that 133.50g of ethyl orthosilicate, Ti (SO)4)294.61g additionally, step six: 19.42g of Co (N0) were weighed out3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G;
step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Using 100-200 uW/cm2Irradiating by ultraviolet rays, aging for 12h in a helium environment, drying at 110 ℃ overnight, then placing the aged raw materials in a muffle furnace, heating the muffle furnace from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, heating to 500 ℃ at a speed of 10 ℃/min, and roasting at 500 ℃ for 3h to prepare the catalyst Co/La-Ce-O/TiO2-SiO2。
Example B1
The method comprises the following steps: 97.62g of Ti (SO) was dissolved in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving 112.70g of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration of the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: 45.40g of Ce (NO) are weighed3)3·6H2O, 22.59g of La (NO)3)3·6H20 and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-200r/min to form a solution E with the metal cation concentration of 0.1 mol/L:
step four: crushing the filter cake D dried in the step two into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: placing the gel in a vacuum environment for 30min under an absolute pressure of-0.1 Mpa, placing the gel F in a drying oven, drying at 110 ℃ for 24h, placing in a muffle furnace, heating with 10-20 GHZ microwave from normal temperature to 200 ℃/min at 2 ℃/min, keeping the temperature for 30min, and then placing the gel F in the drying ovenHeating to 320 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 500 ℃ at the speed of 10 ℃/min, and roasting at 500 ℃ for 5h to prepare the catalyst La-Ce-O/TiO2-SiO2。
Example B2
This example differs from example B1 in that 104.03g of ethyl orthosilicate, Ti (SO)4)290.11g otherwise, step six: 19.42g of Co (N0) were weighed out3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G;
step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Using 100-200 uW/cm2Irradiating by ultraviolet rays, aging for 12h in a helium environment, drying at 110 ℃ overnight, then placing the aged raw materials in a muffle furnace, heating the muffle furnace from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, heating to 500 ℃ at a speed of 10 ℃/min, and roasting at 500 ℃ for 3h to prepare the catalyst Co/La-Ce-O/TiO2-SiO2。
Example C1
The method comprises the following steps: 90.86g of Ti (SO) were dissolved in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving 85.82g of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration of the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: 58.01g of Ce (NO) was weighed3)3·6H2O, 29.24g of La (NO)3)3·6H2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step two into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: placing the gel in a vacuum environment for 30min under the absolute pressure of-0.1 Mpa, placing the gel F in a drying oven, drying at 110 ℃ for 24h, placing in a muffle furnace, heating the muffle furnace by 10-20 GHz microwave, heating to 200 ℃/min at 2 ℃/min from normal temperature, keeping the temperature for 30min, heating to 320 ℃ at 2 ℃/min, keeping the temperature for 30min, heating to 500 ℃ at 10 ℃/min, and roasting at 500 ℃ for 5h to prepare the catalyst La-Ce-O/TiO2-SiO2。
Example C2
This example differs from example C1 in that 78.02g of ethyl orthosilicate, Ti (SO)4)282.60g additionally, step six: 19.42g of Co (N0) were weighed out3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G;
step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Using 100-200 uW/cm2Irradiating by ultraviolet rays, aging for 12h in a helium environment, drying at 110 ℃ overnight, then placing the aged raw materials in a muffle furnace, heating the muffle furnace from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, heating to 500 ℃ at a speed of 10 ℃/min, and roasting at 500 ℃ for 3h to prepare the catalyst Co/La-Ce-O/TiO2-SiO2。
Example D1
The method comprises the following steps: 90.86g of Ti (SO) were dissolved in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving 85.82g of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration in the solution A and the solution B is 0.1mol/L,dropwise adding the solution A into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: 45.40g of Ce (NO) are weighed3)3·6H2O, 59.23g of Zr (NO)3)4·5H2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step two into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: placing the gel in a vacuum environment for 30min under the absolute pressure of-0.1 Mpa, placing the gel F in a drying oven, drying at 110 ℃ for 24h, placing in a muffle furnace, heating the muffle furnace by 10-20 GHz microwave, heating to 200 ℃/min at 2 ℃/min from normal temperature, keeping the temperature for 30min, heating to 500 ℃ at 10 ℃/min, and roasting at 500 ℃ for 5h to prepare the catalyst Zr-Ce-O/TiO2-SiO2。
Example D2
This example differs from example D1 in that 104.03g of ethyl orthosilicate, Ti (SO)4)290.11 g; in addition, step six: 19.42g of Co (NO) are weighed3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G; step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Using 100-200 uW/cm2Irradiating by ultraviolet rays, aging for 12h in a helium environment, drying at 110 ℃ overnight, then placing the aged raw materials in a muffle furnace, heating the muffle furnace from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, heating to 500 ℃ at a speed of 10 ℃/min, and roasting at 500 ℃ for 3h to prepare the catalyst Co/Zr-Ce-O/TiO2-SiO2。
Example E1
The method comprises the following steps: 97.62g of Ti (SO) was dissolved in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving 112.70g of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration of the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: 45.40g of Ce (NO) are weighed3)3·6H2O, 71.59g of Ca (NO)3)2·4H2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step two into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: placing the gel in a vacuum environment for 30min under the absolute pressure of-0.1 Mpa, placing the gel F in a drying oven, drying at 110 ℃ for 24h, placing in a muffle furnace, heating with 10-20 GHZ microwave in the muffle furnace, heating to 200 ℃/min at 2 ℃/min from normal temperature, keeping the temperature for 30min, heating to 320 ℃ at 2 ℃/min, and keeping the temperature for 30minThen heating to 500 ℃ at a speed of 10 ℃/min, and roasting for 5 hours at 500 ℃ to prepare the catalyst Ca-Ce-O/TiO2-SiO2。
Example E2
This example differs from example E1 in that 104.03g of ethyl orthosilicate, Ti (SO)4)290.11 g; in addition, step six: 19.42g of Co (N0) were weighed out3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G; step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Using 100-200 uW/cm2Irradiating by ultraviolet rays, aging for 12h in a helium environment, drying at 110 ℃ overnight, then placing the aged raw materials in a muffle furnace, heating the muffle furnace from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, heating to 500 ℃ at a speed of 10 ℃/min, and roasting at 500 ℃ for 3h to prepare the catalyst Co/Ca-Ce-O/TiO2-SiO2。
Comparative example one:
this comparative example differs from example B2 in that La (NO) is not added3)3·6H2O。
Comparative example two:
the comparative example differs from example B2 in that it has not been UV aged.
Comparative example three:
the difference between the present team's scale and example B2 is that step three directly warms the muffle to 500 ℃.
Comparative example four:
the difference between the present team scale and example B2 is that step three is directly heating the muffle by conventional means.
Example a1, example a2, example B1, example B2, example C1, example C2, example D1, example D2, example E1 and example E2, and comparative examples one to four were tested according to the following test methods:
the test method comprises the following steps:
1. the prepared solution contains 1000ppm of methane chloride and 1000ppm of methane chlorideIntroducing chloroethylene, 1000ppm chlorobenzene and other organic mixed gas which is air into a reaction kettle filled with a catalyst, controlling the reaction temperature of the reaction kettle to be 300-350 ℃, and controlling the flow velocity of air flow to be 5m3Detecting the content/ppm of methane chloride, vinyl chloride and chlorobenzene in tail gas;
2. carrying out compressive strength test/Mpa on the catalyst by using a pressure tester;
3. the prepared catalyst is observed to be cracked;
4. weighing the initial mass of the catalyst and the mass/g after 24h of catalytic combustion;
5. test outlet Cl2And overall conversion of HCl/%)
The test results are shown in table one:
watch 1
As can be seen from the above table, the present application is based on TiO2-SiO2As a carrier, the catalyst has stronger compressive strength. Secondly, the comparison between examples B1 and B2 and examples D1, D2, E1, E2 and comparative example I shows that when M is La, the catalyst has stronger effect of catalyzing chlorine-containing gas and less loss of the catalyst. Furthermore, as can be seen from a comparison of example B2 with comparative example B, the aging operation is beneficial to increasing the catalytic efficiency of the catalyst. As can be seen from the comparison between the example B2 and the third and fourth comparative examples, the microwave stage heating of the catalyst for increasing the temperature is beneficial to ensuring the structural strength of the catalyst and reducing the probability of the catalyst cracking.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. Is used forThe catalyst for catalytic combustion of chlorine-containing volatile organic gas is characterized in that: comprises the compound oxide TiO2-SiO2The carrier is a composite metal oxide M-Ce-O as an active component, wherein M is one of La, Zr and Ca.
2. The catalyst for catalytic combustion of chlorine-containing volatile organic gases as claimed in claim 1, wherein: the M-Ce-O accounts for 25-45% of the total mass of the catalyst.
3. The catalyst for catalytic combustion of chlorine-containing volatile organic gases as claimed in claim 1, wherein: SiO 22Accounting for 45-55% of the total mass of the carrier.
4. The catalyst for catalytic combustion of chlorine-containing volatile organic gases according to claim 1 or 2, wherein: the active component also comprises 5 wt% of CoO.
5. The method for preparing the catalyst for catalytic combustion of chlorine-containing volatile organic gases according to any one of claims 1 to 4, wherein the method comprises the following steps: comprises the following steps of (a) carrying out,
the method comprises the following steps: dissolving a certain amount of Ti (SO) in 10 wt% dilute sulfuric acid4)2Obtaining a solution A, and dissolving a certain amount of tetraethoxysilane in absolute ethyl alcohol to obtain a solution B; the solute concentration of the solution A and the solution B is 0.1mol/L, and the solution A is dripped into the solution B to form a mixed solution C;
step two: slowly dropwise adding 20% ammonia water into the mixed solution C until the pH value of the solution is 9-13 and a precipitate is formed, filtering the precipitate, taking out, repeatedly washing with deionized water, and performing suction filtration at-0.1 MPa negative pressure by using a vacuum pump until Ba (NO) is added into the supernatant obtained after suction filtration3)2Detection of absence of residual SO4 in the wash liquor2-Obtaining a filter cake D, putting the filter cake D into a drying oven, and drying for 24 hours at 110 ℃;
step three: weighing a certain amount according to the mass ratioCe (NO) of3)3·6H2O，M(NO3)x·nH2O and C6H8O7·H2Dissolving O powder in deionized water, and magnetically stirring for 3 hours at the rotating speed of 100-;
step four: crushing the filter cake D dried in the step one into powder of 60-100 meshes, placing the powder into the solution E, and placing the solution E added with the powder into an oil bath at 80 ℃ for magnetic stirring for 6 hours at the rotating speed of 600r/min for 400-;
step five: putting the gel F into a drying oven, drying for 24 hours at 110 ℃, and then putting into a muffle furnace for burning; roasting at 500 ℃ for 5h to prepare the catalyst M-Ce-O/TiO2-SiO2；
Step six: weighing Co (N0) with corresponding mass according to requirements3)2·6H2O and C6H8O7·H2Dissolving O in deionized water to form 0.1mol/L solution G;
step seven: dipping the catalyst M-Ce-O/TiO prepared in the step five with corresponding mass into the solution G2-SiO2Aging the mixture for 12 hours in an inert gas environment, drying the mixture at 110 ℃ overnight, and roasting the dried mixture for 3 hours at 500 ℃ to prepare the catalyst Co/M-Ce-O/TiO2-SiO2。
6. The method for preparing the catalyst for catalytic combustion of chlorine-containing volatile organic gases according to claim 5, wherein the method comprises the following steps: in the seventh step, the aging process is performed by ultraviolet irradiation, and the intensity of the ultraviolet irradiation is controlled to be 100-200 uW/cm2。
7. The method for preparing the catalyst for catalytic combustion of chlorine-containing volatile organic gases according to claim 5, wherein the method comprises the following steps: and step five, before the gel F is roasted, placing the gel F in a vacuum-pumping environment for 30min, wherein the absolute pressure is-0.1 MPa.
8. The method for preparing the catalyst for catalytic combustion of chlorine-containing volatile organic gases according to claim 5, wherein the method comprises the following steps: and fifthly, raising the temperature of the roasting in the step five from the normal temperature to 200 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, then raising the temperature to 320 ℃ at a speed of 2 ℃/min, preserving the heat for 30min, and then raising the temperature to 500 ℃ at a speed of 10 ℃/min, and calcining for 5 h.
9. The method for preparing the catalyst for catalytic combustion of chlorine-containing volatile organic gases according to claim 8, wherein the method comprises the following steps: the roasting process is carried out by microwave, and the power of the microwave is controlled between 10GHz and 20 GHz.
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| CN114832859B (en) * | 2022-06-07 | 2024-02-20 | 浙江天蓝环保技术股份有限公司 | CVOCs purifying catalyst and preparation method thereof |
| CN116272980A (en) * | 2023-03-29 | 2023-06-23 | 昆明理工大学 | Anti-poisoning catalyst and preparation method and application thereof |
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Application publication date: 20200512 |