CN110586073B - Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof - Google Patents

Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof Download PDF

Info

Publication number
CN110586073B
CN110586073B CN201911009509.1A CN201911009509A CN110586073B CN 110586073 B CN110586073 B CN 110586073B CN 201911009509 A CN201911009509 A CN 201911009509A CN 110586073 B CN110586073 B CN 110586073B
Authority
CN
China
Prior art keywords
catalyst
solution
dioxin
catalytic oxidation
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911009509.1A
Other languages
Chinese (zh)
Other versions
CN110586073A (en
Inventor
唐志诚
赵海军
张国栋
韩维亮
董芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN201911009509.1A priority Critical patent/CN110586073B/en
Publication of CN110586073A publication Critical patent/CN110586073A/en
Application granted granted Critical
Publication of CN110586073B publication Critical patent/CN110586073B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention provides a catalyst for catalytic oxidation elimination of dioxin pollutants in kiln smoke and waste gas of garbage incinerators, hazardous waste incinerators, medical waste incinerators, steel sintering furnaces, coal-fired power plants, funeral parlours and chemical plants and a preparation method thereof. The catalyst uses industrial titanium dioxide as a carrier, SnO2‑V2O5‑WO3The composite oxide is used as an active component, La2O3、MoO3、CeO2、Nb2O5、CuO、Pr6O11And Sb2O3Is an auxiliary agent. In the catalyst prepared by the invention, the active component is uniformly dispersed on the surface of the carrier under the complexing action of organic amine, and the catalyst auxiliary agent is uniformly precipitated on the surface of the carrier under the condition of ammonia water, so that the catalyst has high specific surface, high thermal stability and stronger chlorine poisoning resistance, can continuously run for a long time without activation, and has low activation temperature and high dioxin decomposition efficiency in dioxin pollutant elimination.

Description

Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof
Technical Field
The invention relates to a catalyst for eliminating dioxin and a preparation method thereof, in particular to a catalyst for eliminating dioxin in kiln flue gas through catalytic oxidation and a preparation method thereof, and belongs to the field of catalysts and the field of environmental protection.
Background
Dioxin has the characteristics of stable chemical property, good thermal stability, difficult biodegradation and the like, can be accumulated in the environment for a long time, and causes serious harm to organisms and the environment. Dioxin is mainly derived from various human living and production activities, including household garbage incineration, hazardous waste and medical waste incineration, animal carcass incineration treatment, steel sintering (pelletizing) plants, non-ferrous metal smelting, paper pulp and paper making, chemical products, pesticide production and other industries.
Dioxin treatment techniques are numerous and include adsorption, condensation, membrane separation, direct combustion, plasma, photocatalytic, biological, and catalytic oxidation. Among them, the activated carbon adsorption technique in the adsorption method is currently widely used industrially due to its simple operation mode and low single investment cost. However, the activated carbon adsorption technology has the defects of high long-term operation cost and incomplete low-concentration dioxin treatment, so that the activated carbon adsorption technology is redundant and insufficient to the existing standard. In addition, the activated carbon adsorption only seals pollutants such as dioxin in the activated carbon pore canal, so that the dioxin is not really eliminated from the environment, and the activated carbon adsorbing the dioxin has the risk of secondary pollution.
Compared with the activated carbon adsorption technology, the method for eliminating dioxin through catalytic oxidation is to directly decompose and convert dioxin in flue gas into water, carbon dioxide and hydrogen chloride which are non-toxic or have small toxicity, and the method for eliminating dioxin through catalytic oxidation has the characteristics of high treatment efficiency, low later-stage operation cost, easiness in engineering and the like, and is the next generation dioxin elimination technology which is hopeful to replace activated carbon adsorption. The catalysts used for removing dioxin by the catalytic oxidation method mainly comprise three types of noble metal catalysts, molecular sieve catalysts and transition metal oxide catalysts (CN 101693198A, CN101733107 and CN 105107517). CN104226301 discloses a rare earth-based composite multi-component denitration and dioxin removal catalyst. CN102068905 discloses a catalyst for removing dioxin of VWTi honeycomb monomer by vanadium oxalate secondary impregnation, and the preparation of the catalyst needs secondary impregnation, secondary drying and roasting. In addition, CN106732544 reports a dioxin removal catalyst using montmorillonite and titanium dioxide as carriers. However, the dioxin removal catalysts reported in these patents are converted from selective catalytic reduction removal catalysts for nitrogen oxides, and when used for dioxin removal, there are problems that the decomposition temperature of dioxin is high or the emission content of dioxin after treatment does not reach the national standard. In other patents, noble metals or other substances are used as or sexual components, the preparation cost of the catalyst is high, or the reported preparation method of the catalyst is complicated, so that the industrial production and application cannot be really carried out.
Disclosure of Invention
The invention aims to provide a catalyst for removing dioxin pollutants through catalytic oxidation, which has high low-temperature activity and good stability and is easy to industrially produce, and a preparation method thereof, aiming at solving the problems that the existing catalyst for removing dioxin pollutants has high decomposition temperature and low decomposition efficiency and is difficult to industrially produce.
The catalyst for eliminating dioxin in kiln flue gas by catalytic oxidation comprises a catalyst carrier, an active component and an auxiliary agent, wherein the catalyst carrier is industrial titanium dioxide and accounts for 74-91% of the total mass of the catalyst; the active component of the catalyst is SnO2-V2O5-WO3The composite oxide accounts for 5.5-23% of the total mass of the catalyst; the catalyst auxiliary agent is La2O3、MoO3、CeO2、Nb2O5、CuO、Pr6O11And Sb2O3At least one of them, and accounts for 0.1-3.0% of the total mass of the catalyst.
The active component SnO of the catalyst2-V2O5-WO3In the composite oxide, SnO2Accounts for 0.5-4.0% of the total mass of the catalyst, and V2O52.0-9.0% of the total mass of the catalyst, and WO3Accounting for 3.0-10.0% of the total mass of the catalyst.
The preparation method of the catalyst for eliminating dioxin in kiln flue gas by catalytic oxidation comprises the following steps:
(1) completely dissolving precursors of active components of tin, vanadium and tungsten of the catalyst in a deionized water-organic amine mixed solution under vigorous stirring, and marking the solution as A solution; the tin precursor is stannous chloride or stannic chloride, and the vanadium precursor is ammonium metavanadate, vanadyl oxalate or vanadyl sulfate; the tungsten precursor is ammonium metatungstate or ammonium paratungstate. The mass of the deionized water is 5.0-15.0 times of that of the precursors of tin, vanadium and tungsten; the organic amine is one or more of monoethanolamine, diethanolamine, triethanolamine or formamide, and the mass of the organic amine is 0.5-4.5 times that of the precursors of tin, vanadium and tungsten;
(2) adding the catalyst carrier industrial titanium dioxide into the solution A, stirring the mixture fully and uniformly, and marking the mixture as a solution B;
(3) the catalyst promoter was dissolved in deionized water and labeled as solution C. The using amount of the deionized water is 1.0-8.0 times of the total mass of the precursors of the tin, the vanadium and the tungsten;
(4) and slowly adding the solution C and ammonia water into the solution B under vigorous stirring to uniformly mix, and marking as a solution D. Wherein the adding amount of ammonia water is 0.1-3.0 times of the total mass of the precursors of tin, vanadium and tungsten;
(5) heating the solution D in a water bath to 30-60 ℃, and stirring for 2-8 hours to form paste; and drying the paste, and then calcining the paste in a muffle furnace at high temperature to obtain the catalyst. Drying is carried out in a forced air drying oven at the temperature of 80-100 ℃ for 12-24 hours; the calcination is carried out at 300-600 ℃ for 3-10 hours.
Compared with the prior art, the invention has the following advantages:
1. in the catalyst prepared by the invention, the active component is uniformly dispersed on the surface of the carrier under the complexing action of organic amine, and the catalyst auxiliary agent is uniformly precipitated on the surface of the carrier under the condition of ammonia water, so that the catalyst has high specific surface, high thermal stability and strong chlorine poisoning resistance, and can continuously run for a long time without activation;
2. the catalyst has low activation temperature and high decomposition efficiency of dioxin during the elimination of dioxin pollutants, can treat dioxin with different concentrations, and has the dioxin content in a flue gas outlet lower than 0.1 ng TEQ/Nm3；
3. The catalyst is easy to form and can be prepared into honeycomb, granular and clover forms according to the use requirement;
4. the catalyst does not contain noble metal, and the raw materials are cheap and easy to obtain; the preparation method is simple, has lower cost and is easy to implement in industrial production;
5. the catalyst of the invention can be used for the catalytic oxidation elimination of dioxin pollutants and the removal of other chlorine-containing volatile organic pollutants in flue gas, so that the content of dioxin pollutants at the outlet of the flue gas or waste gas is lower than the national emission standard when the catalyst is used for the treatment of the flue gas or waste gas.
Drawings
FIG. 1 is a graph showing catalytic oxidation elimination activity of dioxin analog o-dichlorobenzene on the catalysts of examples 1 to 3.
FIG. 2 is a graph showing the catalytic oxidation elimination activity of the dioxin analog o-dichlorobenzene on the catalysts of examples 4 to 7.
FIG. 3 is a graph showing the catalytic oxidation elimination activity of the dioxin analog o-dichlorobenzene on the catalysts of examples 8 to 10.
Detailed Description
The composition and preparation of the catalyst of the invention are further illustrated by the following specific examples.
Example 1
(1) Fully dissolving 0.64g of ammonium metavanadate, 0.54 g of ammonium metatungstate and 0.35 g of stannic chloride in a mixed solution of 10 g of deionized water and 3 g of monoethanolamine, and marking as a solution A;
(2) adding 8.75 g of titanium dioxide into the solution A, and fully and uniformly dispersing to obtain a solution B;
(3) adding 0.12 g of ammonium molybdate into 3 g of deionized water, and stirring to fully dissolve the ammonium molybdate to obtain a solution C;
(4) slowly adding the solution C and 0.5 g of ammonia water into the solution B at the same time under vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 5 hours under the condition of water bath at the temperature of 40 ℃; after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 100 ℃ for 12 hours;
(6) calcining the dried blocks in a muffle furnace at 400 ℃, at the heating rate of 2 ℃/min and for 5 hours to obtain the catalyst; the catalyst was tableted and sieved to form 40-60 mesh catalyst particles, designated catalyst 1. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 1.
Example 2
(1) Fully dissolving 1.15 g of ammonium metavanadate, 0.54 g of ammonium metatungstate and 0.08 g of stannous chloride in a mixed solution of 15 g of deionized water and 2 g of monoethanolamine, and marking as a solution A;
(2) adding 8.5 g of titanium dioxide into the solution A, and fully and uniformly dispersing to obtain a solution marked as solution A;
(3) adding 0.13 g of cerium nitrate into 3 g of deionized water, and stirring to fully dissolve the cerium nitrate to obtain a solution C;
(4) slowly adding the solution C and 1.0 g of ammonia water into the solution B at the same time under vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 4 hours under the condition of water bath at 50 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 80 ℃ for 20 hours;
(6) calcining the dried blocks in a muffle furnace at 500 ℃, at the heating rate of 2 ℃/min for 3 hours to obtain a catalyst; the catalyst was tableted and sieved to form 40-60 mesh catalyst particles, designated catalyst 2. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 1.
Example 3
(1) Fully dissolving 1.02 g of ammonium metavanadate, 0.37 g of ammonium paratungstate and 0.23 g of stannic chloride in a mixed solution of 20 g of deionized water and 1 g of monoethanolamine, and marking as a solution A;
(2) adding 8.7 g of titanium dioxide into the solution A, and stirring to fully dissolve the titanium dioxide to obtain a solution B;
(3) adding 0.26 g of lanthanum nitrate into 5g of deionized water, and stirring to fully dissolve the lanthanum nitrate to obtain a solution C;
(4) slowly adding the solution C and 1.5 g of ammonia water into the solution B at the same time under vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 7 hours under the condition of water bath at the temperature of 30 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 80 ℃ for 15 hours;
(6) placing the dried blocks in a muffle furnace for calcining at 600 ℃, wherein the heating rate is 2 ℃/min, and the calcining time is 7 hours to obtain a catalyst; the catalyst was tableted and sieved to form catalyst particles of 40-60 mesh size and designated catalyst 3. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 1.
Example 4
(1) Fully dissolving 0.80 g of vanadyl oxalate, 0.97 g of ammonium metatungstate and 0.47 g of stannic chloride in a mixed solution of 25 g of deionized water and 1.5 g of diethanolamine, and marking as a solution A;
(2) adding 8.5 g of titanium dioxide into the solution A, and fully and uniformly dispersing to obtain a solution B;
(3) adding 0.30 g of copper nitrate into 3 g of deionized water, and stirring to fully dissolve the copper nitrate to obtain a solution C;
(4) slowly adding the solution C and 2.0 g of ammonia water into the solution B at the same time under vigorous stirring, and marking as a solution D;
(5) continuously stirring the solution D for 5 hours under the condition of water bath at 40 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 100 ℃ for 12 hours;
(6) and (3) calcining the dried blocks in a muffle furnace at 400 ℃, at the heating rate of 2 ℃/min for 5 hours to obtain a catalyst, tabletting and sieving the catalyst to form 40-60-mesh catalyst particles, and marking as catalyst 4. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 2.
Example 5
(1) Fully dissolving 0.90 g of ammonium metavanadate, 0.54 g of ammonium metatungstate and 0.12 g of stannic chloride in a mixed solution of 15 g of deionized water and 6 g of monoethanolamine, and marking as a solution A;
(2) adding 8.7 g of titanium dioxide into the solution A, fully and uniformly dispersing, and marking as a solution B;
(3) adding 0.13 g of praseodymium nitrate into 5g of deionized water, and stirring to fully dissolve the praseodymium nitrate to obtain a solution C;
(4) slowly adding the solution C and 4.6 g of ammonia water into the solution B at the same time under the condition of vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 3 hours under the condition of water bath at 50 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 100 ℃ for 12 hours;
(6) and (3) calcining the dried blocks in a muffle furnace at 400 ℃, at the heating rate of 2 ℃/min for 3 hours to obtain a catalyst, tabletting and sieving the catalyst to form catalyst particles of 40-60 meshes, and marking as catalyst 5. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 2.
Example 6
(1) Dissolving 1.39 g of vanadyl sulfate, 0.86 g of ammonium metatungstate and 0.45 g of stannous chloride in a mixed solution of 10 g of deionized water and 8 g of monoethanolamine, and marking as solution A;
(2) adding 8.35 g of titanium dioxide into the solution A, fully and uniformly dispersing, and marking as a solution B;
(3) adding 0.2 g of niobium oxalate into 7 g of deionized water, and stirring to fully dissolve the niobium oxalate to obtain a solution C;
(4) slowly adding the solution C and 4.0 g of ammonia water into the solution B at the same time under vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 8 hours under the condition of water bath at 40 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 90 ℃ for 15 hours;
(6) and (3) placing the dried blocks into a muffle furnace for calcining at 500 ℃, at the heating rate of 2 ℃/min for 7 hours to obtain a catalyst, tabletting and sieving the catalyst to form catalyst particles of 40-60 meshes, and marking as a catalyst 6. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 2.
Example 7
(1) Fully dissolving 0.64g of ammonium metavanadate, 0.62 g of ammonium paratungstate and 0.93 g of stannic chloride in a mixed solution of 15 g of deionized water and 8 g of triethanolamine, and marking as a solution A;
(2) adding 8.55g of titanium dioxide into the solution A, and fully and uniformly dispersing to obtain a solution B;
(3) adding 0.106 g of antimony acetate into 15 g of deionized water, stirring to fully dissolve the antimony acetate, and marking as a solution C;
(4) slowly adding the solution C and 3.5 g of ammonia water into the solution B at the same time under violent stirring to obtain a solution D;
(5) continuously stirring the solution D for 5 hours under the condition of water bath at 60 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 80 ℃ for 24 hours;
(6) and calcining the dried block in a muffle furnace at 600 ℃, at the heating rate of 2 ℃/min for 3 hours to obtain a catalyst, tabletting and sieving the catalyst to form 40-60-mesh catalyst particles, and marking as catalyst 7. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 2.
Example 8
(1) Fully dissolving 0.51 g of ammonium metavanadate, 0.54 g of ammonium metatungstate and 0.47 g of stannic chloride in a mixed solution of 21 g of deionized water and 6 g of formamide, and marking as a solution A;
(2) adding 8.8 g of titanium dioxide into the solution A, and fully and uniformly dispersing to obtain a solution B;
(3) adding 0.13 g of cerium nitrate and 0.2 g of niobium oxalate into 6.0 g of deionized water, stirring and fully dissolving to obtain a solution C;
(4) slowly adding the solution C and 3 g of ammonia water into the solution B at the same time under violent stirring to obtain a solution D;
(5) continuously stirring the solution D for 5 hours under the condition of water bath at the temperature of 60 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 80 ℃ for 20 hours;
(6) and calcining the dried block in a muffle furnace at 500 ℃, at the heating rate of 2 ℃/min for 8 hours to obtain a catalyst, tabletting and sieving the catalyst to form catalyst particles of 40-60 meshes, and marking as the catalyst 8. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 3.
Example 9
(1) Fully dissolving 2.15 g of vanadyl oxalate, 0.97 g of ammonium metatungstate and 0.82 g of stannic chloride in a mixed solution of 30 g of deionized water and 10 g of monoethanolamine, and marking as a solution A;
(2) adding 7.8 g of titanium dioxide into the solution A, fully and uniformly dispersing, and marking as a solution B;
(3) adding 0.13 g of cerium nitrate and 0.27 g of lanthanum nitrate into 4.0 g of deionized water, and stirring to fully dissolve the cerium nitrate and the lanthanum nitrate to obtain a solution C;
(4) slowly adding the solution B and 0.8 g of ammonia water into the solution C at the same time under vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 7 hours under the condition of water bath at 50 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 80 ℃ for 24 hours;
(6) and (3) calcining the dried blocks in a muffle furnace at 400 ℃, at the heating rate of 2 ℃/min for 8 hours to obtain a catalyst, tabletting and sieving the catalyst to form catalyst particles of 40-60 meshes, and marking as catalyst 9. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 3.
Example 10
(1) Fully dissolving 0.25 g of ammonium metavanadate, 0.43 g of ammonium metatungstate and 0.23 g of stannic chloride in a mixed solution of 9 g of deionized water and 4g of monoethanolamine, and marking as a solution A;
(2) adding 9.1 g of titanium dioxide into the solution A, fully and uniformly dispersing, and marking as a solution B;
(3) adding 0.4 g of niobium oxalate and 0.21 g of antimony acetate into 7 g of deionized water, and stirring to fully dissolve the niobium oxalate and the antimony acetate to obtain a solution C;
(4) slowly adding the solution C and 0.6 g of ammonia water into the solution B at the same time under the condition of vigorous stirring to obtain a solution D;
(5) continuously stirring the solution D for 8 hours under the condition of water bath at 60 ℃, after the water in the mixed solution is evaporated and dried to form a pasty mixture, further drying the mixture in a forced air drying oven at the drying temperature of 90 ℃ for 15 hours;
(6) and calcining the dried block in a muffle furnace at 600 ℃, at the heating rate of 2 ℃/min for 7 hours to obtain a catalyst, tabletting and sieving the catalyst to form catalyst particles of 40-60 meshes, and marking as the catalyst 10. The performance test of the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene is carried out in a fixed bed, and the test result of the catalyst performance is shown in figure 3.
From the above examples, it can be seen that the catalyst prepared by the catalyst composition and the preparation method of the present invention has better reaction activity in the catalytic oxidation elimination of the dioxin analogue o-dichlorobenzene. Under the conditions of high ortho-dichlorobenzene concentration (1000 ppm) and space velocity of 15000 ml/(h.g), the elimination rate of ortho-dichlorobenzene can reach 98% when the temperature of the catalyst prepared in examples 1-3 is 210 ℃; when the space velocity is 25000 ml/(h.g), and the temperature of the catalyst prepared in examples 4-7 is 220 ℃, the elimination rate of o-dichlorobenzene can reach 99 percent; when the space velocity is 35000 ml/(h.g), and the temperature of the catalyst prepared in examples 8-10 is 230 ℃, the elimination rate of ortho-dichlorobenzene can reach 98%. Therefore, when the catalyst is applied to the catalytic oxidation elimination of dioxin analogue o-dichlorobenzene, the removal efficiency is equivalent to or better than that of the existing catalyst.

Claims (8)

1. A preparation method of a catalyst for removing dioxin in kiln flue gas through catalytic oxidation comprises the following steps:
(1) completely dissolving precursors of active components of tin, vanadium and tungsten of the catalyst in a deionized water-organic amine mixed solution under vigorous stirring, and marking the solution as A solution;
(2) adding the catalyst carrier industrial titanium dioxide into the solution A, stirring the mixture fully and uniformly, and marking the mixture as a solution B;
(3) dissolving one or more of lanthanum nitrate, ammonium molybdate, cerium nitrate, niobium oxalate, copper nitrate, praseodymium nitrate or antimony acetate catalyst promoter precursors into deionized water, and marking the solution as a solution C;
(4) slowly adding the solution C and ammonia water into the solution B under vigorous stirring to uniformly mix, and marking as a solution D;
(5) heating the solution D in a water bath to 30-60 ℃, and stirring for 2-8 hours to form paste; drying the paste, and then calcining at high temperature in a muffle furnace to obtain a catalyst;
the obtained catalyst consists of a catalyst carrier, an active component and an auxiliary agent, wherein the catalyst carrier is industrial titanium dioxide and accounts for 74-91% of the total mass of the catalyst; the active component of the catalyst is SnO2-V2O5-WO3The composite oxide accounts for 5.5-23% of the total mass of the catalyst; the catalyst auxiliary agent is La2O3、MoO3、CeO2、Nb2O5、CuO、Pr6O11And Sb2O3At least one of the components (a) and (b) accounts for 0.1-3.0% of the total mass of the catalyst; SnO as active component of catalyst2-V2O5-WO3In the composite oxide, SnO2Accounts for 0.5-4.0% of the total mass of the catalyst, and V2O52.0-9.0% of the total mass of the catalyst, and WO3Accounting for 3.0-10.0% of the total mass of the catalyst.
2. The preparation method of the catalyst for catalytic oxidation elimination of dioxin in kiln flue gas according to claim 1, characterized by comprising the following steps: the tin precursor is stannous chloride or stannic chloride; the vanadium precursor is ammonium metavanadate, vanadyl oxalate or vanadyl sulfate; the tungsten precursor is ammonium metatungstate or ammonium paratungstate.
3. The preparation method of the catalyst for catalytic oxidation elimination of dioxin in kiln flue gas according to claim 1, characterized by comprising the following steps: in the step (1), the organic amine is one or more of monoethanolamine, diethanolamine, triethanolamine or formamide.
4. The preparation method of the catalyst for catalytic oxidation elimination of dioxin in kiln flue gas according to claim 1, characterized by comprising the following steps: in the step (1), the mass of the deionized water is 5.0-15.0 times of that of the precursors of tin, vanadium and tungsten; the mass of the organic amine is 0.5-4.5 times of that of the precursors of tin, vanadium and tungsten.
5. The preparation method of the catalyst for catalytic oxidation elimination of dioxin in kiln flue gas according to claim 1, characterized by comprising the following steps: in the step (3), the amount of the deionized water is 1.0-8.0 times of the total mass of the precursors of tin, vanadium and tungsten.
6. The preparation method of the catalyst for eliminating dioxin in kiln gas by catalytic oxidation according to claim 1, characterized by comprising the following steps: in the step (4), the adding amount of ammonia water is 0.1-3.0 times of the total mass of the precursors of tin, vanadium and tungsten.
7. The preparation method of the catalyst for eliminating dioxin in kiln gas by catalytic oxidation according to claim 1, characterized by comprising the following steps: in the step (5), the drying is carried out in a forced air drying oven at the temperature of 80-100 ℃ for 12-24 hours.
8. The preparation method of the catalyst for eliminating dioxin in kiln gas by catalytic oxidation according to claim 1, characterized by comprising the following steps: in the step (5), the calcination is carried out at 300-600 ℃ for 3-10 hours.
CN201911009509.1A 2019-10-23 2019-10-23 Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof Active CN110586073B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911009509.1A CN110586073B (en) 2019-10-23 2019-10-23 Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911009509.1A CN110586073B (en) 2019-10-23 2019-10-23 Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110586073A CN110586073A (en) 2019-12-20
CN110586073B true CN110586073B (en) 2022-03-25

Family

ID=68850058

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911009509.1A Active CN110586073B (en) 2019-10-23 2019-10-23 Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110586073B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112191267A (en) * 2020-09-30 2021-01-08 中国科学院兰州化学物理研究所 Honeycomb catalyst for removing dioxin in flue gas through catalytic oxidation and preparation method thereof
CN113181590A (en) * 2021-04-14 2021-07-30 南京师范大学 Method for degrading dioxin in fly ash through wet catalytic oxidation
CN113655170A (en) * 2021-08-04 2021-11-16 安徽迪诺环保新材料科技有限公司 Method for measuring denitration rate of nano titanium dioxide powder for flue gas denitration catalyst

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001286733A (en) * 2000-04-06 2001-10-16 Mitsubishi Chemicals Corp Method for decomposing chlorinated organic compound and method for treating combustion exhaust gas
KR20030078258A (en) * 2002-03-28 2003-10-08 한국전력기술 주식회사 Vanadium/titania-based catalyst containing vanadium trioxide for removing nitrogen oxide and/or dioxin at wide active temperature window
CN1668373A (en) * 2002-07-31 2005-09-14 独立行政法人产业技术综合研究所 Chemical reaction system of electrochemical cell type, method for activation thereof and method for reaction
CN105251477A (en) * 2015-11-17 2016-01-20 广东电网有限责任公司电力科学研究院 High-temperature SCR denitration catalyst in vanadium wide window and preparing method and application of high-temperature SCR denitration catalyst
CN106732544A (en) * 2016-12-20 2017-05-31 浙江德创环保科技股份有限公司 A kind of catalyst for removing bioxin and preparation method thereof
CN107952449A (en) * 2017-12-15 2018-04-24 江苏龙净科杰催化剂再生有限公司 Low temperature collaboration denitration Tuo bioxin demercuration honeycombed catalysts and preparation method thereof
CN109126773A (en) * 2018-09-28 2019-01-04 航天凯天环保科技股份有限公司 A kind of garbage-incineration smoke purifying catalyst and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001286733A (en) * 2000-04-06 2001-10-16 Mitsubishi Chemicals Corp Method for decomposing chlorinated organic compound and method for treating combustion exhaust gas
KR20030078258A (en) * 2002-03-28 2003-10-08 한국전력기술 주식회사 Vanadium/titania-based catalyst containing vanadium trioxide for removing nitrogen oxide and/or dioxin at wide active temperature window
CN1668373A (en) * 2002-07-31 2005-09-14 独立行政法人产业技术综合研究所 Chemical reaction system of electrochemical cell type, method for activation thereof and method for reaction
CN105251477A (en) * 2015-11-17 2016-01-20 广东电网有限责任公司电力科学研究院 High-temperature SCR denitration catalyst in vanadium wide window and preparing method and application of high-temperature SCR denitration catalyst
CN106732544A (en) * 2016-12-20 2017-05-31 浙江德创环保科技股份有限公司 A kind of catalyst for removing bioxin and preparation method thereof
CN107952449A (en) * 2017-12-15 2018-04-24 江苏龙净科杰催化剂再生有限公司 Low temperature collaboration denitration Tuo bioxin demercuration honeycombed catalysts and preparation method thereof
CN109126773A (en) * 2018-09-28 2019-01-04 航天凯天环保科技股份有限公司 A kind of garbage-incineration smoke purifying catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"邻二氯苯在钒-钨-钛催化剂上的完全催化氧化";段明华等;《工业催化》;20150315;第23卷(第3期);第200页左栏第3段，第1.1节 *

Also Published As

Publication number Publication date
CN110586073A (en) 2019-12-20

Similar Documents

Publication Publication Date Title
CN109107567B (en) M-MnOX-CeO2Catalyst and application thereof
CN110586073B (en) Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof
CN108295840A (en) Manganese-based catalyst and its preparation and application of a kind of efficient synergistic purification nitrogen oxides He bioxin
CN109126773B (en) Catalyst for purifying waste incineration flue gas and preparation method thereof
CN102335604B (en) SCR (selective catalyctic reduction) low-temperature denitrification catalyst with nano core-shell structure and preparation method thereof
CN113786828B (en) Catalyst for synergistic removal of NOx and CVOCs, and preparation method and application thereof
CN109351358A (en) A kind of transition metal oxide composite catalyst and its preparation method and application
CN110548518A (en) Transition metal composite catalyst for purifying coal-fired organic waste gas and preparation method and application thereof
CN105771961B (en) A kind of CeO2Nanotube supported denitrating catalyst and preparation method thereof
CN106540693A (en) A kind of catalyst of low temperature Synergistic degradation bioxin and NOx and preparation method thereof
CN105879879A (en) High-sulfur-resistant ultralow-temperature SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof
CN114210320A (en) Heterogeneous diatom low-temperature sulfur-resistant SCR catalyst and preparation method thereof
CN114308088A (en) Acid site separation catalyst for synergistically converting nitrogen oxide and chlorine-containing volatile organic compound, and preparation method and application thereof
CN114160147B (en) Composite oxide catalyst for synchronously removing VOCs and NOx in sulfur-containing flue gas and preparation method and application thereof
CN109603808B (en) Preparation method and application of zirconium pillared montmorillonite-loaded Ce-Nb composite catalyst
CN106362733A (en) High-temperature resistant manganite catalyst and preparation method thereof
CN113694933A (en) High-entropy co-doped low-temperature SCR denitration catalyst and preparation method and application thereof
CN111151241A (en) Integral honeycomb coating catalyst and preparation method and application thereof
CN105817234A (en) Method for extracting nanometer multi-metal oxide loaded activated carbon fibers
CN112316941A (en) Bifunctional catalyst for synergistic purification of nitrogen oxide and volatile organic compound and preparation method thereof
KR100402430B1 (en) Catalyst for decomposition of toxic pollutants and producing process thereof
CN112473657B (en) Low-vanadium catalyst for synergistically removing dioxin and mercury in flue gas and preparation method and application thereof
CN111151260A (en) Non-alum-based catalyst and preparation method and application thereof
KR100382050B1 (en) Catalyst for Removing Dioxin and Nitrogen Oxides in Flue Gas and Method for Treating Combustion Exhaust Gases Using the Same
CN113600176A (en) Preparation method of flue gas synergistic denitration and demercuration catalyst and catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant