CN107913711B - Catalyst for oxidative decyanation of cyanogen-containing waste gas - Google Patents

Catalyst for oxidative decyanation of cyanogen-containing waste gas Download PDF

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CN107913711B
CN107913711B CN201610881456.2A CN201610881456A CN107913711B CN 107913711 B CN107913711 B CN 107913711B CN 201610881456 A CN201610881456 A CN 201610881456A CN 107913711 B CN107913711 B CN 107913711B
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catalyst
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waste gas
cyanogen
copper
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CN107913711A (en
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陈航宁
郭宗英
吴粮华
姜家乐
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01D2257/40—Nitrogen compounds
    • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
    • 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

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Abstract

The invention relates to a cyanogen-containing waste gas oxidation decyanation catalyst and a preparation method thereof. The method is used for solving the problem that the content of NOx in the tail gas after the cyanogen-containing waste gas is treated by the existing catalyst is high. The invention adopts cyanide-containing waste gas oxidation decyanation catalyst, which comprises the following components in parts by weight: (1) 10-90 parts of a catalyst carrier; (2) the technical scheme of 0.1-20 parts of copper oxide better solves the problem and can be used for removing cyanide in cyanide-containing waste gas.

Description

Catalyst for oxidative decyanation of cyanogen-containing waste gas
Technical Field
The invention relates to a cyanide-containing waste gas oxidation decyanation catalyst and a preparation method thereof.
Technical Field
The main pollution source of industrial cyanide-containing waste gas is from coking plants, cyanide plants, electroplating plants and carbon fiber production processes, the waste gas is a highly toxic pollutant harmful to biological health, and the waste gas can be discharged after being strictly treated and qualified through detection. At present, in the new standard of cyanide emission in China, the content of acrylonitrile is required to be lower than 0.5mg/m3, and the content of hydrogen cyanide is lower than 1.9mg/m 3. The decyanation method mainly comprises the technologies of absorption, adsorption, combustion, catalytic oxidation, hydrolysis and the like. The catalytic oxidation method is an effective method for treating organic waste gas, and has the advantages of low ignition temperature, no secondary pollution, recyclable waste heat, convenient operation and management, low operating cost and the like, so the catalytic oxidation method has unique advantages in the aspect of treating tail gas and is a promising method.
CN101362051 discloses a process for treating acrylonitrile device tail gas, which is suitable for acrylonitrile waste gas discharged from an acrylonitrile device, and is characterized in that the acrylonitrile tail gas is separated from free water by a gas-liquid separator, mixed with air, and subjected to catalytic oxidation reaction by taking a noble metal honeycomb catalyst as a catalyst to convert harmful volatile organic compounds into carbon dioxide and water; and then taking the selective reduction honeycomb catalyst as a catalyst to perform selective catalytic reduction reaction with the supplemented ammonia, so as to reduce the nitrogen oxides in the tail gas into nitrogen and water. The method is complex to operate, ammonia needs to be supplemented, and the material consumption is high.
CN1416950 discloses a preparation method of a catalyst for removing HCN-containing waste gas. H is to be2PtCl6Dissolved in H2In O, then in Al2O3Adding equal volume of H into the carrier2PtCl6Dipping in solution, drying, calcining and reducing. In a reaction furnace filled with the catalyst, the temperature of the furnace is raised to 250-450 ℃, and HCN and NH are contained3The mixed gas of tar and air is introduced into the reaction furnace, and the waste gas is removed through catalytic combustion. However, the catalyst cost in this process is high.
CN102734812 discloses a method for removing cyanogen-containing waste gas, which adopts transition metal loaded mesoporous molecular sieve catalyst to carry out catalytic reaction for removing cyanogen-containing waste gas. Wherein the mesoporous molecular sieve carrier is: MCM-41, MCM-48, SBA-15, SBA-16, KIT-5 or KIT-6, and transition metal active components: one or more of Cu, Co, Cr, Mn, Ag or V, the mass ratio of the carrier to the transition metal component is 1: 0.02-0.07, the molecular sieve catalyst is placed in a fixed bed quartz reactor, the temperature of the reaction furnace is raised to 350-650 ℃ under normal pressure, and the mixed gas of cyanogen-containing waste gas, oxygen and nitrogen is used at the airspeed of 17000-24000 h-1Introducing into a reaction furnace, and removing waste gas through catalytic combustion. The method has low removal efficiency.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of high content of NOx in the tail gas after cyanide-containing waste gas is treated by the existing catalyst, and provide a novel catalytic oxidation catalyst which has the advantages of good cyanide removal efficiency and low content of NOx in the tail gas after cyanide removal.
The second technical problem to be solved by the invention is the preparation method of the catalyst in the first technical problem.
The invention also aims to solve the technical problem of application of the catalyst in catalytic oxidation decyanation of cyanogen-containing waste gas.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the cyanogen-containing waste gas oxidation decyanation catalyst comprises the following components in parts by weight:
(1) 10-90 parts of a catalyst carrier;
(2) 0.1-20 parts of copper oxide.
In the above technical scheme, the carrier is not particularly limited, for example, but not limited to, the catalyst carrier is selected from TiO2、ZrO2、SiO2And Al2O3One kind of (1).
In the above technical solution, the geometric shape of the catalyst is not particularly limited, such as but not limited to honeycomb, clover, column or sphere.
In the technical scheme, the catalyst also preferably comprises (3)0.1-70 parts of tungsten oxide, and the copper oxide and the tungsten oxide have a synergistic effect in the aspect of reducing the NOx generation amount.
In the above technical scheme, any crystal form of tungsten oxide can be used, but hexagonal phase tungsten oxide nanowires are preferred. The hexagonal phase tungsten oxide nano wire can be obtained from a commercial channel and can also be prepared by a hydrothermal method.
In the technical scheme, 0.01-1 part of sodium sulfate is further included, generation of NOx in the decyanation process is further inhibited by adding the sodium sulfate, and the sodium sulfate and tungsten oxide have a synergistic effect. We have surprisingly found that neither sodium chloride, which is also a sodium salt, nor potassium sulphate, which is also an alkali metal sulphate, has found this effect. The sodium sulfate may be used in the form of an anhydride or water of crystallization, but the amount of the sodium sulfate used is based on the anhydride, and the sodium sulfate used in the embodiment is anhydrous.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method of preparing a catalyst according to any of the preceding claims, comprising mixing a solution comprising a copper compound with the support, drying, and calcining.
When the catalyst contains tungsten oxide, a preferred preparation method is as follows: comprises mixing the solution containing copper compound with tungsten oxide and carrier, drying, and calcining.
More preferably, the tungsten oxide and the solution containing the copper compound are mixed and dried to obtain a catalyst precursor, and then the catalyst precursor is mixed with the catalyst carrier to be molded, dried and roasted to obtain the catalyst. Namely, the preparation method comprises the following steps:
1) mixing the solution containing the copper compound with tungsten oxide, and drying to obtain a catalyst precursor;
2) and mixing and molding the catalyst precursor and the catalyst carrier, drying and roasting to obtain the catalyst.
When the catalyst further contains (4)0.01 to 1 part of sodium sulfate, the preparation method of the catalyst preferably comprises mixing a solution containing a copper compound and sodium sulfate with tungsten oxide and a carrier, drying, and calcining. More preferably, the tungsten oxide is firstly mixed with a solution containing a copper compound and sodium sulfate, and then dried to obtain a catalyst precursor, and then the catalyst precursor is mixed with a catalyst carrier to be molded, dried and roasted to obtain the catalyst, namely, the preparation method comprises the following steps:
i) mixing a solution containing a copper compound and sodium sulfate with tungsten oxide, and drying to obtain a catalyst precursor;
and ii) mixing and molding the catalyst precursor and the catalyst carrier, and drying and roasting to obtain the catalyst.
We have found that the catalyst obtained in this way comprising step 1) or i) above is more effective in reducing NOx formation than the catalyst obtained by directly mixing the copper compound solution with tungsten oxide and the carrier.
In the technical scheme, the drying temperature is not particularly limited, for example, but not limited to, 60-110 ℃, and the drying time is not particularly limited, for example, but not limited to, 6-24 hours.
In the above technical scheme, the roasting process conditions are not particularly limited, for example, but not limited to, the roasting temperature is 300-800 ℃, and the roasting time is, for example, but not limited to, 2-8 hours.
In the above technical scheme, the method for mixing and molding in steps 2) and ii) is not particularly limited, and those skilled in the art can make reasonable selection among well-known methods, such as but not limited to adding a molding aid including a binder to knead, extrude or sheet the catalyst, and molding the catalyst.
In the above-mentioned technical solutions, the solvent used in the solution is not particularly limited as long as it can dissolve the desired composition, and water is preferred from the viewpoint of economy and safety. For convenience of comparison, the solvents in the embodiments of the present invention are all water.
In the above technical solution, the copper-containing compound is preferably a copper salt.
In the above technical solution, the copper salt is preferably at least one selected from copper nitrate, copper chloride, copper sulfate and copper acetate.
To solve the third technical problem, the technical scheme of the invention is as follows: the application of the catalyst in the technical scheme of one of the technical problems in the catalytic oxidation decyanation of the cyanogen-containing waste gas.
The technical key point of the invention is the selection of the catalyst component and the further preparation method, and the technical conditions of the catalyst component in the catalytic oxidation decyanation of the cyanogen-containing waste gas can be reasonably selected by the technical personnel in the field on the basis of the disclosure of the invention.
For example, the specific application method may be:
a process for the catalytic oxidation treatment of a cyanide-containing waste gas, characterized in that the cyanide in the waste gas is removed by reacting the cyanide-containing waste gas with an oxygen-containing oxidizing agent in a reactor in the presence of a catalyst as defined in any of the preceding claims.
In the above technical solution, the oxidant is preferably air or oxygen-enriched air.
In the technical scheme, the reaction temperature is preferably 280-500 ℃.
In the technical scheme, the airspeed is 1000-30000 h based on the total feeding volume of the cyanide-containing waste gas and the oxidant-1。
In the above technical solutions, the kind of cyanogen in the cyanogen-containing waste gas is not limited, as long as the C.ident.N group contained in the molecule has the effect of removing, for example, but not limited to, cyanogen gas ((CN)2) Thiocyanide ((SCN)2) Oxygen cyanide ((OCN)2) HCN, HSCN, HOCN, saturated nitriles of C2 to C10 (such as but not limited to acetonitrile), unsaturated nitriles of C3 to C10 (such as but not limited to acrylonitrile, methacrylonitrile, benzonitrile, m-tolunitrile), and the like.
The catalyst of the present invention has no particular limitation on the total amount of cyanogen, the catalyst of the present invention can achieve the technical effect of the same ratio, and in order to facilitate the same ratio, the model gas of the cyanogen-containing waste gas used in the embodiment of the present invention is formed by mixing air and acrylonitrile hydrogen cyanide, wherein the acrylonitrile content is 1925mg/m3The hydrogen cyanide content was 240mg/m3。
At the reaction temperature of 390 ℃ and the space velocity of 10000h-1After the model gas of cyanogen-containing waste gas is treated by the catalyst of the invention, the acrylonitrile content is from 1,925mg/m3Reduced to 0.4mg/m3(ii) a Hydrogen cyanide from 240mg/m3Reduced to 1.3mg/m3The content of NOx in the tail gas is 16.2mg/m3And a better technical effect is achieved.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
[ example 1 ]
1. Catalyst preparation
In weight ratio, TiO2CuO 85: 15.
Corresponding to Cu (NO) containing 15 parts of CuO3)2With 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 2 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3The catalyst was prepared at 85: 15.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
15 parts of WO3With 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 3 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3CuO 85:10: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, evaporating at 80 deg.C under stirring until no visible running water is present, drying at 80 deg.C for 12 hr to obtain catalystA body.
Will correspond to 10 parts of WO3And 5 parts of a catalyst precursor of CuO and 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 4 ]
1. Catalyst preparation
Calculated by weight ratio, Al2O3:WO3CuO 85:10: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to 10 parts of WO3And 5 parts of a catalyst precursor of CuO and 85 parts of Al2O30.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1)925mg/m3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 5 ]
1. Catalyst preparation
In terms of weight ratio, SiO2:WO3CuO 85:10: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to 10 parts of WO3And 5 parts of a catalyst precursor of CuO and 85 parts of SiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 6 ]
1. Catalyst preparation
In weight ratio, ZrO2:WO3CuO 85:10: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to 10 parts of WO3And 5 parts of CuO and 85 parts of ZrO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 7 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3:CuO:Na2SO4The catalyst was prepared at 85:9.95:5: 0.05.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Will correspond to 5 parts CuO and 0.05 part Na2SO4Cu (NO) of3)2100 parts of sodium sulfate mixed aqueous solution and 9.95 parts of WO3Mixing, stirring, and evaporating at 80 deg.C until no solvent is availableAnd (4) drying the mixture for 12 hours at 80 ℃ in flowing water to obtain a catalyst precursor.
Will correspond to the content of 9.95 parts of WO35 parts of CuO and 0.05 part of Na2SO4With 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3:CuO:Na2SO4The catalyst was prepared at 85:9.95:5: 0.05.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO and 0.05 part of NaCl3)2100 parts of mixed aqueous solution of sodium chloride and 9.95 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to the content of 9.95 parts of WO35 parts of CuO and 0.05 part of NaCl, and 85 parts of TiO2Mixing 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneading for 30 minutes, extruding and molding, drying at room temperature, roasting at 500 ℃ for 4 hours to obtain a cylindrical catalyst with the diameter of 0.5cm and the length of 1cm, and combining the catalyst groups for convenience of comparisonThe composition and preparation characteristics are shown in Table 1.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3:CuO:K2SO4The catalyst was prepared at 85:9.95:5: 0.05.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Will correspond to 5 parts CuO and 0.05 part K2SO4Cu (NO) of3)2100 parts of potassium sulfate mixed aqueous solution and 9.95 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to the content of 9.95 parts of WO35 parts of CuO and 0.05 part of K2SO4With 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
1. Catalyst preparation
In weight ratio, TiO2:Na2SO4The catalyst was prepared at 85: 15.
15 portions of Na2SO4With 85 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 8 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3CuO 75:20: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 20 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will be equivalent to containing 20 parts of WO3And 5 parts of CuO and 75 parts of TiO20.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water, kneading for 30 minutes, extruding, drying at room temperature, and calcining at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in the table for convenience of comparison1。
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 9 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3CuO is 60:35: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 5 parts of CuO3)2100 parts of aqueous solution and 35 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to 35 parts of WO3And 5 parts of CuO and 60 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 10 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3CuO isCatalyst preparation 60:30: 10.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Corresponding to Cu (NO) containing 10 parts of CuO3)2100 parts of aqueous solution and 30 parts of WO3Mixing, evaporating at 80 ℃ under stirring until no visible running water exists, and drying at 80 ℃ for 12 hours to obtain the catalyst precursor.
Will correspond to 30 parts of WO3And 10 parts of CuO and 60 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 11 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3CuO 85:10: 5.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
Adding 10 parts of WO35 parts of CuO and 85 parts of TiO20.5 part of carboxymethyl cellulose and 2 parts of nitreThe acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
[ example 12 ]
1. Catalyst preparation
In weight ratio, TiO2:WO3:CuO:Na2SO4The catalyst was prepared at 85:9.95:5: 0.05.
Hexagonal phase tungsten oxide nanowires (WO)3) The preparation of (1):
dissolving 2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid in 80mL of water, transferring the solution into a 100mL autoclave after the solution is completely dissolved, heating to 180 ℃, stirring for 12h, cooling to room temperature, washing with 100mL of distilled water for 6 times respectively, and drying at 100 ℃ overnight to obtain WO3。
9.95 parts of WO35 parts of CuO and 0.05 part of Na2SO485 parts of TiO20.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to obtain a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
Cyanogen-containing waste gas model gas (acrylonitrile 1925 mg/m)3Hydrogen cyanide 240mg/m3) Through a fixed bed reactor packed with 800mL of catalyst. The reaction temperature in the reactor is 390 ℃, and the reaction space velocity is 10000h-1. The reaction results are shown in Table 1.
TABLE 1
Figure BDA0001126723800000121
Note: in the preparation step column I, the solution containing the copper compound is first mixed with tungsten oxide; II, mixing the solution containing the copper compound and the tungsten oxide carrier together; - - -means that I and II are not involved.

Claims (8)

1. The cyanogen-containing waste gas oxidation decyanation catalyst comprises the following components in parts by weight:
(1) 10-90 parts of a catalyst carrier;
(2) 0.1-20 parts of copper oxide;
(3)0.1-70 parts of tungsten oxide;
(4)0.01 to 1 portion of sodium sulfate,
the catalyst carrier is SiO2。
2. The catalyst of claim 1, wherein the catalyst is in the form of a honeycomb, clover, column or sphere.
3. A process for preparing a catalyst for the oxidative decyanation of cyanogen-containing exhaust gas comprising copper oxide, tungsten oxide, sodium sulfate and a catalyst carrier according to claim 1, which comprises
i) Mixing a solution containing a copper compound and sodium sulfate with tungsten oxide, and drying to obtain a catalyst precursor;
and ii) mixing and molding the catalyst precursor and the catalyst carrier, and drying and roasting to obtain the catalyst.
4. The method according to claim 3, wherein the calcination temperature is 300 to 800 ℃.
5. The method according to claim 3, wherein the calcination is carried out for 2 to 8 hours.
6. The method according to claim 3, wherein the copper-containing compound is a copper salt.
7. The method according to claim 6, wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper chloride, copper sulfate and copper acetate.
8. Use of a catalyst according to claim 1 or 2 for the catalytic oxidative decyanation of cyanogen-containing exhaust gases.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1370618A (en) * 2000-12-05 2002-09-25 Zeo技术公司 Oxidizing catalyst and its preparation, regeneration process and usage in treating waste water
CN1511615A (en) * 2002-12-31 2004-07-14 中国人民解放军63971部队 Cyanogen-containing gas purification catalyst and preparation method thereof
CN102734812A (en) * 2011-04-14 2012-10-17 北京化工大学 Method for removing cyanogens-containing waste gas
CN102872704A (en) * 2012-10-17 2013-01-16 浙江大学 Device and method for purifying residual HCN (hydrogen cyanide) through electro-Fenton

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1370618A (en) * 2000-12-05 2002-09-25 Zeo技术公司 Oxidizing catalyst and its preparation, regeneration process and usage in treating waste water
CN1511615A (en) * 2002-12-31 2004-07-14 中国人民解放军63971部队 Cyanogen-containing gas purification catalyst and preparation method thereof
CN102734812A (en) * 2011-04-14 2012-10-17 北京化工大学 Method for removing cyanogens-containing waste gas
CN102872704A (en) * 2012-10-17 2013-01-16 浙江大学 Device and method for purifying residual HCN (hydrogen cyanide) through electro-Fenton

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