CN107913595B - Catalytic oxidation treatment method of cyanogen-containing waste gas - Google Patents
Catalytic oxidation treatment method of cyanogen-containing waste gas Download PDFInfo
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Abstract
The invention relates to a catalytic oxidation treatment method of cyanogen-containing waste gas. 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 removes cyanide in waste gas by adopting a catalytic oxidation treatment method of cyanide-containing waste gas, in the presence of a catalyst, enabling the cyanide-containing waste gas to react with an oxidant containing oxygen in a reactor, wherein the catalyst comprises the following components in parts by weight: (1) 10-90 parts of a catalyst carrier; (2) the technical scheme of 0.1-65 parts of tungsten oxide better solves the problem and can be used for removing cyanide in cyanide-containing waste gas.
Description
Technical Field
The invention relates to a catalytic oxidation treatment method of cyanogen-containing waste gas.
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.
Dissolving H 2 PtCl 6 in H 2 O, adding an equal volume of H 2 PtCl 6 solution into an Al 2 O 3 carrier, soaking, drying, roasting and reducing, heating the furnace to 250-450 ℃ in a reaction furnace filled with the catalyst, introducing a mixed gas containing HCN, NH 3, tar and air into the reaction furnace, and removing the waste gas through catalytic combustion.
CN102734812 discloses a method for removing cyanogen-containing waste gas, which adopts a transition metal loaded mesoporous molecular sieve catalyst to carry out catalytic reaction on cyanogen-containing waste gas, wherein the mesoporous molecular sieve carrier is MCM-41, MCM-48, SBA-15, SBA-16, KIT-5 or KIT-6, the active component of the transition metal is 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 reaction furnace temperature is increased to 350-650 ℃ under normal pressure, mixed gas containing cyanogen-containing waste gas, oxygen and nitrogen is introduced into the reaction furnace at the space velocity of 17000-24000 h -1, and the waste gas is removed through catalytic combustion.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the problem of high NOx content in the tail gas of the cyanide-containing waste gas treated by the existing catalyst and provide a novel catalytic oxidation treatment method of the cyanide-containing waste gas, and the catalytic oxidation treatment method of the cyanide-containing waste gas has the advantages of good cyanide removal efficiency and low NOx content in the tail gas after cyanide removal.
In order to solve the technical problems, the technical scheme of the invention is as follows:
A method for treating cyanogen-containing waste gas by catalytic oxidation, in the presence of a catalyst, enabling the cyanogen-containing waste gas and an oxidant containing oxygen to react in a reactor to remove cyanides in the waste gas, wherein the catalyst comprises the following components in parts by weight:
(1) 10-90 parts of a catalyst carrier;
(2)0.1 to 65 parts of tungsten oxide.
In the technical scheme, the preferable part of the tungsten oxide is 1-50.
in the above technical solutions, any crystal form of tungsten oxide may be used, but hexagonal phase tungsten oxide is preferable, and hexagonal phase tungsten oxide nanowires are more preferable. 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 above technical solution, the carrier is not particularly limited, for example, but not limited to, the catalyst carrier is selected from one of TiO 2, ZrO 2, SiO 2, and Al 2 O 3.
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) 0.1-20 parts of copper oxide, and the copper oxide and tungsten oxide have a synergistic effect in the aspect of reducing the NOx generation amount.
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.
The preparation method of the catalyst in any one of the above technical schemes comprises the steps of mixing tungsten oxide and a carrier, and molding.
In the above technical scheme, when the catalyst component contains CuO, the preparation method of the catalyst comprises the steps of mixing a solution containing a copper compound with tungsten oxide and a carrier, drying and roasting.
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.
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:
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 space velocity is 1000-30000 h -1 based on the total feeding volume of the cyanide-containing waste gas and the oxidant.
In the above technical solutions, the kind of the cyanogen in the cyanogen-containing waste gas is not limited as long as it has the effect of removing all C.ident.N groups contained in the molecule, such as, but not limited to, cyanogen gas ((CN) 2), thiocyanide ((SCN) 2), oxocyanide ((OCN) 2), HCN, HSCN, HOCN, saturated nitriles of C2-C10 (such as, but not limited to, acetonitrile), unsaturated nitriles of C3-C10 (such as, but not limited to, acrylonitrile, methacrylonitrile, benzonitrile, m-tolunitrile), and the like.
The catalyst of the invention has no particular limitation on the total cyanogen content, the catalyst of the 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 adopted in the embodiment of the invention is formed by mixing air and acrylonitrile hydrogen cyanide, wherein the acrylonitrile content is 1925mg/m 3, and the hydrogen cyanide content is 240mg/m 3.
When the reaction temperature is 390 ℃, the space velocity is 10000h -1, and the model gas of cyanogen-containing waste gas is treated by the method, the acrylonitrile is reduced to 0.4mg/m 3 from 1,925mg/m 3, the hydrogen cyanide is reduced to 1.3mg/m 3 from 240mg/m 3, and the content of NOx in tail gas is 16.2mg/m 3, thereby obtaining better technical effects.
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
The weight ratio of TiO 2 to CuO is 85:15 to prepare the catalyst.
Cu (NO 3) 2 corresponding to 15 parts of CuO was mixed with 85 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 2 ]
1. Catalyst preparation
The weight ratio of TiO 2 to WO 3 is 85: 15.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
15 parts of WO 3 were mixed with 85 parts of TiO 2, 0.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into strands, dried at room temperature, and 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
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 3 ]
1. Catalyst preparation
the weight ratio of TiO 2 to WO 3 to CuO is 85:10: 5.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 5 parts of CuO, and 10 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 10 parts of WO 3 and 5 parts of CuO was mixed with 85 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 4 ]
1. Catalyst preparation
According to the weight ratio, Al 2 O 3, WO 3 and CuO are 85:10:5 to prepare the catalyst.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 5 parts of CuO, and 10 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 10 parts of WO 3 and 5 parts of CuO was mixed with 85 parts of Al 2 O 3, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 5 ]
1. catalyst preparation
According to the weight ratio, the SiO 2, the WO 3 and the CuO are 85, 10 and 5 to prepare the catalyst.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 5 parts of CuO, and 10 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
a catalyst precursor corresponding to a catalyst containing 10 parts of WO 3 and 5 parts of CuO was mixed with 85 parts of SiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 6 ]
1. Catalyst preparation
The catalyst is prepared from ZrO 2, WO 3 and CuO in a weight ratio of 85:10: 5.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 5 parts of CuO, and 10 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 10 parts of WO 3 and 5 parts of CuO was mixed with 85 parts of ZrO 2, 0.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in Table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 7 ]
1. Catalyst preparation
The catalyst is prepared from TiO 2, WO 3, CuO, Na 2, SO 4 and 85, 9.95, 5 and 0.05 in weight ratio.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of a mixed aqueous solution of Cu (NO 3) 2 -sodium sulfate corresponding to 5 parts of CuO and 0.05 part of Na 2 SO 4 was mixed with 9.95 parts of WO 3, and evaporated at 80 ℃ with stirring until NO visible running water was observed, and dried at 80 ℃ for 12 hours to obtain a catalyst precursor.
a catalyst precursor corresponding to a catalyst containing 9.95 parts of WO 3,5 parts of CuO and 0.05 part of Na 2 SO 4 was mixed with 85 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a bar, dried at room temperature, and calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
the cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
The catalyst is prepared from TiO 2, WO 3, CuO, Na 2, SO 4 and 85, 9.95, 5 and 0.05 in weight ratio.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of a mixed aqueous solution of Cu (NO 3) 2 -sodium chloride, which corresponds to 5 parts of CuO and 0.05 part of NaCl, and 9.95 parts of WO 3 were mixed, and evaporated at 80 ℃ with stirring until NO visible running water was present, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 9.95 parts of WO 3,5 parts of CuO and 0.05 part of NaCl was mixed with 85 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
1. Catalyst preparation
The catalyst is prepared from TiO 2, WO 3, CuO, K 2, SO 4 and 85, 9.95, 5 and 0.05 in weight ratio.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of a mixed aqueous solution of Cu (NO 3) 2 -potassium sulfate, which corresponds to 5 parts of CuO and 0.05 part of K 2 SO 4, and 9.95 parts of WO 3 are mixed, stirred and evaporated at 80 ℃ until NO visible running water exists, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 9.95 parts of WO 3,5 parts of CuO and 0.05 part of K 2 SO 4 was mixed with 85 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a bar, dried at room temperature, and calcined at 500 ℃ for 4 hours to prepare 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
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
1. Catalyst preparation
The weight ratio of TiO 2 to Na 2 SO 4 is 85: 15.
15 parts of Na 2 SO 4, 85 parts of TiO 2, 0.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a bar, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare 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
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 8 ]
1. Catalyst preparation
The weight ratio of TiO 2 to WO 3 to CuO is 75:20: 5.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of a Cu (NO 3) 2 aqueous solution containing 5 parts of CuO and 20 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water exists, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to 20 parts of WO 3 and 5 parts of CuO was mixed with 75 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare 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
the cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 9 ]
1. Catalyst preparation
The weight ratio of TiO 2 to WO 3 to CuO is 60:35: 5.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 5 parts of CuO, and 35 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 35 parts of WO 3 and 5 parts of CuO was mixed with 60 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 10 ]
1. Catalyst preparation
the weight ratio of TiO 2 to WO 3 to CuO is 60:30: 10.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
100 parts of an aqueous solution of Cu (NO 3) 2, which is equivalent to 10 parts of CuO, and 30 parts of WO 3 are mixed, evaporated at 80 ℃ under stirring until NO visible running water is formed, and dried at 80 ℃ for 12 hours to prepare a catalyst precursor.
A catalyst precursor corresponding to a catalyst containing 30 parts of WO 3 and 10 parts of CuO was mixed with 60 parts of TiO 2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water, kneaded for 30 minutes, extruded into a shape, dried at room temperature, and then calcined at 500 ℃ for 4 hours to prepare a cylindrical catalyst having a diameter of 0.5cm and a length of 1cm, and the composition and preparation characteristics of the catalyst were listed in table 1 for convenience of comparison.
2. Catalyst evaluation
the cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 11 ]
1. Catalyst preparation
The weight ratio of TiO 2 to WO 3 to CuO is 85:10: 5.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
10 parts of WO 3,5 parts of CuO, 85 parts of TiO 2, 0.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water were mixed, kneaded for 30 minutes, extruded into a strip 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
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
[ example 12 ]
1. Catalyst preparation
The catalyst is prepared from TiO 2, WO 3, CuO, Na 2, SO 4 and 85, 9.95, 5 and 0.05 in weight ratio.
Preparation of hexagonal phase tungsten oxide nanowires (WO 3):
2.13g of ammonium tungstate, 8.32g of ammonium sulfate and 2.10g of oxalic acid are dissolved in 80mL of water, and after the ammonium tungstate, the ammonium sulfate and the oxalic acid are completely dissolved, and then the solution is transferred to a 100mL autoclave, heated to 180 ℃, stirred for 12 hours, cooled to room temperature, washed with 100mL of distilled water respectively for 6 times, and dried at 100 ℃ overnight, so that WO 3 is prepared.
A cylindrical catalyst having a diameter of 0.5cm and a length of 1cm was prepared by mixing 9.95 parts of WO 3,5 parts of CuO, 0.05 part of Na 2 SO 4, 85 parts of TiO 2, 0.5 part of carboxymethylcellulose, 2 parts of nitric acid and 15 parts of water, kneading for 30 minutes, extruding into strips, drying at room temperature, and calcining at 500 ℃ for 4 hours, and the composition and preparation characteristics of the catalyst are shown in Table 1 for convenience of comparison.
2. Catalyst evaluation
The cyanogen-containing waste gas model gas (acrylonitrile 1925mg/m 3, hydrogen cyanide 240mg/m 3) was passed through a fixed bed reactor packed with 800mL of a catalyst, the reaction temperature in the reactor was 390 ℃, the reaction space velocity was 10000h -1, and the reaction results are shown in Table 1.
TABLE 1
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, the tungsten oxide and the carrier together; - - -means that I and II are not involved.
Claims (9)
1. A method for treating cyanogen-containing waste gas by catalytic oxidation, in the presence of a catalyst, enabling the cyanogen-containing waste gas and an oxidant containing oxygen to react in a reactor to remove cyanides in the waste gas, wherein the catalyst comprises the following components in parts by weight:
(1) 10-90 parts of a catalyst carrier;
(2) 0.1-65 parts of tungsten oxide;
(3) 0.1-20 parts of copper oxide;
(4) 0.01-1 part of sodium sulfate.
2. The method according to claim 1, wherein the tungsten oxide is present in an amount of 1 to 50 parts.
3. the process of claim 1, wherein the tungsten oxide is hexagonal phase tungsten oxide.
4. The process as set forth in claim 1 wherein the catalyst support is selected from the group consisting of TiO 2, ZrO 2, SiO 2 and Al 2 O 3.
5. the process of claim 1 wherein the catalyst is in the form of a honeycomb, clover, cylinder or sphere.
6. The process of claim 1, wherein the catalyst is prepared by mixing a solution of a copper-containing compound with the tungsten oxide and the support, drying, and calcining.
7. The process of claim 1 wherein said oxidant is air or oxygen-enriched.
8. The method according to claim 1, wherein the reaction temperature is 280 to 500 ℃.
9. the treatment method as set forth in claim 1, wherein the space velocity is 1000 to 30000h -1 based on the total volume of the cyanide-containing waste gas and the oxidizing agent.
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| CN1564710A (en) * | 2001-10-09 | 2005-01-12 | 阿克森斯公司 | Use of a TiO2 composition as catalyst for hydrolyzing COS and/or HCN in a gas mixture |
| CN101112685A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Process for preparation of high activity W-based catalysts and uses thereof |
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| CN1511615A (en) * | 2002-12-31 | 2004-07-14 | 中国人民解放军63971部队 | Purifying catalyst for gas containing cyanogen and its preparing method |
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