CN111068680A - Catalyst for treating benzene-containing waste gas and application thereof - Google Patents
Catalyst for treating benzene-containing waste gas and application thereof Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention relates to a catalyst for treating benzene-containing waste gas and application thereof. The catalyst is used for solving the problem of high content of benzene series in the tail gas treated by the existing catalyst. The catalyst for treating the benzene-containing waste gas comprises the following components in parts by weight: (1) 60-90 parts of a carrier; (2) 10-40 parts of active component; the technical scheme that the active component comprises at least one selected from the group consisting of Cu, V, W, Cr, Fe and Ni better solves the problem and can be used for removing benzene series in the benzene-containing waste gas.
Description
Technical Field
The invention relates to a catalyst for treating benzene-containing waste gas and application thereof.
Technical Field
Benzene series is one of the most important pollutants in air, and is benzeneAnd derivatives thereof, generally include benzene, toluene, ethylbenzene, xylene, nitrobenzene, chlorobenzene, styrene, trimethylbenzene, and the like. In the 80 s of the 20 th century, Ken Sexton et al studied the volatile organic compounds in non-methane hydrocarbons in the air of 7 cities, such as Houston, Philadelphia and Boston, and showed that 20-30% of the volatile organic compounds were aromatic hydrocarbons, mainly toluene and xylene. Aromatic hydrocarbons are dominant in some cities of our country such as Shanghai non-methane hydrocarbons. The main pollution source of the benzene-containing waste gas comes from volatilization of paint, solvent and adhesive; release of building finishing materials; incomplete combustion of fossil fuels such as petroleum and coal, and organic matters such as wood and tobacco, and automobile exhaust emission. Benzene series as a representative of volatile organic compounds has great harm to human bodies and strong toxicity, wherein benzene is a strong carcinogenic substance and can enter human bodies through respiratory tracts, digestive tracts and skins, and has great relevance to high incidence of leukemia; toluene and xylene have great toxic action on the central nervous system and blood system of people, so the benzene series must be strictly treated and can be discharged after being detected to be qualified. At present, in the latest standard of benzene series emission in China, the benzene content needs to be lower than 4mg/m3Toluene content of less than 15mg/m3. The debenzolization method mainly comprises the technologies of absorption, adsorption, catalytic combustion and the like. The catalytic combustion 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 operation cost and the like, so the catalytic combustion method has unique advantages in the aspect of treating waste gas and is a promising method.
CN101733165B discloses a preparation method and application of a low-content noble metal monolithic catalyst, the invention adopts a chemical plating method, hydrazine or sodium hypophosphite is used as a reducing agent, the hydrazine or sodium hypophosphite and palladium chloride or chloroplatinic acid in a plating solution are subjected to oxidation-reduction reaction, and simultaneously, metal Pd and/or Pt is directly deposited on the surfaces of cordierite honeycomb ceramic pore channels under the autocatalysis effect of Pd or Pt, so that the supported low-content Pt and/or Pd noble metal monolithic catalyst is obtained; the noble metal monolithic catalyst prepared by the invention is applied to the catalytic combustion and purification treatment of toluene; at a lower temperature of 186-244 ℃, the conversion rate of toluene reaches 99 percentThe toluene concentration was reduced to 40mg/m3The following. Although the toluene removal rate in the method reaches 99%, the method still does not reach the emission standard, and the cost of the noble metal is relatively high.
CN102909031B discloses a catalyst for catalytic elimination of toluene in air and a preparation method thereof; the active component of the catalyst is a composite oxide of Fe and Mn, and the composite oxide of Fe and Mn has a mesoporous structure; the preparation method of the catalyst comprises the steps of primary impregnation, primary roasting, secondary impregnation, secondary roasting, template agent removal, water washing, drying and the like. The catalyst of the invention takes the composite oxide with a mesoporous structure formed by non-noble metal manganese and iron as an active component, greatly reduces the cost of the catalyst, and has high reaction space velocity (66,000 ml.h)-1·g-1) And the low reaction temperature (523K) shows good toluene catalytic combustion activity and has good low-temperature toluene catalytic combustion activity. However, the preparation process of the catalyst in the method is complicated, and the repeatability is not easy to control.
Disclosure of Invention
The invention aims to solve the technical problem that the content of benzene series in tail gas after benzene-containing waste gas is treated by the existing catalyst is high, and provides a novel catalyst for treating benzene-containing waste gas, which has the advantage of high benzene series removal efficiency.
The second technical problem to be solved by the invention is the preparation method of the catalyst in the first technical problem.
The invention aims to solve the third technical problem of application of the catalyst in catalytic combustion of benzene-containing waste gas to remove benzene compounds.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the catalyst for treating the benzene-containing waste gas comprises the following components in parts by weight:
(1) 60-90 parts of a carrier;
(2) 10-40 parts of active component;
the active component includes at least one selected from the group consisting of Cu, V, W, Cr, Fe and Ni.
The technical key of the invention is the choice of the active ingredient, as far as the carrier is concerned, it is reasonable and without inventive effort for the person skilled in the art to choose. For example, but not limited to, the support includes at least one selected from the group consisting of alumina, titania, natural zeolite powder, and Activated Carbon (AC).
In the above technical solution, the active component preferably includes both a main active element and an auxiliary active element, the main active element includes Cu, and the auxiliary active element includes at least one selected from a group consisting of V, W and Cr. The main active elements and the auxiliary active elements have a synergistic effect in the aspect of improving the removal efficiency of the benzene series. At this time, the ratio of the primary active element to the auxiliary active element is not particularly limited as long as a comparable synergistic effect can be obtained by simultaneously including the primary active element and the auxiliary active element. By way of non-limiting example, the mass ratio of the primary active element to the secondary active element may be 1.2 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 1.5, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and so forth.
In the technical scheme, the active components simultaneously comprise V and W, and the V and the W have a synergistic effect on the aspect of improving the removal efficiency of the benzene series. The ratio of V to W is not particularly limited, and any ratio can achieve a comparable synergistic effect if V and W are included at the same time. By way of non-limiting example, the mass ratio of V to W may be 0.1 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the technical scheme, the active components simultaneously comprise V and Cr, and the V and the Cr have a synergistic effect on the aspect of improving the removal efficiency of the benzene series. The ratio of V to Cr is not particularly limited, and any ratio can achieve a comparable synergistic effect if V and Cr are included at the same time. By way of non-limiting example, the mass ratio of V to Cr may be 0.1 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the technical scheme, the active components simultaneously comprise W and Cr, and the W and the Cr have a synergistic effect on the aspect of improving the removal efficiency of the benzene series. The ratio of W to Cr is not particularly limited, and any ratio can achieve a comparable synergistic effect if W and Cr are included at the same time. As a non-limiting example, the mass ratio of W to Cr may be 0.1 to 10, and within this mass ratio, non-limiting specific point values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
In the above technical solution, the carrier preferably comprises both alumina and natural zeolite, and the combination of the two carriers has a synergistic effect in improving the removal efficiency of benzene compounds. The ratio of alumina to natural zeolite is not particularly limited as long as any ratio of the support including both alumina and natural zeolite can achieve a comparable synergistic effect. By way of non-limiting example, the mass ratio of alumina to natural zeolite may be 0.1 to 10, and within this mass ratio, non-limiting specific values may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 4.0, 4.5, 5, 6, 7, 8, 9, and the like.
When the carrier simultaneously comprises alumina and the natrual zeolite powder, the alumina and the natrual zeolite powder can be mixed and formed to prepare a composite carrier in advance when the catalyst is prepared, and then the active component is loaded on the composite carrier; or the alumina, the day-heat zeolite powder, the active component or the active component powder can be mixed and molded. Both ways can achieve comparable technical results.
In the above technical scheme, those skilled in the art know that both the alumina and the nathermitic zeolite powder are solid, and both the alumina and the nathermitic zeolite powder are used in the form of powder in the mixing and forming process, and the particle size of the powder is not particularly limited, and those skilled in the art can select the powder reasonably. For example, but not limited to, the particle size of the powder may be 100 to 600 mesh, such as, but not limited to, 300 mesh, 400 mesh, 500 mesh, and the like. In order to facilitate the same proportion, the alumina adopted in the specific embodiment of the invention is 400 meshes, and the natured zeolite powder is 200 meshes.
In the technical scheme, the mass ratio of the alumina to the nathermite powder in the complex is preferably 1: 2-2: 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.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any of the preceding technical aspects, comprising the steps of:
1) mixing the carrier and the binder, molding, drying and roasting to obtain a molded carrier;
2) and mixing the formed carrier with the solution of the active element, drying and roasting to obtain the catalyst.
In the technical scheme, the drying temperature is not particularly limited, for example, but not limited to, 70-110 ℃, and the drying time is not particularly limited, for example, but not limited to, 10-20 hours.
In the above technical scheme, the roasting process conditions are not particularly limited, such as but not limited to
The roasting temperature in the step 1) is 400-600 ℃, more preferably 450-550 ℃, and the roasting time is preferably 3.0-4.5 h;
the roasting temperature in the step 2) is 350-500 ℃, more preferably 400-500 ℃, and the roasting time is preferably 4.0-5.5 h.
In the above technical solution, the method for mixing and molding in step 1) is not particularly limited, and those skilled in the art can reasonably select from well-known methods, such as but not limited to adding a molding aid including a binder to knead, extrude or sheet 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 active ingredient-containing compound is preferably an active ingredient salt.
In the above technical solution, the active ingredient salt is preferably at least one selected from the group consisting of nitrate, acid ammonium salt and 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 and benzene removal of benzene-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 and benzene removal of the benzene-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 treating benzene-containing waste gas by catalytic combustion, which comprises reacting the benzene-containing waste gas with an oxygen-containing oxidizing agent in a reactor in the presence of the catalyst according to any one of the above-mentioned technical problems to remove benzene compounds in the waste gas.
In the above technical solution, the oxidant is preferably air or oxygen-enriched air.
In the technical scheme, the reaction temperature is preferably 160-250 ℃.
In the technical scheme, the airspeed is 1000-10000 ml.h based on the total feeding volume of the benzene-containing waste gas and the oxidant-1·g-1。
In the above technical scheme, the kind of benzene series in the benzene-containing waste gas is not limited, and the benzene series has the effect of removing benzene ring groups contained in the molecule, such as but not limited to benzene (C)6H6) Toluene (C)7H8) Xylene (C)8H10) Nitrobenzene (C)6H5NO2) Chlorobenzene (C)6H5Cl), styrene (C)8H8) "Sanjia" (Chinese character of ' Bian ' and ' SanjiaBenzene (C)9H12) And so on.
The total benzene content of the catalyst of the invention is not particularly limited, the catalyst of the invention can achieve the technical effect of the same proportion, and the model gas of the benzene-containing waste gas adopted in the embodiment of the invention is formed by air and aromatic hydrocarbon VOCs (volatile organic compounds), wherein the benzene content is 565mg/m3Toluene content 225mg/m3。
At a reaction temperature of 190 ℃ and a space velocity of 7000ml h-1·g-1After the model gas containing benzene waste gas is treated by the catalyst of the invention, the benzene content is 565mg/m3The minimum is 2.4mg/m3(ii) a Toluene from 225mg/m3The minimum is 3.5mg/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. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of an aqueous solution of copper nitrate (containing 30 parts by weight of Cu), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 2 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of an aqueous solution of ammonium metavanadate (containing 30 parts by weight of V), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by calcination at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 3 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of an aqueous solution of ammonium metatungstate (containing 30 parts by weight of W), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 4 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of an aqueous solution of chromium nitrate (containing 30 parts by weight of Cr), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 5 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a mixed aqueous solution of copper nitrate-ammonium metavanadate (containing 18 parts by weight of Cu and 12 parts by weight of V), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) By chargingFixed bed reactor with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 6 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a mixed aqueous solution of copper nitrate-ammonium metatungstate (containing 18 parts by weight of Cu and 12 parts by weight of W), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by baking at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 7 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a copper nitrate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu and 12 parts by weight of Cr), allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 8 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a mixed aqueous solution of copper nitrate-ammonium metavanadate-ammonium metatungstate (containing 18 parts by weight of Cu, 6 parts by weight of V and 6 parts by weight of W), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by calcination at 400 ℃ for 5.0 hours in a muffle furnace.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 9 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 6 parts by weight of W and 6 parts by weight of Cr), allowed to stand at room temperature for 4 hours, then dried in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 10 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of the spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 6 parts by weight of V and 6 parts by weight of Cr), allowed to stand at room temperature for 4 hours, and then dried in an oven at 110 ℃ for 16 hours, followed by calcination at 400 ℃ in a muffle furnace for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 11 ]
1. Preparation of the support
61 parts by weight of alumina powder (average particle size of 400 mesh) was put into a kneader and mixed, 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, and ball-rolled to form, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain a spherical carrier having a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of a spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 4 parts by weight of V, 4 parts by weight of W and 4 parts by weight of Cr), allowed to stand at room temperature for 4 hours, followed by drying in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 12 ]
1. Preparation of the support
70 parts by weight of natural zeolite powder (average particle size of 200 meshes) is put into a kneader to be mixed, 2.4 parts by weight of methylcellulose, 3 parts by weight of inorganic acid and 80 parts by weight of water are poured, kneaded, extruded and formed into balls, dried for 16h at 100 ℃, and then roasted for 3.0h at 550 ℃ in a muffle furnace to obtain the spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of a spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 4 parts by weight of V, 4 parts by weight of W and 4 parts by weight of Cr), allowed to stand at room temperature for 4 hours, followed by drying in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 13 ]
1. Preparation of the support
26 parts by weight of alumina powder (average particle size of 400 mesh) and 35 parts by weight of natural zeolite powder (average particle size of 200 mesh) were mixed in a kneader, 30 parts by weight of alumina sol (30% wt), 3 parts by weight of inorganic acid and 50 parts by weight of water were poured, kneaded, extruded, rolled into balls, dried at 100 ℃ for 16 hours, and then calcined at 550 ℃ in a muffle furnace for 3.0 hours to obtain spherical carriers with a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of a spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 4 parts by weight of V, 4 parts by weight of W and 4 parts by weight of Cr), allowed to stand at room temperature for 4 hours, followed by drying in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 14 ]
1. Preparation of the support
Mixing 36 parts by weight of alumina powder (average particle size of 400 mesh) and 25 parts by weight of natural zeolite powder (average particle size of 200 mesh) in a kneader, pouring 30 parts by weight of alumina sol (30% wt), 3 parts by weight of inorganic acid and 50 parts by weight of water, kneading, extruding, rolling ball molding, drying at 100 ℃ for 16h, and then calcining at 550 ℃ in a muffle furnace for 3.0h to obtain a spherical carrier with a diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of a spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 4 parts by weight of V, 4 parts by weight of W and 4 parts by weight of Cr), allowed to stand at room temperature for 4 hours, followed by drying in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
[ example 15 ]
1. Preparation of the support
Mixing 16 parts by weight of alumina powder (average particle size of 400 meshes) and 45 parts by weight of natural zeolite powder (average particle size of 200 meshes) in a kneader, pouring 30 parts by weight of alumina sol (30% by weight), 3 parts by weight of inorganic acid and 50 parts by weight of water, kneading, extruding, rolling ball molding, drying at 100 ℃ for 16h, and then roasting at 550 ℃ in a muffle furnace for 3.0h to obtain a spherical carrier with the diameter of 3 mm.
2. Catalyst preparation
70 parts by weight of a spherical carrier was mixed with 100 parts by weight of a copper nitrate-ammonium metavanadate-ammonium metatungstate-chromium nitrate mixed aqueous solution (containing 18 parts by weight of Cu, 4 parts by weight of V, 4 parts by weight of W and 4 parts by weight of Cr), allowed to stand at room temperature for 4 hours, followed by drying in an oven at 110 ℃ for 16 hours, and then calcined in a muffle furnace at 400 ℃ for 5.0 hours.
3. Catalyst evaluation
Model gas containing benzene waste gas (benzene 565 mg/m)3Toluene 225mg/m3) Passed through a fixed bed reactor packed with 100g of catalyst. The reaction temperature in the reactor was 190 ℃ and the space velocity was 7000ml · h-1·g-1。
The catalyst composition and the evaluation results are shown in Table 1.
TABLE 1
(parts by weight)
Claims (9)
1. The catalyst for treating the benzene-containing waste gas comprises the following components in parts by weight:
(1) 60-90 parts of a carrier;
(2) 10-40 parts of active component;
the active component includes at least one selected from the group consisting of Cu, V, W, Cr, Fe and Ni.
2. The catalyst as set forth in claim 1, wherein the carrier comprises at least one member selected from the group consisting of alumina, titania, natural zeolite powder and activated carbon.
3. The catalyst of claim 1, wherein the catalyst is in the form of a honeycomb, clover, column or sphere.
4. A process for preparing a catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
1) mixing the carrier and the binder, molding, drying and roasting to obtain a molded carrier;
2) and mixing the formed carrier with the solution of the active element, drying and roasting to obtain the catalyst.
5. The method according to claim 4, wherein the temperature of the calcination in the step 1) is 400 to 600 ℃.
6. The method according to claim 4, wherein the temperature of the calcination in the step 2) is 350 to 500 ℃.
7. The method according to claim 4, wherein the active ingredient-containing compound is an active ingredient salt.
8. The method according to claim 6, wherein the active ingredient salt is at least one selected from the group consisting of nitrate, acid ammonium salt and acetate.
9. The use of the catalyst of any one of claims 1 to 3 in the catalytic combustion of benzene-containing exhaust gas to remove benzene compounds.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716511A (en) * | 2009-11-27 | 2010-06-02 | 南京工业大学 | Catalyst for catalytic combustion of industrial organic waste gas and preparation method thereof |
| CN106902838A (en) * | 2017-03-06 | 2017-06-30 | 西南化工研究设计院有限公司 | One kind catalysis burning VOCs monoblock types composite catalyst, preparation method and application |
| CN107376929A (en) * | 2017-08-09 | 2017-11-24 | 南京工业大学 | A kind of catalyst for catalytic combustion and preparation and application |
| CN107866260A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of wet oxidation waste water |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101716511A (en) * | 2009-11-27 | 2010-06-02 | 南京工业大学 | Catalyst for catalytic combustion of industrial organic waste gas and preparation method thereof |
| CN107866260A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of wet oxidation waste water |
| CN106902838A (en) * | 2017-03-06 | 2017-06-30 | 西南化工研究设计院有限公司 | One kind catalysis burning VOCs monoblock types composite catalyst, preparation method and application |
| CN107376929A (en) * | 2017-08-09 | 2017-11-24 | 南京工业大学 | A kind of catalyst for catalytic combustion and preparation and application |
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