CN111545040A - Composite denitration agent and preparation method thereof - Google Patents
Composite denitration agent and preparation method thereof Download PDFInfo
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- CN111545040A CN111545040A CN202010279226.5A CN202010279226A CN111545040A CN 111545040 A CN111545040 A CN 111545040A CN 202010279226 A CN202010279226 A CN 202010279226A CN 111545040 A CN111545040 A CN 111545040A
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- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
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Abstract
The invention belongs to the technical field of denitration, and discloses a composite denitration agent which is mainly prepared from talcum powder, layered silicate, ferric oxide, lanthanum oxide, barium oxide, urea, an oxidant, an organic binder, an inorganic binder, carboxymethyl cellulose, a surfactant, a dispersing agent, polyhydric alcohol and the like. Wherein, the talcum powder and the layered silicate are used as carriers of the denitrifier, compared with TiO2The thermal stability of the denitration agent as a carrier at high temperature is higher; potassium oxide is loaded on the carrier, so that the denitration efficiency of the denitration agent can be effectively improved; iron oxide, lanthanum oxide, barium oxide and urea are used as denitration active components, so that the composite effect is exerted efficiently, and a complex with stable performance is formed; the organic binder and the inorganic binder are added simultaneously, so that the active centers of the active components can be highly dispersed, the structural collapse caused by the calcination of the denitration agent is prevented, and the high activity and high thermal stability of the denitration agent are further ensured. The invention also provides the denitrationThe preparation method of the agent.
Description
Technical Field
The invention belongs to the technical field of denitration, and particularly relates to a composite denitration agent and a preparation method thereof.
Background
Smoke, sulfur dioxide, Nitrogen Oxides (NO) contained in flue gasX) The harmful substances are the main sources of the environmental problems such as air pollution, acid rain, greenhouse effect and the like, and how to effectively remove SO in the flue gas2And NOXArouse the attention of researchers in various countries in the world. Among them, nitrogen oxide is one of the most important air pollutants at present, mainly comes from waste gas generated by burning coal, petroleum, natural gas and the like used in production and life, wherein about 70% of the waste gas comes from direct burning of coal, is a main cause of acid rain, photochemical smog and ozone layer cavities, and generates great harm to ecological environment, industrial and agricultural production and human health.
The denitration agent is adopted to denitrate the flue gas, so that the emission of nitrogen oxides is expected to be fundamentally controlled, but the existing denitration agent is mainly V2O5-WO3(MoO3)/TiO2In the series, wherein TiO2As a carrier, the denitration agent component accounts for a large proportion, the cost of titanium dioxide is high, the production cost of the denitration agent is too high, and the denitration activity of the denitration agent is high, but the thermal stability is poor, and the denitration effect is not ideal enough, so that the denitration agent cannot meet the actual demand.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the composite denitration agent which can convert nitrogen oxides into nitrogen gas, so that the nitrogen oxides in the flue gas can be removed at high precision, and the composite denitration agent has the advantages of obvious denitration effect, high activity, high thermal stability and low cost. Also provides a preparation method of the composite denitration agent.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
the composite denitration agent is mainly prepared from the following raw materials in parts by weight: 30-80 parts of talcum powder, 10-20 parts of phyllosilicate, 5-10 parts of potassium oxide, 5-10 parts of ferric oxide, 5-10 parts of lanthanum oxide, 5-10 parts of barium oxide, 5-10 parts of urea, 1-5 parts of oxidant, 2-5 parts of organic binder, 5-20 parts of inorganic binder, 1-5 parts of carboxymethyl cellulose, 0.5-2 parts of surfactant, 1-10 parts of dispersant and 0.1-10 parts of polyalcohol.
As a further improvement of the scheme, the paint is mainly prepared from the following raw materials in parts by weight: 55 parts of talcum powder, 15 parts of phyllosilicate, 7 parts of potassium oxide, 7 parts of ferric oxide, 7 parts of lanthanum oxide, 7 parts of barium oxide, 7 parts of urea, 3 parts of oxidant, 3 parts of organic binder, 12 parts of inorganic binder, 3 parts of carboxymethyl cellulose, 1 part of surfactant, 5 parts of dispersant and 5 parts of polyol.
In a further improvement of the above aspect, the phyllosilicate is at least one selected from vermiculite, beidellite, rectorite, and saponite, preferably vermiculite. Vermiculite is a natural, inorganic, non-toxic mineral substance, which expands under the action of high temperature. It is a rare mineral and belongs to silicate. Its crystal structure is monoclinic, and looks like mica in its appearance. Vermiculite is produced when certain granites are hydrated. It is generally produced simultaneously with asbestos. Because vermiculite has ion exchange capacity, it has great effect on soil nutrition. The total vermiculite production in the world in 2000 exceeds 50 ten thousand tons. The most prominent countries of production are china, south africa, australia, zimbabwe and the united states. The volume of the vermiculite sheet can be rapidly expanded by 6-20 times after high-temperature roasting, and the specific gravity of the expanded vermiculite sheet is 60-180kg/m3Has strong heat preservation and heat insulation performance.
As a further improvement of the above aspect, the organic binder is at least one selected from the group consisting of a phenol resin, polyvinyl alcohol, and polyacrylamide.
As a further improvement of the scheme, the inorganic binder is attapulgite clay and/or kaolin.
As a further improvement of the above aspect, the surfactant is selected from at least one of calcium lignosulfonate, calcium dodecylsulfonate, or calcium dodecylphenylsulfonate.
As a further improvement of the above aspect, the oxidizing agent comprises potassium permanganate; the polyol comprises glycerol; the dispersant comprises fly ash.
The application method of the denitration agent comprises the following steps: filling the denitrifier in the reactor, or spraying the denitrifier powder into a flue gas channel, carrying out denitration treatment on the flue gas at the temperature of 200-500 ℃, and reducing nitrogen oxides in the flue gas into nitrogen.
A preparation method of a composite denitration agent comprises the following steps:
a. weighing raw material components, uniformly mixing iron oxide, lanthanum oxide, barium oxide and urea, and carrying out activation heat treatment to obtain a composition A;
b. placing talcum powder, phyllosilicate and oxidant into mixed solution of proper amount of ethanol and water, and adjusting pH to 3.5 with acid to obtain composition B;
c. adding potassium oxide, an organic binder, an inorganic binder, carboxymethyl cellulose, a surfactant, a dispersant and polyol into a mixing roll, heating and stirring until the temperature is raised to 80 ℃ to obtain a composition C;
d. adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug;
e. kneading the pug, and then granulating or extruding and forming;
f. and e, drying and calcining the product obtained in the step e to obtain the composite denitration agent.
As a further improvement of the scheme, the activation heat treatment is carried out in an inert atmosphere, the temperature of the activation heat treatment is 200-500 ℃, and the time of the activation heat treatment is 2-3 h.
As a further improvement of the scheme, the calcination temperature of the calcination is 300-800 ℃, and the calcination time is 24-72 h.
The invention has the beneficial effects that: the invention provides a composite denitrifier, which mainly comprises raw materials such as talcum powder, layered silicate, ferric oxide, lanthanum oxide, barium oxide, urea, an oxidant, an organic binder, an inorganic binder, carboxymethyl cellulose, a surfactant, a dispersant, polyhydric alcohol and the like. Wherein, talcum powder and phyllosilicate are adopted as carriers of the denitrifier, compared with TiO2To be loadedThe thermal stability of the denitrifier is higher under the high-temperature condition, and the potassium oxide is loaded on the carrier, so that the denitration efficiency of the denitrifier can be effectively improved; iron oxide, lanthanum oxide, barium oxide and urea are used as denitration active components, so that the composite effect is exerted efficiently, and a complex with stable performance is formed; meanwhile, the organic binder and the inorganic binder are adopted, so that structural collapse caused by calcination of the denitration agent is prevented, and high activity and high thermal stability of the denitration agent are further ensured. The invention also provides a preparation method of the denitration agent, the preparation method is simple and easy to control, free of pollutant emission, rich in raw material source, low in cost, small in production investment and suitable for large-scale industrial production, the denitration agent prepared by the method can convert nitrogen oxide into nitrogen gas, so that the nitrogen oxide in flue gas can be removed at high precision, the denitration effect is obvious, the activity is high, the thermal stability is high, the cost is low, and the denitration agent is an efficient composite denitration agent and has a wide application prospect.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
Uniformly mixing 5Kg of iron oxide, 5Kg of lanthanum oxide, 5Kg of barium oxide and 5Kg of urea, and performing activation heat treatment for 2 hours at 200 ℃ in a nitrogen atmosphere to obtain a composition A; putting 30Kg of talcum powder, 10Kg of phyllosilicate and 1Kg of potassium permanganate into a mixed solution of ethanol and water (the volume ratio of ethanol to water is 1: 1) together, and adjusting the pH value to 3.5 by using acid to obtain a composition B; adding 5Kg of potassium oxide, 2Kg of organic binder, 5Kg of inorganic binder, 1Kg of carboxymethylcellulose, 0.5Kg of surfactant, 1Kg of dispersant and 0.1Kg of glycerin into a mixer, and heating while stirring until the temperature is raised to 80 ℃ to obtain composition C; adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug; kneading the pug, and then granulating or extruding and forming; drying at 120 ℃ for 3h, and calcining at 300 ℃ for 24h to obtain the finished product 1 of the composite denitration agent.
Example 2
Uniformly mixing 10Kg of iron oxide, 10Kg of lanthanum oxide, 10Kg of barium oxide and 10Kg of urea, and performing activation heat treatment for 3 hours at 500 ℃ in a nitrogen atmosphere to obtain a composition A; putting 80Kg of talcum powder, 20Kg of phyllosilicate and 5Kg of potassium permanganate into a mixed solution of a proper amount of ethanol and water (the volume ratio of the ethanol to the water is 1: 1), and adjusting the pH value to 3.5 by using acid to obtain a composition B; adding 10Kg of potassium oxide, 5Kg of organic binder, 20Kg of inorganic binder, 5Kg of carboxymethyl cellulose, 2Kg of surfactant, 10Kg of dispersant and 10Kg of glycerin into a mixing roll, and heating while stirring until the temperature rises to 80 ℃ to obtain composition C; adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug; kneading the pug, and then granulating or extruding and forming; drying at 200 ℃ for 5h, and calcining at 800 ℃ for 72h to obtain the finished product 2 of the composite denitration agent.
Example 3
Uniformly mixing 7Kg of iron oxide, 7Kg of lanthanum oxide, 7Kg of barium oxide and 7Kg of urea, and performing activation heat treatment for 2.5 hours at 300 ℃ in a nitrogen atmosphere to obtain a composition A; putting 55Kg of talcum powder, 15Kg of phyllosilicate and 3Kg of potassium permanganate into a mixed solution of a proper amount of ethanol and water (the volume ratio of the ethanol to the water is 1: 1), and adjusting the pH value to 3.5 by using acid to obtain a composition B; adding 7Kg of potassium oxide, 3Kg of organic binder, 12Kg of inorganic binder, 3Kg of carboxymethyl cellulose, 1Kg of surfactant, 5Kg of dispersant and 5Kg of glycerin into a mixing roll, and heating while stirring until the temperature rises to 80 ℃ to obtain composition C; adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug; kneading the pug, and then granulating or extruding and forming; drying at 160 ℃ for 4h, and calcining at 550 ℃ for 48h to obtain the finished product 3 of the composite denitration agent.
Example 4
Uniformly mixing 7Kg of iron oxide, 7Kg of lanthanum oxide, 7Kg of barium oxide and 7Kg of urea, and performing activation heat treatment for 3 hours at 300 ℃ in a nitrogen atmosphere to obtain a composition A; putting 60Kg of talcum powder, 20Kg of phyllosilicate and 3Kg of potassium permanganate into a mixed solution of a proper amount of ethanol and water (the volume ratio of the ethanol to the water is 1: 1), and adjusting the pH value to 3.5 by using acid to obtain a composition B; adding 7Kg of potassium oxide, 3Kg of organic binder, 10Kg of inorganic binder, 2Kg of carboxymethyl cellulose, 1Kg of surfactant, 4Kg of dispersant and 4Kg of glycerin into a mixing roll, and heating while stirring until the temperature rises to 80 ℃ to obtain a composition C; adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug; kneading the pug, and then granulating or extruding and forming; drying at 200 ℃ for 5h, and calcining at 600 ℃ for 72h to obtain the finished product 4 of the composite denitration agent.
Example 5
Uniformly mixing 8Kg of iron oxide, 8Kg of lanthanum oxide, 8Kg of barium oxide and 8Kg of urea, and performing activation heat treatment for 3 hours at 300 ℃ in a nitrogen atmosphere to obtain a composition A; putting 55Kg of talcum powder, 15Kg of phyllosilicate and 2Kg of potassium permanganate into a mixed solution of a proper amount of ethanol and water (the volume ratio of the ethanol to the water is 1: 1), and adjusting the pH value to 3.5 by using acid to obtain a composition B; adding 7Kg of potassium oxide, 3Kg of organic binder, 12Kg of inorganic binder, 5Kg of carboxymethyl cellulose, 1Kg of surfactant, 8Kg of dispersant and 8Kg of glycerin into a mixing roll, and heating while stirring until the temperature rises to 80 ℃ to obtain composition C; adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug; kneading the pug, and then granulating or extruding and forming; drying at 200 ℃ for 5h, and calcining at 800 ℃ for 72h to obtain the finished product 5 of the composite denitration agent.
Comparative example 1
Comparative example 1 is a blank control.
Comparative example 2
Talc powder in the raw material composition of example 3 was replaced with anatase TiO2Other Components and conditions were the same as in example 3Likewise, the obtained denitration agent finished product was used as comparative example 2.
Evaluation of denitration reactivity
The denitration reaction activity evaluation of the composite denitration agent finished products 1-5 of examples 1-5 and the denitration agent finished products of comparative examples 1-2 is respectively carried out in a self-made tubular SCR reactor, and the denitration efficiency of each group of denitration agents is shown in the following table 1:
calculating the denitration efficiency: NO removed after operation of denitration systemxConcentration (C) of1-C2) With NO in flue gas before denitrationxConcentration (C)1) The ratio of (A) is the denitration efficiency, wherein C2Is NO in the denitrated flue gasxThe concentration of (C) is calculated by the following formula of η ═ C1-C2)×100％/C1；C1、C2In mg/standard cubic meter.
TABLE 1 denitration efficiency results of the denitration agents of examples 1 to 5 and comparative examples 1 to 2
In table 1, it can be seen from examples 1 to 5 and comparative examples 1 to 2 that the denitration catalysts obtained in examples 1 to 5 have higher denitration efficiency and significant beneficial effects than those of comparative examples 1 and 2, and the denitration catalyst provided by the invention uses talc powder as a carrier, so that the production cost is lower, the talc powder has better lubricity, is easier to separate from a grinding tool, has higher extrusion rate and higher production efficiency, is convenient for industrial popularization and application, is an efficient composite denitration agent, and has a wide application prospect.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (10)
1. The composite denitration agent is characterized by being mainly prepared from the following raw materials in parts by weight: 30-80 parts of talcum powder, 10-20 parts of phyllosilicate, 5-10 parts of potassium oxide, 5-10 parts of ferric oxide, 5-10 parts of lanthanum oxide, 5-10 parts of barium oxide, 5-10 parts of urea, 1-5 parts of oxidant, 2-5 parts of organic binder, 5-20 parts of inorganic binder, 1-5 parts of carboxymethyl cellulose, 0.5-2 parts of surfactant, 1-10 parts of dispersant and 0.1-10 parts of polyalcohol.
2. The composite denitration agent of claim 1, which is mainly prepared from the following raw materials in parts by weight: 55 parts of talcum powder, 15 parts of phyllosilicate, 7 parts of potassium oxide, 7 parts of ferric oxide, 7 parts of lanthanum oxide, 7 parts of barium oxide, 7 parts of urea, 3 parts of oxidant, 3 parts of organic binder, 12 parts of inorganic binder, 3 parts of carboxymethyl cellulose, 1 part of surfactant, 5 parts of dispersant and 5 parts of polyol.
3. The composite denitrifier according to claim 1, wherein the phyllosilicate is selected from at least one of vermiculite, beidellite, rectorite and saponite, preferably vermiculite.
4. The composite denitration agent according to claim 1, wherein the organic binder is at least one selected from the group consisting of a phenol resin, polyvinyl alcohol and polyacrylamide.
5. The composite denitrifier according to claim 1, wherein the inorganic binder is attapulgite clay and/or kaolin.
6. The composite denitration agent of claim 1, wherein the surfactant is at least one selected from calcium lignosulfonate, calcium dodecylsulfonate and calcium dodecylbenzenesulfonate.
7. The composite denitrifier of claim 1, wherein the oxidant comprises potassium permanganate; the polyol comprises glycerol; the dispersant comprises fly ash.
8. The preparation method of the composite denitration agent is characterized by comprising the following steps:
a. weighing raw material components, uniformly mixing iron oxide, lanthanum oxide, barium oxide and urea, and carrying out activation heat treatment to obtain a composition A;
b. placing talcum powder, phyllosilicate and oxidant into mixed solution of ethanol and water, and adjusting pH to 3.5 with acid to obtain composition B;
c. adding potassium oxide, an organic binder, an inorganic binder, carboxymethyl cellulose, a surfactant, a dispersant and polyol into a mixing roll, heating and stirring until the temperature is raised to 80 ℃ to obtain a composition C;
d. adding the composition A, the composition B and the composition C into a mixer together, and adding water for mixing to obtain pug;
e. kneading the pug, and then granulating or extruding and forming;
f. and e, drying and calcining the product obtained in the step e to obtain the composite denitration agent as claimed in any one of claims 1 to 7.
9. The method as claimed in claim 8, wherein the activation heat treatment is performed under an inert atmosphere at a temperature of 200 ℃ to 500 ℃ for 2-3 h.
10. The preparation method as claimed in claim 8, wherein the calcination temperature is 300-800 ℃ and the calcination time is 24-72 h.
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Cited By (5)
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| CN113144897A (en) * | 2021-04-25 | 2021-07-23 | 河北和悦环保科技有限公司 | Dry-process denitration agent and application method thereof |
| CN113828278A (en) * | 2021-10-29 | 2021-12-24 | 辽宁基伊能源科技有限公司 | Efficient denitration agent for waste gas treatment and preparation method thereof |
| CN114272752A (en) * | 2022-01-27 | 2022-04-05 | 江苏扬农化工集团有限公司 | Organic coated denitration agent and preparation method thereof |
| CN115501748A (en) * | 2021-08-31 | 2022-12-23 | 嘉兴沃特泰科环保科技股份有限公司 | Denitration agent and preparation method thereof |
| CN117599604A (en) * | 2023-10-24 | 2024-02-27 | 上海全熙环保科技股份有限公司 | Special denitration agent composite material for alkali furnace and preparation method thereof |
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| CN115501748A (en) * | 2021-08-31 | 2022-12-23 | 嘉兴沃特泰科环保科技股份有限公司 | Denitration agent and preparation method thereof |
| CN113828278A (en) * | 2021-10-29 | 2021-12-24 | 辽宁基伊能源科技有限公司 | Efficient denitration agent for waste gas treatment and preparation method thereof |
| CN114272752A (en) * | 2022-01-27 | 2022-04-05 | 江苏扬农化工集团有限公司 | Organic coated denitration agent and preparation method thereof |
| CN117599604A (en) * | 2023-10-24 | 2024-02-27 | 上海全熙环保科技股份有限公司 | Special denitration agent composite material for alkali furnace and preparation method thereof |
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