CN113828130A - Preparation method and application of graphene-based modified calcium carbonate denitration agent - Google Patents
Preparation method and application of graphene-based modified calcium carbonate denitration agent Download PDFInfo
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- CN113828130A CN113828130A CN202111260614.XA CN202111260614A CN113828130A CN 113828130 A CN113828130 A CN 113828130A CN 202111260614 A CN202111260614 A CN 202111260614A CN 113828130 A CN113828130 A CN 113828130A
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- calcium carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
Abstract
The invention discloses a preparation method and application of a graphene-based modified calcium carbonate denitration agent, and belongs to the technical field of preparation of denitration agents. The method comprises the steps of putting a coupling agent, graphene and calcium carbonate powder into a ball mill for primary ball milling to obtain pre-modified calcium carbonate powder; then adding attapulgite and a denitration catalyst for secondary ball milling; and finally, adding a proper amount of water, uniformly stirring, and kneading into a required shape in a kneading machine to obtain the graphene-modified calcium carbonate powder denitration agent. The obtained denitration agent can effectively resist the poisoning effect of sulfide and water on the denitration catalyst, has good flue gas adsorbing effect and high denitration efficiency, maintains high denitration efficiency for a longer time, and reduces the use cost of the denitration catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of denitration agents, and particularly relates to a preparation method and application of a graphene-based modified calcium carbonate denitration agent.
Background
In recent years, the problem of air pollution is more and more emphasized by people, wherein nitrogen oxides (NOx) in flue gas of a coal-fired power plant are an important source of pollution, and denitration treatment of the flue gas is not slow enough. Research shows that NH3Selective catalytic reduction of NOx (NH)3SCR) is the most effective method for flue gas denitration of coal-fired power plants and is already mature to be applied in the field of flue gas denitration. SCR (selective Catalytic reduction) is a selective Catalytic reduction denitration technique. The technology has the advantages of no by-product, no secondary pollution, simple device structure, high removal efficiency of more than 90 percent, reliable operation, convenient maintenance and the like, and is widely applied to denitration engineering.
The most key in the SCR technology is the denitration catalyst used in the SCR technology, however, most denitration catalysts in the SCR technology have the problem of easy water and sulfur poisoning, and the high-efficiency utilization of the catalysts is seriously influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a graphene modified calcium carbonate denitration agent. The technical problem to be solved by the invention is to provide the denitration agent prepared by the preparation method of the graphene modified calcium carbonate denitration agent. The invention finally aims to solve the technical problem of providing the application of the denitration agent.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a graphene-based modified calcium carbonate denitration agent comprises the following steps: putting the coupling agent, the graphene and the calcium carbonate powder into a ball mill for primary ball milling to obtain pre-modified calcium carbonate powder; then adding attapulgite and a denitration catalyst for secondary ball milling; and finally, adding a proper amount of water, uniformly stirring, and kneading into a required shape in a kneading machine to obtain the graphene-modified calcium carbonate powder denitration agent.
Further, the coupling agent is titanate.
Further, the first ball milling time is 1-2h, and the coupling agent, the graphene and the calcium carbonate powder are effectively and uniformly mixed to prevent the calcium carbonate powder from caking.
Furthermore, the time of the second ball milling is 1-2h, so that the calcium carbonate powder modified by the graphene is effectively mixed with the attapulgite uniformly, and the later kneading and forming are facilitated.
Further, the preparation method of the graphene-based modified calcium carbonate denitration agent specifically comprises the following steps:
1) putting 2-3 parts by mass of titanate coupling agent, 1-4 parts by mass of graphene and 80-100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1-2 hours to obtain pre-modified calcium carbonate powder;
2) continuously adding 50-100 parts by mass of attapulgite and 100-200 parts by mass of a denitration catalyst into the ball mill, and continuously ball-milling for 1-2h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Further, the denitration catalyst is prepared by reacting cerous nitrate and tetraethyl silicate under an alkaline condition.
The invention also provides a denitration agent prepared by the preparation method based on the graphene modified calcium carbonate denitration agent.
The invention also provides an application of the graphene-based modified calcium carbonate denitration agent in flue gas denitration.
Compared with the prior art, the invention has the beneficial effects that:
the denitration agent prepared by the preparation method of the graphene modified calcium carbonate denitration agent provided by the invention is prepared by coupling graphene, calcium carbonate powder, attapulgite and a denitration catalyst together by using a coupling agent in a proper proportion, and taking the graphene, the calcium carbonate powder and the attapulgite as desulfurization components in the denitration agent, so that the poisoning effect of sulfide and water on the denitration catalyst is resisted, meanwhile, the attapulgite increases the surface area of the denitration agent adsorbed to flue gas and is beneficial to increasing the use efficiency of the denitration catalyst, the high denitration efficiency for a longer time is maintained, and the use cost of the denitration catalyst is reduced.
Detailed Description
The invention is further described with reference to specific examples.
Example 1:
preparing an SCR denitration catalyst: adding cerous nitrate and tetraethyl silicate into a beaker according to the molar ratio of cerium to silicon of 1:3, adding a proper amount of mixed solution of ethanol and distilled water to dissolve the cerous nitrate and the tetraethyl silicate, and uniformly stirring the mixed solution by using a magnetic stirrer. And then, dropwise adding ammonia water into the mixed solution for precipitation, adjusting the pH value of the solution to 9, stopping dropwise adding the ammonia water, continuously stirring for 1 hour, and stopping stirring. Standing for 24h for aging, suction-filtering with Buchner funnel, washing precipitate with distilled water for 3 times, and drying the obtained precipitate in an oven at 110 deg.C for 3 h. And transferring the obtained solid substance into a mortar, grinding the solid substance into powder, finally putting the powder into a muffle furnace, roasting the powder for 4 hours at the temperature of 500 ℃, taking out a sample after the muffle furnace is cooled to the room temperature, and bagging the sample to obtain the denitration catalyst.
Example 2:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 2 parts by mass of titanate coupling agent, 1 part by mass of graphene and 80 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1h to obtain pre-modified calcium carbonate powder;
2) continuously adding 100 parts by mass of attapulgite and 50 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 3:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 2 parts by mass of titanate coupling agent, 1 part by mass of graphene and 80 parts by mass of calcium carbonate powder into a ball mill for ball milling for 2 hours to obtain pre-modified calcium carbonate powder;
2) continuously adding 100 parts by mass of attapulgite and 50 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 2 hours to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 4:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 3 parts by mass of titanate coupling agent, 1 part by mass of graphene and 100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1h to obtain pre-modified calcium carbonate powder;
2) continuously adding 100 parts by mass of attapulgite and 100 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 5:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 3 parts by mass of titanate coupling agent, 2 parts by mass of graphene and 100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1h to obtain pre-modified calcium carbonate powder;
2) continuously adding 100 parts by mass of attapulgite and 100 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 6:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 3 parts by mass of titanate coupling agent, 4 parts by mass of graphene and 100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1h to obtain pre-modified calcium carbonate powder;
2) continuously adding 100 parts by mass of attapulgite and 100 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 7:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) putting 3 parts by mass of titanate coupling agent, 4 parts by mass of graphene and 100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1h to obtain pre-modified calcium carbonate powder;
2) continuously adding 50 parts by mass of attapulgite and 200 parts by mass of the denitration catalyst prepared in the example 1 into a ball mill, and continuously ball-milling for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Comparative example 8:
the preparation method of the graphene-modified calcium carbonate powder-based denitration agent comprises the following steps:
1) continuously ball-milling 3 parts by mass of titanate coupling agent, 50 parts by mass of attapulgite and 200 parts by mass of commercially available denitration catalyst for 1h to obtain graphene modified calcium carbonate powder denitration agent powder;
2) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 1), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
Example 9:
the graphene modified calcium carbonate powder denitration agent obtained in examples 2 to 7 and comparative example 8 was used in a denitration device corresponding to a catalyst to perform a denitration experiment, and the test results are shown in table 1, with the removal rate of NO in flue gas being the denitration rate.
TABLE 1 denitration efficiency and maintenance time
From table 1, it can be seen that the denitration catalyst effect of comparative example 8 is the highest in efficiency in a short time, slightly higher than that of examples 6 and 7, but is rapidly decreased, probably due to water or sulfur poisoning of the denitration catalyst therein, while the denitration efficiencies of examples 6 and 7 are not much different, but the denitration agent prepared in example 6 maintains higher denitration efficiency than that of example 7 in a longer time.
Claims (8)
1. A preparation method of a graphene-based modified calcium carbonate denitration agent is characterized by comprising the following steps: putting the coupling agent, the graphene and the calcium carbonate powder into a ball mill for primary ball milling to obtain pre-modified calcium carbonate powder; then adding attapulgite and a denitration catalyst for secondary ball milling; and finally, adding a proper amount of water, uniformly stirring, and kneading into a required shape in a kneading machine to obtain the graphene-modified calcium carbonate powder denitration agent.
2. The preparation method of the graphene-modified calcium carbonate denitration agent based on claim 1, wherein the coupling agent is titanate.
3. The preparation method of the graphene-based modified calcium carbonate denitration agent according to claim 1, wherein the first ball milling time is 1-2 h.
4. The preparation method of the graphene-modified calcium carbonate denitration agent based on claim 1, wherein the time of the second ball milling is 1-2 h.
5. The preparation method of the graphene-modified calcium carbonate denitration agent based on claim 1 is characterized by specifically comprising the following steps:
1) putting 2-3 parts by mass of titanate coupling agent, 1-4 parts by mass of graphene and 80-100 parts by mass of calcium carbonate powder into a ball mill for ball milling for 1-2 hours to obtain pre-modified calcium carbonate powder;
2) continuously adding 50-100 parts by mass of attapulgite and 100-200 parts by mass of a denitration catalyst into the ball mill, and continuously ball-milling for 1-2h to obtain graphene modified calcium carbonate powder denitration agent powder;
3) adding a proper amount of water into the graphene modified calcium carbonate powder denitration agent powder obtained in the step 2), uniformly stirring, and kneading into a strip-shaped or granular denitration agent in a kneading machine for later use.
6. The preparation method of the graphene-modified calcium carbonate denitration agent according to claim 5, wherein the denitration catalyst is prepared by reacting cerous nitrate and tetraethyl silicate under an alkaline condition.
7. The denitration agent prepared by the preparation method of any one of claims 1 to 6 based on the graphene modified calcium carbonate denitration agent.
8. The application of the graphene-based modified calcium carbonate denitration agent disclosed by claim 7 in flue gas denitration.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114146702A (en) * | 2021-12-01 | 2022-03-08 | 通化鑫鸿新材料有限公司 | Graphene-based modified calcium carbonate denitration agent and preparation method and application thereof |
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