(19) State Intellectual Property Office of the People's Republic of China (12) Invention patent application (10) Application publication number CN A (43) Application publication date 2022.03.08 (21) Application number 2.53/04 (2006.01) B01D 53/60 (2006.01 ) (22) Application date 2021.12.01 (71) Applicant's address: North of Binhe East Road, Yayuan Town, Erdaojiang District, Tonghua City, Jilin Province (72) Inventor Wei Jiuhong Feng Yanfeng Wei Yushan Weishan Li Yan (74) Patent Agent Shanghai New Boli Intellectual Property Agency (General Partnership) Attorney Wang Jing (51) Int.Cl.B01J 23/10 (2006.01) B01J 33/00 (2006.01) B01J 27/232 (2006.01) B01D 53/ 86 (2006.01) B01D 53/56 (2006.01) 1 page of claims, 4 pages of instructions (54) Invention name based on graphene modified calcium carbonate denitrification agent and its preparation method and application (57) Abstract This invention discloses a graphene-based Denitrification and denitrification agent graphene-modified calcium carbonate The invention relates to a medicament and its preparation method and application, and belongs to the technical field of denitrification agent preparation. In the present invention, the coupling agent, graphene, and calcium carbonate powder are put into the ball mill for the first ball milling to obtain the pre-modified calcium carbonate powder; then the attapulgite and the denitration catalyst are added for the second ball milling; finally, an appropriate amount of water is added to stir Evenly, put it into a kneader and knead it into the desired shape, and then get the graphene-modified calcium carbonate powder denitrification agent.

The prepared denitration agent can effectively resist the poisoning effect of sulfide and water on the denitration catalyst, has a good effect of effectively absorbing flue gas, and has high denitration efficiency.  A2 0 7 6 4 1 4 1 1NC CN A 1/1 page 1. A method for preparing a graphene-modified calcium carbonate denitrification agent is characterized in that it comprises: a coupling agent, graphene, and calcium carbonate powder. The ball mill is used for the first ball milling to obtain pre-modified calcium carbonate powder; then, attapulgite and denitration catalysts are added to the pre-modified calcium carbonate powder for secondary ball milling to obtain graphene-based modified calcium carbonate powder. Semi-finished calcium powder denitrification agent; Finally, add an appropriate amount of water to the semi-finished graphene-modified calcium carbonate powder denitrification agent, stir evenly, put it into a kneader, and knead it into the desired shape, that is graphene-based modified calcium carbonate Agent of powder denitrification agent.  2. the preparation method based on a graphene-modified calcium carbonate denitrification agent according to claim 1, is characterized in that, the described coupling agent is titanate.  3. the preparation method based on a graphene-modified calcium carbonate denitrification agent according to claim 1, is characterized in that, described ball milling time for the first time is 1-2h.  4. the preparation method based on a graphene-modified calcium carbonate denitrification agent according to claim 1, is characterized in that, described ball milling time for the second time is 1-2h.  5. the preparation method based on graphene-modified calcium carbonate denitrification agent according to claim 2, is characterized in that, specifically comprises the following steps: 1) the titanate coupling agent of 2-3 mass parts, 1-4 Graphene of mass parts, the calcium carbonate powder of 80-100 mass parts is put into ball mill and carry out ball milling 1-2h, obtains pre-modified calcium carbonate powder; 2) continue to add 50-100 mass parts attapulgite and 100 mass parts in ball mill Parts by mass-200 parts by mass of denitration catalyst, continuous ball mill for 1-2h, obtain the semi-finished product of graphene-modified calcium carbonate denitrification agent; 3) add an appropriate amount of water in the semi-finished product of graphene-modified calcium carbonate denitrification agent obtained in step 2) and stir Put it into a kneader and knead it into strips or granules to get graphene-modified calcium carbonate denitrification powder agent.

6. a denitrification agent prepared based on the preparation method of the graphene-modified calcium carbonate denitrification agent described in any one of claims 1-5.  7. The application of denitration agent described in claim 6 in flue gas denitrification.  22 CN A Instruction manual 1/4 page Graphene modified calcium carbonate denitrification agent and it's preparation method and application Technical field Preparation method and application of denitrification agent. Background technology [0002] In recent years, the air pollution problem has been paid more and more attention by people, wherein nitrogen oxides (NOx) in the flue gas of coal-fired power plants are important sources of pollution, and it is an urgent need to carry out denitrification treatment to the flue gas. Studies have shown that NH selective catalytic reduction of 3 NOx (NH‑SCR) is the most effective method for flue gas denitrification in coal-fired power plants, and has been maturely applied in the field of flue gas denitrification.  SCR3() is a selective catalytic reduction denitrification technology. This technology has the advantages of no by-products, no secondary pollution, simple device structure, the removal efficiency of over 90%, reliable operation, convenient maintenance, etc., and has been widely used in denitrification projects.  The most critical thing in SCR technology is the denitrification catalyst used. Its activity directly affects denitrification efficiency. However, most denitrification catalysts in SCR technology are prone to water and sulfur poisoning, which will cause the denitrification efficiency to fail to meet the design requirements. , the NOx emission in the flue gas is not up to the standard, and the ammonia slip rate increases, which seriously affects the efficient utilization of the catalyst.

For the above-mentioned problems existing in the prior art, the technical problem to be solved by this invention is to provide a kind of preparation method of graphene-modified calcium carbonate denitrifying agent, improve the problem making the problem of denitrifying agent easy water body sulfur poisoning, Extend the service life of the denitrification agent. The technical problem to be solved by the present invention is to provide a denitrification agent prepared by the preparation method of a graphene-modified calcium carbonate denitrification agent. The ultimate technical problem to be solved by the present invention is to provide the application of the above-mentioned denitration agent. To solve the above-mentioned technical problems, the technical scheme adopted in the present invention is as follows: A preparation method based on a graphene-modified calcium carbonate denitrification agent, comprising: a coupling agent, graphene, and calcium carbonate powder enter the ball mill for the first ball milling, to obtain pre-modified calcium carbonate powder; then add attapulgite and denitration catalyst to the pre-modified calcium carbonate powder for secondary ball milling to obtain a semi-finished denitrification agent based on graphene-modified calcium carbonate powder; finally, in graphene Add an appropriate amount of water to the semi-finished product of the modified calcium carbonate powder denitrification agent, stir evenly, put it into a kneader and knead it into a desired shape, and obtain a graphene-based modified calcium carbonate powder denitrification agent. Further, the coupling agent is titanate.  Further, described ball milling time for the first time is 1-2h, coupling agent, Graphene, and calcium carbonate powder can be mixed effectively, preventing calcium carbonate powder from agglomerating.  Further, described ball milling time for the second time is 1-2h, and the calcium carbonate powder after graphene modification can be mixed with attapulgite effectively, which is conducive to later-stage mixing molding.

Further, the described preparation method based on graphene-modified calcium carbonate denitrification agent specifically comprises: 1) with the titanate coupling agent of 2-3 mass parts, graphene, 80-100 mass parts Calcium carbonate powder is put into a ball mill and carry out ball milling 1-2h, obtains pre-modified calcium carbonate powder; 2) continue to add 50-100 mass parts attapulgite and 100 mass parts 200 mass parts denitrification catalysts in ball mill, continue ball milling 1- 2h, obtain graphene-modified calcium carbonate denitrifying agent semi-finished product; 33 CN A 2/4 [0013] 3) step 2) gained graphene-modified calcium carbonate denitrifying agent semi-finished product adds the appropriate amount of water, stirs evenly, puts into kneader Knead into strips or granules to obtain a graphene-modified powdered calcium carbonate denitrification agent. The present invention also provides a denitrification agent prepared based on the preparation method of the graphene-modified calcium carbonate denitrification agent. The invention also provides the application of the denitration agent in flue gas denitration. Compared with the prior art, the beneficial effects of the present invention are: the denitration agent prepared by the preparation method of the graphene-modified calcium carbonate denitrification agent provided by the invention is to utilize a coupling agent to combine graphene and calcium carbonate powder with an appropriate It is composed of a combination of attapulgite and denitration catalyst. Graphene, calcium carbonate powder, and attapulgite are used as desulfurization components in the denitration agent to resist the poisonous effect of sulfide and water on the denitration catalyst. At the same time, the attapulgite increases the adsorption surface area of the denitrification agent to the flue gas, which helps to improve the use efficiency of the denitrification catalyst and reduce the use cost of the denitrification catalyst.

The specific embodiment [0018] The present invention will be further described below in conjunction with the specific embodiment. Example 1: Preparation of SCR denitrification catalyst: Add cerium nitrate and tetraethyl silicate to a beaker at a molar ratio of cerium to silicon of 1:3, add an appropriate amount of a mixed solution of ethanol and distilled water to dissolve it, and use a magnetic force to dissolve the mixed solution. Blend with a mixer until smooth. Then add ammonia water to the mixed solution for precipitation, adjust the pH value of the solution to 9, then stop the dropwise addition of ammonia water, continue stirring for 1 hour, and then stop stirring. After standing for 24 hours to age, filter with a Buchner funnel, wash the precipitate with distilled water three times, and dry the obtained precipitate in an oven at 110° C. for 3 hours. Then the obtained solid material was transferred into a mortar and ground into powder, and finally put into a muffle furnace and baked at 500 °C for 4 hours. After the muffle furnace is cooled to room temperature, the sample is taken out and packed into a bag to obtain the denitration catalyst. Embodiment 2: [0022] The preparation method based on graphene-modified powder calcium carbonate denitrification agent: 1) by the titanate coupling agent of 2 mass parts, the graphene of 1 mass part, the powder of 80 mass parts The calcium carbonate composition is put into a ball mill for ball milling for 1 hour to obtain pre-modified calcium carbonate powder; continue ball mill for 1 hour to obtain a semi-finished graphene-modified calcium carbonate denitrification agent; or granular, that is, a graphene-based modified calcium carbonate powder denitrification agent.

Embodiment 3: The preparation method based on the powder calcium carbonate denitrification agent of graphene modification: 1) by the titanate coupling agent of 2 mass parts, the graphene of 1 mass part, the powder of 80 mass parts Calcium carbonate composition enters the ball mill and carries out ball milling 2h, obtains pre-modified calcium carbonate powder; Namely obtains the semi-finished product of graphene-modified calcium carbonate denitrification agent; 3) the semi-finished product of graphene-modified calcium carbonate denitrification agent obtained in step 2) adds the appropriate amount of water and stirs evenly, put into a mixer and knead into strips or granules to obtain graphene-modified calcium carbonate denitration agent powder. Embodiment 4: [0032] The preparation method based on graphene-modified powder calcium carbonate denitrification agent: 44CN A instruction manual 3/4 page [0033] 1) with the titanate coupling agent of 3 mass parts, 1 mass part 100 parts by mass of graphene, put 100 parts by mass of calcium carbonate powder into a ball mill and carry out ball milling for 1h to obtain pre-modified calcium carbonate powder; to obtain a semi-finished graphene-modified calcium carbonate denitrification agent; kneading into strips or granules to obtain a denitrification agent based on graphene-modified calcium carbonate powder.

Embodiment 5: The preparation method based on the powder calcium carbonate denitrification agent of graphene modification: 1) by the titanate coupling agent of 3 mass parts, the graphene of 2 mass parts, and the powder of 100 mass parts The calcium carbonate composition is put into a ball mill for ball milling for 1 hour to obtain pre-modified calcium carbonate powder; that is, a semi-finished product of graphene-modified calcium carbonate denitrification agent is obtained; and a denitrification agent based on graphene-modified calcium carbonate powder is obtained. Embodiment 6: The preparation method based on the powder calcium carbonate denitrification agent of graphene modification: 1) by the titanate coupling agent of 3 mass parts, the graphene of 4 mass parts, the powder of 100 mass parts Calcium carbonate composition enters the ball mill and carries out ball milling 1h, obtains pre-modified calcium carbonate powder; Namely obtains graphene modified calcium carbonate denitrification agent semi-finished product; 3) step 2) gained graphene modified powder calcium carbonate denitrification agent powder is added Stir the water evenly, put it into a kneader and knead it into strips or granules, and then get the graphene-modified powder calcium carbonate denitrification agent.

Embodiment 7: The preparation method based on the powder calcium carbonate denitrification agent of graphene modification: 1) by the titanate coupling agent of 3 mass parts, the graphene of 4 mass parts, the powder of 100 mass parts Calcium carbonate composition enters the ball mill and carries out ball milling 1h, obtains pre-modified calcium carbonate powder; Namely obtains the semi-finished product of graphene-modified calcium carbonate denitrification agent; 3) adds the appropriate amount of water and stirs evenly, put into the mixing machine and knead into strips or granules to obtain graphene-modified calcium carbonate denitration agent powder. Comparative Example 1: [005