CN114146702A - Graphene-based modified calcium carbonate denitration agent and preparation method and application thereof - Google Patents
Graphene-based modified calcium carbonate denitration agent and preparation method and application thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 56
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 238000004898 kneading Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000892 attapulgite Drugs 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- -1 graphene modified calcium carbonate Chemical class 0.000 claims description 30
- 239000011265 semifinished product Substances 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01D53/04—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 with stationary adsorbents
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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
- B01D53/8628—Processes characterised by a specific catalyst
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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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/702—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a graphene-based modified calcium carbonate denitration agent, and a preparation method and application thereof, 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, and has good flue gas adsorbing effect and high denitration efficiency.
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 by the SCR technology, the activity of the denitration catalyst directly influences the denitration efficiency, however, most of the denitration catalysts in the SCR technology have the problem of easy water-sulfur poisoning, the denitration efficiency cannot reach the design value, the emission of NOx in flue gas cannot reach the standard, the ammonia escape rate is increased, and the high-efficiency utilization of the catalyst 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, so that the problem that the prepared denitration agent is easy to be poisoned by water and sulfur is solved, and the service life of the denitration agent is prolonged. 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 into the pre-modified calcium carbonate powder for secondary ball milling to obtain a semi-finished product of the graphene-based modified calcium carbonate powder denitration agent; and finally, adding a proper amount of water into the semi-finished product of the graphene-based modified calcium carbonate powder denitration agent, uniformly stirring, and kneading into a required shape in a kneading machine to obtain the graphene-based modified calcium carbonate powder denitration agent.
Further, the coupling agent is titanate.
Furthermore, the first ball milling time is 1-2h, the coupling agent, the graphene and the calcium carbonate powder can be effectively and uniformly mixed, and the calcium carbonate powder is prevented from caking.
Furthermore, the time of the second ball milling is 1-2h, so that the calcium carbonate powder modified by the graphene can be effectively mixed with the attapulgite, 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 a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
The invention also provides the denitration agent prepared by the preparation method of the graphene modified calcium carbonate denitration agent.
The invention also provides application of the 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, is beneficial to increasing the use efficiency of the denitration catalyst, and reduces the use cost of the denitration catalyst.
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 a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
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 a commercially available denitration catalyst into the ball mill, and continuously ball-milling for 2 hours to obtain a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
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 a commercially available denitration catalyst into the ball mill, and continuously ball-milling for 1h to obtain a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
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 a commercially available denitration catalyst into the ball mill, and continuously ball-milling for 1h to obtain a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
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 a commercially available denitration catalyst into the ball mill, and continuously ball-milling for 1h to obtain a semi-finished product of the graphene modified calcium carbonate denitration agent;
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 strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
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 a commercially available denitration catalyst into the ball mill, and continuously ball-milling for 1h to obtain a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
Comparative example 1:
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 a semi-finished product of the denitration agent;
2) adding a proper amount of water into the semi-finished product of the denitration agent obtained in the step 1), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the denitration agent.
Application example 1:
the denitration agent obtained in the embodiments 2 to 7 and the comparative example 1 is used in a denitration device corresponding to a catalyst for denitration experiment, and specifically comprises the following steps: filling the denitration agent product into a reaction tube of a tube type fixed bed, wherein the tube diameter of the reaction tube of the tube type fixed bed is 100mm, and the filling height of the denitration agent in the reaction tube is 65% of the length of the reaction tube; the heat exchange medium is molten salt, and the waste gas contacts with the denitration agent through the tubular fixed bed to start the adsorption process. The concentration of the nitrogen-containing compound in the simulated exhaust gas used in the test was 1450mg/m3The flow rate of flue gas is 10m/s, and the temperature is 500 ℃. The removal rate of NO in the flue gas is taken as the denitration rate, the highest denitration rate and the retention time are recorded, and the test results are shown in Table 1.
TABLE 1 denitration efficiency and maintenance time
| Highest denitration efficiency | Maintenance time | |
| Example 2 | 90％ | 4.5h |
| Example 3 | 92％ | 5.5h |
| Example 4 | 90％ | 6h |
| Example 5 | 90％ | 4.5h |
| Example 6 | 90％ | 3h |
| Example 7 | 92％ | 3.5h |
| Comparative example 1 | 78％ | 1.5h |
From the above table 1, it can be found that the denitration agent prepared by the invention has a high catalytic effect which is more than 90%, and can maintain high-efficiency denitration for a long time.
Claims (7)
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 into the pre-modified calcium carbonate powder for secondary ball milling to obtain a semi-finished product of the graphene-based modified calcium carbonate powder denitration agent; and finally, adding a proper amount of water into the semi-finished product of the graphene-based modified calcium carbonate powder denitration agent, uniformly stirring, and kneading into a required shape in a kneading machine to obtain the graphene-based 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 2 is characterized by 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 a semi-finished product of the graphene modified calcium carbonate denitration agent;
3) adding a proper amount of water into the semi-finished product of the graphene modified calcium carbonate denitration agent obtained in the step 2), uniformly stirring, and kneading into strips or granules in a kneading machine to obtain the graphene modified calcium carbonate powder denitration agent.
6. The denitration agent prepared by the preparation method of any one of claims 1 to 5 based on the graphene modified calcium carbonate denitration agent.
7. The use of the denitrifier of claim 6 in the denitration of flue gas.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345269A (en) * | 2016-10-24 | 2017-01-25 | 马鞍山科宇环境工程有限公司 | Coal denitration agent |
| CN113828130A (en) * | 2021-10-28 | 2021-12-24 | 辽宁基伊能源科技有限公司 | Preparation method and application of graphene-based modified calcium carbonate denitration agent |
-
2021
- 2021-12-01 CN CN202111458247.4A patent/CN114146702A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345269A (en) * | 2016-10-24 | 2017-01-25 | 马鞍山科宇环境工程有限公司 | Coal denitration agent |
| CN113828130A (en) * | 2021-10-28 | 2021-12-24 | 辽宁基伊能源科技有限公司 | Preparation method and application of graphene-based modified calcium carbonate denitration agent |
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Application publication date: 20220308 |