CN114471353A - Organic coated denitration agent and preparation method thereof - Google Patents
Organic coated denitration agent and preparation method thereof Download PDFInfo
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- CN114471353A CN114471353A CN202210101129.6A CN202210101129A CN114471353A CN 114471353 A CN114471353 A CN 114471353A CN 202210101129 A CN202210101129 A CN 202210101129A CN 114471353 A CN114471353 A CN 114471353A
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- coating
- polyol
- pigment
- spherical particles
- isocyanate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 118
- 238000000576 coating method Methods 0.000 claims abstract description 116
- 239000000049 pigment Substances 0.000 claims abstract description 81
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004202 carbamide Substances 0.000 claims abstract description 66
- 239000012798 spherical particle Substances 0.000 claims abstract description 59
- 239000012948 isocyanate Substances 0.000 claims abstract description 58
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims description 55
- 150000003077 polyols Chemical class 0.000 claims description 55
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 27
- 238000005469 granulation Methods 0.000 claims description 22
- 230000003179 granulation Effects 0.000 claims description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 polymethylene Polymers 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 9
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 235000019482 Palm oil Nutrition 0.000 claims description 5
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- 239000002540 palm oil Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004814 polyurethane Substances 0.000 abstract description 11
- 229920002635 polyurethane Polymers 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 229920006254 polymer film Polymers 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011527 polyurethane coating Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003672 ureas Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 1
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940088990 ammonium stearate Drugs 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229940078456 calcium stearate Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- 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
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/003—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic followed by coating of the granules
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/006—Coating of the granules without description of the process or the device by which the granules are obtained
-
- 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
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/12—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic in rotating drums
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an organic coated denitration agent and a preparation method thereof, wherein the preparation method comprises the following steps: melting urea, granulating and molding to obtain spherical particles; and putting the obtained spherical particles into coating equipment, uniformly rotating the spherical particles, and spraying isocyanate and a polyol-pigment mixture for coating to obtain the organic coated denitration agent. According to the method, the surface of the molded particles is modified in a coating mode to form the polyurethane polymer film, so that the slow release effect is achieved, the ineffective decomposition of urea in the denitration process is reduced, the urea is fully used for reducing nitric oxide, and the utilization rate of the urea is improved; the raw materials of the coating used in the method also comprise pigment, which is helpful for distinguishing whether the formed coating is complete and uniform, and meanwhile, metal ions in the pigment can play a role of a catalyst in a denitration reaction, so that the denitration effect is improved; the method has the advantages of simple operation steps, wide raw material source, low equipment investment and production cost and easy industrial implementation.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration, and relates to an organic coated denitration agent and a preparation method thereof.
Background
With the rapid development of economy and the improvement of living standard, coal-fired units are in a growing trend, the problem of air pollution caused by the growth of the coal-fired units is gradually aggravated, and the removal of nitrogen oxides in coal-fired flue gas is the key point for preventing environmental pollution, so that flue gas denitration technology is the key point of current research and application, and the current mainstream denitration technology mainly comprises Selective Catalytic Reduction (SCR) denitration and selective non-catalytic reduction (SNCR), wherein the former means that a reducing agent and NO in flue gas are subjected to the action of a catalystxReact to generate harmless nitrogen and water, thereby removing NO in the flue gasxThe method has the advantages of low reaction temperature and high denitration efficiency, but has the defects of large equipment investment, easy inactivation of the catalyst, high price and the like; the latter does not need catalyst, but the treatment temperature is higher, and the denitration efficiency is lower.
In the denitration process, in addition to the catalyst, the selection of the reducing agent is also a key factor, and the commonly used denitration agent is mainly ammonia, but in many cases, the denitration agent is not suitable for using a gas-phase denitration agent, but needs to be used as a solid-phase denitration agent, urea is one of the solid-phase denitration agents frequently selected, and urea is unstable and easy to decompose at a high temperature, so that the required addition amount is large, the loss is also large, and the urea needs to be modified to improve the utilization rate of the urea in order to control the use amount of the urea.
CN 107115773A discloses a modified urea denitration agent and a preparation method thereof, wherein the modified urea denitration agent comprises urea, a high molecular component, a modified component and a synergistic component, the mass ratio of the modified urea denitration agent to the modified component is respectively 100 (0.5-10) (0.1-10.0) (0.001-0.5), wherein the high molecular component comprises at least one of polyethylene glycol, polyacrylic acid, sodium polyacrylate, polyvinyl alcohol or polyvinylpyrrolidone, the modified component comprises at least one of ammonium stearate, magnesium stearate, calcium stearate, precipitated calcium carbonate, magnesium oxide or zeolite, and the synergistic component is a silicon dioxide vesicle loaded with metal sulfate; although the denitration agent can improve the denitration rate and expand the denitration temperature range, the composition and the preparation process are complex, the components are not clearly mixed simply, the coating structure and the like are not clearly formed, and the problem of urea self-decomposition is not effectively solved.
CN 108057326A discloses a preparation method of a slow-release flue gas denitration agent, which takes 3, 3' -diaminobenzidine, 3, 4-diaminobenzoic acid and isophthalic acid as precursors, takes polyphosphoric acid as a solvent, synthesizes polybenzimidazole copolymer at low temperature through catalysis under the irradiation of ultraviolet light, and then coats urea to prepare the flue gas denitration agent with the slow-release function; the focus of this process is on the preparation of polybenzimidazole copolymers, and there is no explicit description of how to coat urea.
In summary, for the preparation and use of the solid-phase denitration agent, improvement of the solid-phase raw material such as urea and the like is needed, so that the solid-phase raw material has better heat resistance, and the ineffective decomposition of the solid-phase raw material at high temperature is avoided, thereby improving the utilization rate and reducing the cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an organic coated denitration agent and a preparation method thereof, wherein the surface of urea molding particles is subjected to surface modification in a coating mode to form a polyurethane polymer film, so that the heat resistance of the polyurethane polymer film is improved, the ineffective decomposition of urea at a denitration temperature is effectively slowed down, and the utilization rate of the urea is improved; meanwhile, the pigment is added into the coating raw material, so that whether the formed coating is complete and uniform is favorably distinguished, the yield of the denitration agent is improved, and metal ions in the pigment can play a role in catalyzing denitration reaction, so that the denitration efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea, granulating and molding to obtain spherical particles;
(2) and (2) putting the spherical particles obtained in the step (1) into coating equipment, uniformly rotating the spherical particles, and spraying isocyanate and a polyol-pigment mixture for coating to obtain the organic coating denitration agent.
In the invention, for the preparation and application of the denitration agent, the utilization rate and denitration efficiency of the denitration agent are considered, and because urea is decomposed at the denitration temperature, the surface of the urea molding particles is subjected to surface modification in a coating mode to form a polyurethane polymer film, and the polyurethane polymer film has heat resistance, can slow down ineffective decomposition of the urea, is fully used for reducing nitric oxide and improves the utilization rate of the urea; meanwhile, the pigment is added into the raw materials for the polyurethane coating, the color development characteristics of the pigment are utilized to help to distinguish whether the formed coating is complete and uniform, and metal ions contained in the pigment can also play a role of a catalyst in a denitration reaction, so that the denitration efficiency is improved; the method has the advantages of simple operation steps, wide raw material source, low equipment investment and production cost and easy industrial implementation.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical means of the present invention, the urea melting conditions in the step (1) are as follows: the temperature is 132 to 140 ℃, for example 132 ℃, 134 ℃, 135 ℃, 136 ℃, 137 ℃ or 140 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the atmosphere for melting the urea in the step (1) is air.
In the invention, as the urea is likely to be decomposed during heating, the process conditions are controlled to ensure that the urea is molten and is convenient to form uniform granules.
As a preferred embodiment of the present invention, the granulation molding in the step (1) is carried out in a granulation apparatus.
Preferably, the temperature for the granulation molding in step (1) is 95 to 115 ℃, for example, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or 115 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the granulation molding adopts a fluidized bed granulation mode, and the fused urea is pressurized and sprayed to the surface of urea seed crystal to grow into the required urea particles, wherein the temperature is the operating temperature of the fluidized bed.
Preferably, the spherical particles of step (1) have a particle size of 2 to 5mm, such as 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, or 5mm, but not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferable technical scheme of the invention, the coating device in the step (2) comprises a coating machine, and the coating machine comprises a drum assembly.
Preferably, the speed of rotation of the drum is 20 to 50r/min, such as 20r/min, 25r/min, 30r/min, 35r/min, 40r/min or 50r/min, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the spherical particles follow the drum uniformly.
As a preferred technical scheme of the invention, the isocyanate in the step (2) comprises a kettle residue of diphenylmethane diisocyanate.
Preferably, the bottoms of the diphenylmethane diisocyanates comprise diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PAPI).
Preferably, the mass fraction of diphenylmethane diisocyanate in the kettle residue is 65 to 70 wt%, such as 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt% or 70 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In the invention, the isocyanate adopts the kettle residue obtained after the separation of the diphenylmethane diisocyanate as the preparation raw material of the polyurethane, so that the raw material cost can be reduced, and the recycling and comprehensive utilization of the kettle residue are realized.
The diphenylmethane diisocyanate is obtained by carrying out phosgenation reaction on polyamine and phosgene in a solvent, and then carrying out phosgene removal, desolventizing and rectification separation, wherein a product at the top of the tower is the diphenylmethane diisocyanate, a product at the bottom of the tower is the raw material used by the invention, and is a mixture of the diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, and the mixture is a polymer formed by multi-molecular MDI.
As a preferred technical scheme of the invention, the polyol in the step (2) comprises plant polyol.
Preferably, the vegetable polyol comprises any one of, or a combination of at least two of, a soy oil polyol, a castor oil polyol, a palm oil polyol, or a rapeseed oil polyol, typical but non-limiting examples of which are: a combination of soybean oil polyol and castor oil polyol, a combination of castor oil polyol and rapeseed oil polyol, a combination of soybean oil polyol, palm oil polyol and rapeseed oil polyol, and the like.
In the invention, the polyol is selected from plant polyol, the polyol is bio-based polyol synthesized by renewable vegetable oil and different alcohol compounds, and then the bio-based polyurethane is obtained by reacting the bio-based polyol with isocyanate, and the polyurethane coating has better degradation performance and is environment-friendly, has a slow release effect at a denitration temperature, and reduces ineffective decomposition of urea in a denitration process.
Preferably, the pigment in step (2) is a pigment containing transition metal ions, and the transition metal ions include copper ions, iron ions and the like.
Preferably, the pigment in step (2) comprises any one of phthalocyanine blue, phthalocyanine green or iron oxide red or a combination of at least two of them, and the combination is exemplified by typical but not limiting examples: a combination of phthalocyanine blue and phthalocyanine green, a combination of phthalocyanine green and iron oxide red, a combination of phthalocyanine blue, phthalocyanine green and iron oxide red, and the like.
Preferably, the pigment is used in an amount of 0.1 to 5 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, or 5 wt%, based on the amount of the polyol, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the isocyanate and the polyol-pigment mixture are sprayed in the sequence of step (2): the isocyanate is sprayed first and then the polyol-pigment mixture is sprayed.
In the invention, the isocyanate and the polyol-pigment mixture are sprayed in sequence according to the following steps: the isocyanate is active in chemical property and is easier to react with moisture in the air at high temperature, and if the isocyanate is sprayed on the outermost layer of the urea particles, the dosage of the isocyanate is increased and the formed denitration agent is adhered, so that the isocyanate is sprayed at room temperature, then the polyol-pigment mixture is sprayed, and finally the heating coating is carried out.
In a preferred embodiment of the present invention, the total amount of the isocyanate and the polyol-pigment mixture added in step (2) is 0.3 to 5.0 wt% of the spherical particles, for example, 0.3 wt%, 0.6 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, or 5.0 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned values are also applicable.
In the invention, the addition amount of the isocyanate and the polyol is an important factor influencing the formation and the characteristics of the polyurethane film, if the total addition amount of the isocyanate and the polyol is too much, the coating outside the urea is too thick, the relative content of the urea is less, the urea is slowly released, the flue gas denitration rate is influenced, the manufacturing cost of the denitration agent is also improved, and if the total addition amount of the isocyanate and the polyol is too little, the coating outside the urea particles is incomplete, the slow release effect of the urea is weaker, the invalid decomposition is easily caused, and the consumption of the denitration agent in the denitration process is increased.
Preferably, the mass ratio of the isocyanate and the polyol-pigment mixture in step (2) is 1:0.9 to 1:4.0, such as 1:0.9, 1:1.0, 1:1.2, 1:1.5, 1:2.0, 1:2.5, 1:2.8, 1:3.0, 1:3.5 or 1:4.0, but not limited to the recited values, and other values within this range are equally applicable, preferably 1:1.0 to 1: 3.0.
In a preferred embodiment of the present invention, the temperature of the coating film in the step (2) is 60 to 100 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 100 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.
Preferably, hot air is introduced to maintain the temperature of the coating during the coating in the step (2).
Preferably, the coating time in step (2) is 0.25 to 1 hour, such as 0.25 hour, 0.33 hour, 0.4 hour, 0.5 hour, 0.6 hour, 0.75 hour, 0.9 hour or 1 hour, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, unloading and air-drying are carried out after the coating is finished, so as to obtain the polymer denitration agent.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) melting urea at the temperature of 132-140 ℃, putting the urea into granulation equipment, and granulating and forming at the temperature of 95-115 ℃ to obtain spherical particles with the particle size of 2-5 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating cylinder in the coating machine is 20-50 r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate comprises kettle residues of diphenylmethane diisocyanate, the polyol comprises plant polyol, the pigment is a pigment containing transition metal ions, the using amount of the pigment is 0.1-5 wt% of the using amount of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 0.3-5.0 wt% of the spherical particles, the mass ratio of the isocyanate and the polyol-pigment mixture is 1: 1.0-1: 3.0, the temperature of the coating is 60-100 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.25-1 h, and the organic denitration coating agent is obtained after coating is completed.
On the other hand, the invention provides the organic coated denitration agent prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, the surface of the urea molding particles is modified in a coating mode to form the polyurethane polymer film, so that the slow release effect is achieved, the ineffective decomposition of urea in the denitration process is reduced, the urea is fully used for reducing nitric oxide, and the utilization rate of the urea is improved;
(2) according to the method, the pigment is added into the raw materials for the polyurethane coating, the color development characteristics of the pigment are utilized to help to distinguish whether the formed coating is complete and uniform, and metal ions contained in the pigment can also play a role of a catalyst in a denitration reaction, so that the denitration effect is improved, and the denitration rate can reach more than 91%;
(3) the method has the advantages of simple operation steps, wide raw material source, low equipment investment and production cost and easy industrial implementation.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides an organic coated denitration agent and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) melting urea, granulating and molding to obtain spherical particles;
(2) and (2) putting the spherical particles obtained in the step (1) into coating equipment, uniformly rotating the spherical particles, and spraying isocyanate and a polyol-pigment mixture for coating to obtain the organic coating denitration agent.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at the temperature of 132 ℃ in a normal-pressure air atmosphere, then putting the urea into granulation equipment, and performing granulation molding at the temperature of 95 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 3 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 40r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the coating, the isocyanate is the kettle residue containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 65 wt%, the polyol is soybean oil polyol, the pigment is phthalocyanine blue, the using amount of the isocyanate-pigment mixed material is 1 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixed material accounts for 1.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixed material is 1:2, and the temperature of the coating is 80 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.5h, and the organic coating denitration agent is obtained after coating is finished.
Example 2:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at the temperature of 134 ℃, performing in the atmosphere of normal pressure air, then putting into granulation equipment, and performing granulation molding at the temperature of 115 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 2 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 30r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the coating, the isocyanate is the kettle residue containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 68 wt%, the polyol is castor oil polyol, the pigment is phthalocyanine green, the usage amount of the isocyanate-pigment mixture is 3 wt% of the usage amount of the polyol, the total addition amount of the isocyanate and the polyol-pigment mixture accounts for 3.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:3, the temperature of the coating is 60 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.75h, and the organic coating denitration agent is obtained after coating is finished.
Example 3:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at 140 ℃ in a normal-pressure air atmosphere, then putting the urea into granulation equipment, and performing granulation molding at 100 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 4 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 50r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the coating, the isocyanate is the kettle residue containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 70 wt%, the polyol is palm oil polyol, the pigment is iron oxide red, the using amount of the isocyanate-pigment mixed material is 5 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixed material accounts for 5.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixed material is 1:1.5, the temperature of the coating is 100 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.3h, and the organic coating denitration agent is obtained after coating is finished.
Example 4:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at 136 ℃, performing under the atmosphere of normal pressure air, then putting the urea into granulation equipment, and performing granulation molding at 105 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 3.5 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 25r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the coating, the isocyanate is the kettle residue containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 66 wt%, the polyol is rapeseed oil polyol, the pigment is phthalocyanine blue, the using amount of the isocyanate-pigment mixed material is 0.5 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixed material accounts for 0.6 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixed material is 1:1, the temperature of the coating is 90 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.6h, and the organic coating denitration agent is obtained after coating is completed.
Example 5:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at 135 ℃, performing under the atmosphere of normal pressure air, then putting the urea into granulation equipment, and performing granulation molding at 100 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 5 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 35r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the coating, the isocyanate is the residue of a kettle containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 69 wt%, the polyol is soybean oil polyol, the pigment is phthalocyanine green, the using amount of the isocyanate-pigment mixture is 4 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 2.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:2.5, the temperature of the coating is 70 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.8h, and the organic coating denitration agent is obtained after coating is finished.
Example 6:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea at the temperature of 137 ℃, performing in the atmosphere of normal pressure air, then putting into granulation equipment, and performing granulation molding at the temperature of 110 ℃ to obtain spherical particles, wherein the average particle size of the spherical particles is 2.5 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating drum in the coating machine is 45r/min, spraying isocyanate and a polyol-pigment mixture in sequence after the spherical particles uniformly rotate to coat the films, the isocyanate is the kettle residue containing diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate, wherein the content of the diphenylmethane diisocyanate is 67 wt%, the polyol is palm oil polyol, the pigment is iron oxide red, the using amount of the isocyanate-pigment mixture is 2 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 4.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:3.5, and the temperature of the coating is 75 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.4h, and the organic coating denitration agent is obtained after coating is finished.
Example 7:
this example provides a method for preparing an organic coated denitration agent, which is similar to that of example 4 except that: the total amount of isocyanate and polyol-pigment mixture added in step (2) accounted for 0.2 wt% of the spherical particles.
Example 8:
this example provides a method for preparing an organic coated denitration agent, which is similar to that of example 3, except that: the total amount of isocyanate and polyol-pigment blend added in step (2) accounted for 6.0 wt% of the spherical particles.
Comparative example 1:
this comparative example provides a preparation method of a denitration agent, which is similar to that of example 1 except that: the coating of step (2) was not performed.
Comparative example 2:
this comparative example provides a preparation method of a denitration agent, which is similar to that of example 1 except that: no pigment is added in the step (2).
The organic coated denitration agents obtained in the above examples 1 to 8 and comparative example 2 and the denitration agent obtained in comparative example 1 were used in the denitration application test,the conditions of the test include: the reaction temperature is 700-750 ℃, and NO in the flue gas to be treatedxHas a concentration of 500mg/Nm3Testing NO in the outlet flue gasxThe denitration rate was calculated from the concentration of (b), and the results are shown in table 1.
TABLE 1 test results of denitration agent denitration application described in examples 1 to 8 and comparative examples 1 to 2
From the results in table 1, it can be seen that the organic coated denitration agent prepared by the method of the present invention has a denitration rate of 91% or more according to the results of examples 1 to 6; in example 7, too little polyurethane polymer coating results in incomplete coating of the molded particles, which is likely to cause ineffective decomposition of urea and decrease of denitration rate; in example 8, the denitration rate was not significantly increased due to the excessive coating weight of the polyurethane polymer, but rather the denitration rate was lower and the cost was increased.
In the comparative example 1, a polyurethane film is not coated, urea is also decomposed in a large amount in the denitration reaction process, so that the urea utilization rate is reduced, the amount of urea used for denitration is small, and the denitration rate is also obviously reduced and is only 76.20%; in comparative example 2, the pigment is not added, so that the catalyst cannot play a role in the denitration reaction, the denitration rate is reduced to 85.00%, and whether the coating is complete or not cannot be visually identified.
By combining the embodiment and the comparative example, the method disclosed by the invention carries out surface modification on the surface of the urea molding particles in a coating mode to form a polyurethane polymer film, has a slow release effect, reduces ineffective decomposition of urea in a denitration process, fully uses the urea in reduction of nitric oxide, and improves the utilization rate of urea; according to the method, the pigment is added into the raw materials for polyurethane coating, the color development characteristics of the pigment are utilized to help to distinguish whether the formed coating is complete and uniform, and metal ions contained in the pigment can also play a role of a catalyst in a denitration reaction, so that the denitration effect is improved, and the denitration rate can reach more than 91%; the method has the advantages of simple operation steps, wide raw material source, low equipment investment and production cost and easy industrial implementation.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It will be apparent to those skilled in the art that any modification, equivalent substitution of the process of the invention and addition of ancillary operations, selection of specific means, etc., of the present invention are within the scope and disclosure of the invention.
Claims (10)
1. The preparation method of the organic coated denitration agent is characterized by comprising the following steps:
(1) melting urea, granulating and molding to obtain spherical particles;
(2) and (2) putting the spherical particles obtained in the step (1) into coating equipment, uniformly rotating the spherical particles, and spraying isocyanate and a polyol-pigment mixture for coating to obtain the organic coating denitration agent.
2. The preparation method according to claim 1, wherein the temperature of the urea melt in the step (1) is 132-140 ℃;
preferably, the atmosphere in the urea melting in the step (1) is air.
3. The production method according to claim 1 or 2, wherein the granulation molding of step (1) is performed in a granulation apparatus;
preferably, the temperature of the granulation molding in the step (1) is 95-115 ℃;
preferably, the particle size of the spherical particles in the step (1) is 2-5 mm.
4. The method according to any one of claims 1 to 3, wherein the coating apparatus of step (2) comprises a coating machine comprising a drum assembly;
preferably, the rotating speed of the rotating drum is 20-50 r/min;
preferably, the spherical particles follow the drum uniformly.
5. The production method according to any one of claims 1 to 4, wherein the isocyanate in step (2) comprises a still residue of diphenylmethane diisocyanate;
preferably, the kettle residue of the diphenylmethane diisocyanate comprises diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate;
preferably, the mass fraction of the diphenylmethane diisocyanate in the kettle residue is 65-70 wt%.
6. The production method according to any one of claims 1 to 5, wherein the polyol of step (2) comprises a plant polyol;
preferably, the vegetable polyol comprises any one of or a combination of at least two of a soybean oil polyol, a castor oil polyol, a palm oil polyol, or a rapeseed oil polyol;
preferably, the pigment of step (2) is a transition metal ion-containing pigment;
preferably, the pigment in step (2) comprises any one or a combination of at least two of phthalocyanine blue, phthalocyanine green or iron oxide red;
preferably, the amount of the pigment is 0.1-5 wt% of that of the polyol;
preferably, the isocyanate and the polyol-pigment mixture are sprayed in the sequence of step (2): the isocyanate is sprayed first and then the polyol-pigment mixture is sprayed.
7. The method according to any one of claims 1 to 6, wherein the isocyanate and the polyol-pigment mixture in step (2) are added in a total amount of 0.3 to 5.0 wt% based on the spherical particles;
preferably, the mass ratio of the isocyanate to the polyol-pigment mixture in the step (2) is 1: 0.9-1: 4.0, and preferably 1: 1.0-1: 3.0.
8. The method according to any one of claims 1 to 7, wherein the temperature of the coating film in the step (2) is 60 to 100 ℃;
preferably, hot air is introduced to maintain the temperature of the coating during the coating in the step (2);
preferably, the coating time in the step (2) is 0.25-1 h;
preferably, unloading and air-drying are carried out after the coating is finished, so as to obtain the polymer denitration agent.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) melting urea at the temperature of 132-140 ℃, putting the urea into granulation equipment, and granulating and forming at the temperature of 95-115 ℃ to obtain spherical particles, wherein the particle size of the spherical particles is 2-5 mm;
(2) putting the spherical particles obtained in the step (1) into a coating machine, wherein the rotating speed of a rotating cylinder in the coating machine is 20-50 r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate comprises kettle residues of diphenylmethane diisocyanate, the polyol comprises plant polyol, the pigment is a pigment containing transition metal ions, the using amount of the pigment is 0.1-5 wt% of the using amount of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 0.3-5.0 wt% of the spherical particles, the mass ratio of the isocyanate and the polyol-pigment mixture is 1: 1.0-1: 3.0, the temperature of the coating is 60-100 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.25-1 h, and the organic denitration coating agent is obtained after coating is completed.
10. An organic coated denitration agent obtained by the preparation method of any one of claims 1 to 9.
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