CN114425229A - Organic coated denitration agent and preparation method thereof - Google Patents
Organic coated denitration agent and preparation method thereof Download PDFInfo
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- CN114425229A CN114425229A CN202210102517.6A CN202210102517A CN114425229A CN 114425229 A CN114425229 A CN 114425229A CN 202210102517 A CN202210102517 A CN 202210102517A CN 114425229 A CN114425229 A CN 114425229A
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- coating
- polyol
- urea
- 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 113
- 238000000576 coating method Methods 0.000 claims abstract description 112
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000004202 carbamide Substances 0.000 claims abstract description 87
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 67
- 239000000049 pigment Substances 0.000 claims abstract description 63
- 239000012798 spherical particle Substances 0.000 claims abstract description 60
- 239000012948 isocyanate Substances 0.000 claims abstract description 56
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims description 36
- 150000003077 polyols Chemical class 0.000 claims description 36
- 238000005469 granulation Methods 0.000 claims description 30
- 230000003179 granulation Effects 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 28
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 23
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- -1 polypropylene carbonate Polymers 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 10
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 claims description 9
- 235000019233 fast yellow AB Nutrition 0.000 claims description 9
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 229920006254 polymer film Polymers 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007790 solid phase 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 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
- 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
- 238000012797 qualification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 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
- 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether 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
- 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
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- 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
-
- 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
- B01D53/90—Injecting reactants
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (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)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (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, mixing with a catalyst, and granulating 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 catalyst is added in the urea denitration agent forming process, so that the distribution of the catalyst in each local area is ensured when the denitration agent is used, the denitration effect is improved, and the denitration efficiency is improved; the method carries out surface modification on the surface of the molded particle 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 for reduction of nitric oxide, and improves the utilization rate of the urea; 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, 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, the solid-phase raw material such as urea needs to be modified to have better heat resistance, so as to avoid ineffective decomposition at high temperature, improve the utilization rate and reduce 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 catalyst is added in the urea denitration agent forming process, so that the denitration efficiency can be correspondingly improved, and the problem of reduction of the denitration efficiency caused by larger particle size is avoided; meanwhile, the surface of the molded particles is modified in a coating mode to form a polymer film, so that the heat resistance of the polymer film is improved, the ineffective decomposition of urea at the denitration temperature is effectively slowed down, and the utilization rate of the urea 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, mixing with a catalyst, and granulating 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 the denitration efficiency of the denitration agent are considered, in order to ensure the uniform mixing of urea and the catalyst, the urea is firstly formed into a molten state and then mixed with the denitration catalyst for molding, so that the denitration agent can react in each local area when in use, and the denitration efficiency is improved; meanwhile, urea is decomposed at the denitration temperature, the surface of the urea molding particles is modified in a coating mode to form a polyurethane polymer film, and the polyurethane polymer film has heat resistance, can slow down ineffective decomposition of urea, is fully used for reduction of nitric oxide, and improves the utilization rate of urea; meanwhile, pigment is added into the polyurethane preparation raw material, so that whether the formed coating is complete and uniform or not is favorably distinguished, and the yield of the denitration agent 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 preferred embodiment of the present invention, the urea melting conditions in the step (1) are: 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 in the urea melting 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, so that the urea is convenient to mix and form with the denitration catalyst.
As a preferred technical scheme of the invention, the catalyst in the step (1) comprises transition metal oxide.
Preferably, the transition metal oxide comprises any one of, or a combination of at least two of, titanium dioxide, vanadium pentoxide or tungsten trioxide, typical but non-limiting examples of which are: combinations of titanium dioxide and vanadium pentoxide, combinations of vanadium pentoxide and tungsten trioxide, combinations of titanium dioxide, vanadium pentoxide and tungsten trioxide, and the like.
Preferably, the catalyst of step (1) is independently added in an amount of 0 to 500ppm, such as 0, 50ppm, 100ppm, 200ppm, 300ppm, 400ppm or 500ppm, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
In the invention, the catalyst is added mainly to ensure that the catalyst exists in the reaction zone when the urea reacts with the nitrogen oxide, so that the problem of uneven denitration reaction is avoided, the adding amount of the catalyst does not need to be excessive, and the main body of the catalyst is still the urea denitration agent.
As a preferable technical scheme of the invention, the mixture in the step (1) is stirred uniformly.
Preferably, the granulation molding in the step (1) is carried out in a granulation device.
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, the molten urea is pressurized and sprayed to the surface of the urea seed crystal to grow the required urea particles, and 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, the coating equipment 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 solution of the present invention, the isocyanate in the step (2) comprises any one of toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate or a combination of at least two thereof, and the combination is exemplified by the following typical but non-limiting examples: combinations of toluene diisocyanate and hexamethylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and the like.
In the invention, the isocyanate is mainly selected from diisocyanate, including toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate and the like.
Preferably, the polyol of step (2) is polypropylene carbonate (PPC) polyol.
In the invention, the polyol adopts the polypropylene carbonate polyol to replace polyether polyol, polyester polyol and the like, and has the advantages that: the polyurethane generated by the polyol is resistant to hydrolysis, and the prepared denitration agent is high in stability; meanwhile, the polyhydric alcohol is generated from propylene oxide and carbon dioxide, has low cost and is beneficial to reducing CO2The discharge of (2) is matched with the ecological concept of carbon neutralization.
Preferably, the pigment of step (2) comprises any one of or a combination of at least two of lake red, fast yellow or permanent violet, typical but non-limiting examples of which are: a combination of lake red and fast yellow, a combination of fast yellow and permanent violet, a combination of lake red, fast yellow and permanent violet, and the like.
Preferably, the pigment is used in an amount of 0.1 to 3 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 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 criteria: 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 0.5 to 5.0 wt% of the spherical particles, for example, 0.5 wt%, 0.8 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 adding amount of the isocyanate and the polyol is an important factor influencing the formation and the characteristics of the polyurethane film, if the adding amount of the isocyanate and the polyol is excessive, 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, and the manufacturing cost of the denitration agent is also increased; if the total adding amount of the urea and the urea is too small, the urea particle is incompletely coated with a film, the slow release effect of the urea is weak, ineffective decomposition is easily caused, and the consumption of a 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 during the coating in the step (2) to maintain the coating temperature.
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 preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing melted urea with a catalyst, wherein the urea melting temperature is 132-140 ℃, the catalyst comprises a transition metal oxide, the transition metal oxide comprises any one or a combination of at least two of titanium dioxide, vanadium pentoxide or tungsten trioxide, the adding amount of the transition metal oxide is 0-500 ppm independently, the mixture is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out at the granulation molding 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 drum in the coating machine is 20-50 r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixed material for coating, wherein the isocyanate comprises any one or a combination of at least two of toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate, the polyol comprises polypropylene carbonate polyol, the pigment comprises any one or a combination of at least two of lake red, fast yellow or permanent violet, the using amount of the pigment is 0.1-3 wt% of the using amount of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixed material accounts for 0.5-5.0 wt% of the spherical particles, the mass ratio of the isocyanate and the polyol-pigment mixed material is 1: 1.0-1: 3.0, the coating temperature is 60-100 ℃, and hot air is introduced during coating to maintain the coating temperature, the coating time is 0.25-1 h, and the organic coated denitration agent is obtained after coating.
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 catalyst is added in the urea denitration agent forming process, so that the distribution of the catalyst in each local area is ensured when the denitration agent is used, the denitration effect is improved, and the denitration rate can reach more than 94%;
(2) 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;
(3) the use of the pigment in the coating raw material is beneficial to distinguishing whether the coating of the urea particles is complete and uniform, and is beneficial to improving the qualification rate of finished products of the denitration agent;
(4) 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, mixing with a catalyst, and granulating 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, mixing the urea with a catalyst, wherein the melting temperature of the urea is 132 ℃, the melting is carried out in the atmosphere of normal pressure air, the catalyst is titanium dioxide, the adding amount of the catalyst is 500ppm, the mixture is uniformly stirred and then put into granulation equipment, and granulation molding is carried out, wherein the granulation molding temperature is 95 ℃, so that spherical particles are obtained, and 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 cylinder in the coating machine is 40r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is toluene diisocyanate, the polyol is polypropylene carbonate polyol, the pigment is lake red, the using amount of the pigment is 1 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 1.0 wt% of that of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:2, the coating temperature 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.
Example 2:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) mixing melted urea with a catalyst, wherein the urea melting temperature is 134 ℃, the urea melting is carried out in a normal-pressure air atmosphere, the catalyst is titanium dioxide and vanadium pentoxide, the adding amount of the titanium dioxide and the vanadium pentoxide is 200ppm, the adding amount of the titanium dioxide and the vanadium pentoxide is 100ppm, the mixture is uniformly stirred and then put into granulation equipment, and granulation molding is carried out, the granulation molding temperature is 115 ℃, so that spherical particles are obtained, and 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 cylinder in the coating machine is 30r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is hexamethylene diisocyanate, the polyol is polypropylene carbonate polyol, the pigment is fast yellow, the using amount of the pigment is 2 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 3.0 wt% of that of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:3, the coating temperature 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.
Example 3:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) mixing melted urea with a catalyst, wherein the urea melting temperature is 140 ℃, the urea melting is carried out in a normal-pressure air atmosphere, the catalyst is titanium dioxide, vanadium pentoxide and tungsten trioxide, the adding amount of the titanium dioxide, the vanadium pentoxide and the tungsten trioxide is 200ppm, the mixture is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out, wherein the granulation molding temperature is 100 ℃, so that spherical particles are obtained, and 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 cylinder in the coating machine is 50r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is isophorone diisocyanate, the polyol is polypropylene carbonate polyol, the pigment is permanent violet, the using amount of the pigment is 3 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 5.0 wt% of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:1.5, the coating temperature 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.
Example 4:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea, mixing the urea with a catalyst, wherein the melting temperature of the urea is 136 ℃, the melting is carried out in the atmosphere of normal pressure air, the catalyst is tungsten trioxide, the adding amount of the tungsten trioxide is 400ppm, the mixture is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out at the temperature of 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 cylinder in the coating machine is 25r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is toluene diisocyanate, the polyol is polypropylene carbonate polyol, the pigment is lake red, the using amount of the pigment is 0.2 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 0.6 wt% of that of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:1, the coating temperature 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.
Example 5:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea, mixing the urea with a catalyst, wherein the melting temperature of the urea is 135 ℃, the melting is carried out in the atmosphere of normal pressure air, the catalyst is titanium dioxide and tungsten trioxide, the adding amount of the titanium dioxide and the tungsten trioxide is 500ppm, the mixture is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out, wherein the granulation molding temperature is 100 ℃, so that spherical particles are obtained, and 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 cylinder in the coating machine is 35r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is hexamethylene diisocyanate, the polyol is polypropylene carbonate polyol, the pigment is fast yellow, the using amount of the pigment is 1.5 wt% of that of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixture accounts for 2.0 wt% of that of the spherical particles, the mass ratio of the isocyanate to the polyol-pigment mixture is 1:2.5, the coating temperature is 70 ℃, hot air is introduced during coating to maintain the coating temperature, the coating time is 0.8h, and the organic coating agent is obtained after coating.
Example 6:
the embodiment provides a preparation method of an organic coated denitration agent, which comprises the following steps:
(1) melting urea, mixing the melted urea with a catalyst, wherein the melting temperature of the urea is 137 ℃, the melting is carried out in the atmosphere of normal pressure air, the catalyst is vanadium pentoxide, the adding amount of the vanadium pentoxide is 300ppm, the urea is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out 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 cylinder in the coating machine is 45r/min, uniformly rotating the spherical particles, and then sequentially spraying isocyanate and a polyol-pigment mixture for coating, wherein the isocyanate is toluene diisocyanate and hexamethylene diisocyanate in a mass ratio of 1:1, the polyol is polypropylene carbonate polyol, the pigment is permanent violet, the pigment is used in an amount which is 2.5 wt% of that of the polyol, the total addition amount of the isocyanate and the polyol-pigment mixture accounts for 4.0 wt% of the spherical particles, the mass ratio of the isocyanate and the polyol-pigment mixture is 1:3.5, 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 completed.
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 blend added in step (2) accounted for 0.3 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 mixture added in step (2) accounted for 6.0 wt% of the spherical particles.
Comparative example 1:
this comparative example provides a preparation method of an organic coated denitration agent, which is similar to that of example 1 except that: no catalyst is added in the step (1).
Comparative example 2:
this comparative example provides a preparation method of a denitration agent, which is similar to that of example 1 except that: the coating in step (2) is not performed.
The organic coated denitration agents obtained in the above examples 1 to 8 and comparative example 1 and the denitration agent obtained in comparative example 2 were used in denitration application tests, and the test conditions included: the reaction temperature is 700-750 ℃, and NO in the flue gas to be treatedxAt a concentration of 450mg/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
As can be seen from the results in Table 1, the organic coated denitration agent prepared by the method of the invention has denitration rates of more than 94% 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, no catalyst is added during urea forming, the denitration agent cannot achieve a sufficient denitration effect at a lower temperature of 700-750 ℃, and the denitration rate is reduced to 79.78%; in the comparative example 2, the polyurethane film is not coated, urea is also largely decomposed in the denitration reaction process, so that the urea utilization rate is reduced, the urea used for denitration is less, and the denitration rate is also obviously reduced to only 75.11%.
By integrating the embodiment and the comparative example, the method provided by the invention has the advantages that the catalyst is added in the urea denitration agent forming process, the distribution of the catalyst in each local area is ensured when the denitration agent is used, the denitration effect is improved, and the denitration rate can reach more than 94%; according to the method, the surface of the urea molding particles is modified in a coating mode to form a 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 use of the pigment in the coating raw material is beneficial to distinguishing whether the coating of the urea particles is complete and uniform, and is beneficial to improving the qualification rate of finished products of the denitration agent; 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, mixing with a catalyst, and granulating 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 catalyst of step (1) comprises a transition metal oxide;
preferably, the transition metal oxide comprises any one of titanium dioxide, vanadium pentoxide or tungsten trioxide or a combination of at least two of the two;
preferably, the addition amount of the catalyst in the step (1) is independently 0-500 ppm.
4. The method according to any one of claims 1 to 3, wherein the step (1) of mixing is followed by stirring to homogeneity;
preferably, the granulation molding in the step (1) is carried out in a granulation device;
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.
5. The method according to any one of claims 1 to 4, 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.
6. The method according to any one of claims 1 to 5, wherein the isocyanate in step (2) comprises any one of toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate or a combination of at least two thereof;
preferably, the polyol of step (2) is a polypropylene carbonate polyol;
preferably, the pigment in the step (2) comprises any one or a combination of at least two of lake red, fast yellow or permanent violet;
preferably, the amount of the pigment is 0.1-3 wt% of that of the polyol;
preferably, the isocyanate and polyol-pigment blend are sprayed in the following order: the isocyanate is sprayed first and then the polyol-pigment mixture is sprayed.
7. The method of any one of claims 1-6, wherein the isocyanate and the polyol-pigment mixture of step (2) are added in a total amount of 0.5 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) mixing melted urea with a catalyst, wherein the urea melting temperature is 132-140 ℃, the catalyst comprises a transition metal oxide, the transition metal oxide comprises any one or a combination of at least two of titanium dioxide, vanadium pentoxide or tungsten trioxide, the adding amount of the transition metal oxide is independently 0-500 ppm, the mixture is uniformly stirred and then put into granulation equipment, and the granulation molding is carried out, wherein the granulation molding temperature is 95-115 ℃, spherical particles are obtained, and 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 drum in the coating machine is 20-50 r/min, after the spherical particles uniformly rotate, sequentially spraying isocyanate and a polyol-pigment mixed material for coating, wherein the isocyanate comprises any one or a combination of at least two of toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate, the polyol comprises polypropylene carbonate polyol, the pigment comprises any one or a combination of at least two of lake red, fast yellow or permanent violet, the using amount of the pigment is 0.1-3 wt% of the using amount of the polyol, the total adding amount of the isocyanate and the polyol-pigment mixed material accounts for 0.5-5.0 wt% of the spherical particles, the mass ratio of the isocyanate and the polyol-pigment mixed material is 1: 1.0-1: 3.0, the coating temperature is 60-100 ℃, and hot air is introduced during coating to maintain the coating temperature, the coating time is 0.25-1 h, and the organic coated denitration agent is obtained after coating.
10. An organic coated denitration agent obtained by the preparation method of any one of claims 1 to 9.
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