CN115501748A - Denitration agent and preparation method thereof - Google Patents
Denitration agent and preparation method thereof Download PDFInfo
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- CN115501748A CN115501748A CN202211037215.1A CN202211037215A CN115501748A CN 115501748 A CN115501748 A CN 115501748A CN 202211037215 A CN202211037215 A CN 202211037215A CN 115501748 A CN115501748 A CN 115501748A
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- 238000002360 preparation method Methods 0.000 title abstract description 85
- 239000000843 powder Substances 0.000 claims abstract description 250
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 213
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 212
- 239000011572 manganese Substances 0.000 claims abstract description 212
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 185
- 239000003546 flue gas Substances 0.000 claims abstract description 177
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 175
- 239000003054 catalyst Substances 0.000 claims abstract description 160
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 111
- 150000001412 amines Chemical class 0.000 claims abstract description 61
- 239000011230 binding agent Substances 0.000 claims abstract description 37
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 116
- 238000002156 mixing Methods 0.000 claims description 103
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 66
- 239000004202 carbamide Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 65
- 239000002131 composite material Substances 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 51
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000008187 granular material Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- 238000012216 screening Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 46
- 229910021529 ammonia Inorganic materials 0.000 abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 60
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 56
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 37
- 239000011777 magnesium Substances 0.000 description 37
- 229910052749 magnesium Inorganic materials 0.000 description 37
- 238000003756 stirring Methods 0.000 description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 36
- 235000017557 sodium bicarbonate Nutrition 0.000 description 28
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 28
- 150000003672 ureas Chemical class 0.000 description 28
- 238000002485 combustion reaction Methods 0.000 description 27
- 239000002002 slurry Substances 0.000 description 24
- 239000011238 particulate composite Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 229920000881 Modified starch Polymers 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000000230 xanthan gum Substances 0.000 description 13
- 229920001285 xanthan gum Polymers 0.000 description 13
- 229940082509 xanthan gum Drugs 0.000 description 13
- 235000010493 xanthan gum Nutrition 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910000420 cerium oxide Inorganic materials 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000009615 deamination Effects 0.000 description 8
- 238000006481 deamination reaction Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 description 7
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 7
- 239000010813 municipal solid waste Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- HMNUYYJYMOXWTN-UHFFFAOYSA-J strontium;barium(2+);disulfate Chemical compound [Sr+2].[Ba+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HMNUYYJYMOXWTN-UHFFFAOYSA-J 0.000 description 7
- AFNWOEJOULWFIS-BTJKTKAUSA-N (z)-4-hydroxy-4-oxobut-2-enoate;tris(2-hydroxyethyl)azanium Chemical compound OC(=O)\C=C/C(O)=O.OCCN(CCO)CCO AFNWOEJOULWFIS-BTJKTKAUSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004056 waste incineration Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229910002089 NOx Inorganic materials 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 3
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- LUYGICHXYUCIFA-UHFFFAOYSA-H calcium;dimagnesium;hexaacetate Chemical compound [Mg+2].[Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LUYGICHXYUCIFA-UHFFFAOYSA-H 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001607 magnesium mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- NEDFZELJKGZAQF-UHFFFAOYSA-J strontium;barium(2+);dicarbonate Chemical compound [Sr+2].[Ba+2].[O-]C([O-])=O.[O-]C([O-])=O NEDFZELJKGZAQF-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- -1 triethanolamine maleate modified urea Chemical class 0.000 description 1
- QCWXUUIWCKQGHC-BJUDXGSMSA-N zirconium-90 Chemical group [90Zr] QCWXUUIWCKQGHC-BJUDXGSMSA-N 0.000 description 1
Images
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
- B01D53/74—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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a denitration agent and a preparation method thereof, belonging to the technical field of incineration flue gas denitration, wherein the denitration agent comprises the following components: 50-80 parts of reducing agent, 8-20 parts of manganese ore powder-based denitration catalyst, 10-30 parts of denitration synergist and 0.5-2 parts of organic binder; the denitration agent is efficient, ammonia escape is low, and the denitration temperature is 100-1100 ℃. When the denitration agent is a flue gas full-temperature denitration agent, the denitration agent comprises the following components: 50-90 parts by mass of an organic amine reducing agent, 5-30 parts by mass of a denitration synergist and 5-20 parts by mass of a manganese ore powder-based denitration catalyst; the denitration agent is efficient, ammonia escape is low, and the denitration temperature is 100-1050 ℃.
Description
Technical Field
The invention belongs to the technical field of incineration flue gas denitration, and particularly relates to a denitration agent and a preparation method thereof.
Background
Nitrogen Oxides (NO) x ) Mainly comprising Nitric Oxide (NO) and nitrogen dioxide (NO) 2 ) Is the main pollutant of the atmosphere. The high-temperature industrial process such as burning coal and solid waste incineration is NO x Of the exhaust gas system. For reducing NO x Enterprises such as industrial emission, coal-fired heat supply, coal-fired power generation, cement production and solid waste incineration generally adopt a selective non-catalytic reduction (SNCR) denitration technology or a Selective Catalytic Reduction (SCR) denitration technology. In the SNCR denitration process, reducing agent urea solution or ammonia water is atomized and sprayed into high-temperature flue gas at the temperature of 900-1050 ℃, and NO is added x Reduction to N 2 . However, the SNCR technology alone has a low denitration efficiency, usually lower than 50%, and it is difficult to remove NO x The emission level of (A) is continuously controlled at 100 mg/Nm 3 In the following, increasing the amount of reducing agent urea and ammonia water results in increased ammonia slip. In the SCR denitration process, the catalyst module is usually placed at the rear end of the flue gas facility, the reaction temperature is 180-400 ℃, and the commonly used reducing agent is ammonia water. The SCR denitration technology has high denitration efficiency which can reach more than 90 percent, but has large equipment investment and high operating cost. The development of high efficiency, low cost and low ammonia slip denitration technology is still an urgent need in the combustion/incineration field.
The recently developed denitration technology of the solid denitration agent shows higher denitration efficiency compared with the traditional SNCR technology. The technology is that a powder state, a particle state or a particle powder mixed state denitrifier is directly sprayed into the flue gas with the temperature of 450-1050 ℃ by a pneumatic conveying device, and NO in the flue gas can be removed by an SNCR or SCR principle x . The reducing agents in the solid denitrifying agents reported in the patent documents at present are all mixtures of various materials.The reported reductant components include: urea (CN 110639341A, CN 110270325A, CN 111672290A, CN 112403529A, CN 109316892A, CN 111001279A, CN 110026077A), dicyandiamide (CN 113019118A, CN 109316892A), melamine (CN 108187490A), cyanuric acid (CN 107998852A, CN 108187490A), ammonium bicarbonate (CN 113019118A) and other organic amine-based compounds (CN 111686564A, CN 112915751A); other additional ingredients reported include: manganese dioxide, titanium oxide, clay minerals, copper oxide, calcium magnesium acetate, potassium permanganate, sodium hydroxide, sodium bicarbonate, calcium carbonate, carboxymethyl cellulose, high polymer resin and the like. The density and the grain diameter of the components of the materials are greatly different, so that the flow rates of different materials are obviously different during pneumatic conveying, and high-density materials are easy to deposit at a feed opening of feeding equipment or a bent part of a conveying pipeline and easily cause blockage; meanwhile, the granular materials and the powdery materials can be layered in the mixing process, so that the components in the mixed denitration agent are not uniformly distributed, and the denitration efficiency is unstable.
Disclosure of Invention
The invention aims to provide a denitration agent and a preparation method thereof aiming at overcoming the defects in the prior art, and on one hand, the denitration agent solves the problems of layering phenomenon of granular materials and powdery materials and poor flowability of high-density materials in the storage and use processes of the mixed denitration agent. On the other hand, the denitration agent with high efficiency and low ammonia escape is provided, the denitration reaction temperature range of the denitration agent is 100-1100 ℃, the denitration agent can continuously play a denitration role in the subsequent flue gas full-cooling process after being sprayed into the flue gas with the temperature of 950-1100 ℃, and the residual ammonia in the flue gas can be catalyzed and removed by the catalytic substances in the denitration agent.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a denitration agent is a granular composite denitration agent, and the granular composite denitration agent comprises the following components: 50-80 parts of reducing agent, 8-20 parts of manganese ore powder-based denitration catalyst, 10-30 parts of denitration synergist and 0.5-2 parts of organic binder.
Preferably, the reducing agent is prepared from the following raw materials: one or more of powdered urea, powdered ammonium chloride, and powdered melamine.
It should be noted that the granular composite denitration agent of the invention is injected into the flue gas with the temperature of 950-1100 ℃ through the pneumatic transmission of the Roots blower to remove NO in the flue gas x And (4) removing. In the granular composite denitrifier, one or more of powdered urea, powdered ammonium chloride and powdered melamine are mixed as reducing agent, and the granular reducing agent is disintegrated and releases NH in high-temperature flue gas 3 Removing NO in the smoke by SNCR mode x 。
Preferably, the manganese ore powder-based denitration catalyst is cerium-loaded manganese ore powder, the particle size of the manganese ore powder is 200 meshes, and the manganese content is more than 40%.
It should be noted that the manganese ore powder-based denitration catalyst in the granular composite denitration agent can remove NO in flue gas in a catalytic manner at the temperature reduction stage of 600-100 DEG C x . The manganese ore powder contains various variable valence state manganese oxides and can adsorb NO and NH simultaneously 3 And promote electron transfer, thereby realizing efficient denitration. Manganese oxide in manganese ore powder has strong NH adsorption capacity 3 Ability to convert NH in the absence of NO 3 And (3) oxidizing, and realizing high-efficiency catalytic deamination, thereby reducing ammonia escape. In order to ensure high efficiency of catalytic denitration and deamination of manganese ore powder, the invention requires that the particle size of the manganese ore powder in the manganese ore powder-based denitration catalyst is 200 meshes, and the manganese content is more than 40%.
Preferably, the denitration synergist comprises the following raw materials: 20-50 parts of powdery sodium bicarbonate and 50-80 parts of magnesium ore powder.
Preferably, the organic binder comprises the following raw materials: 90-95 parts of pregelatinized starch and 5-10 parts of xanthan gum.
Preferably, the particle size of the magnesium ore powder is 200 meshes.
It should be noted that the granular composite denitration agent comprises a denitration synergist sodium bicarbonate, and can promote a large amount of OH active groups to be generated after being sprayed into flue gas at 950-1100 ℃, so that NH is favorably generated 3 The reduction of NO can greatly improve the denitration reaction efficiency, widen the denitration reaction temperature window and ensure that NH is generated 3 Reaction activity for denitration by SNCR methodThe viscosity decreased to 600 ℃.
The granular composite denitration agent comprises denitration synergist magnesium ore powder, wherein magnesium oxide in the magnesium ore powder has an oxygen defect structure surface, has strong catalytic capability on dissociation of NO in incineration flue gas, and can promote NO to generate N 2 Thereby further increasing the denitration effect of the denitration agent in the range of 100-300 ℃. In order to ensure high catalytic denitration efficiency of the magnesium ore powder, the invention requires that the particle size of the magnesium ore powder is 200 meshes.
The granular composite denitration agent comprises organic binder pregelatinized starch and xanthan gum, wherein the pregelatinized starch and the xanthan gum are common mineral powder and compound fertilizer binders and have extremely strong binding and balling capabilities. When the granular composite denitration agent is sprayed into flue gas at 950-1100 ℃, the organic binder pregelatinized starch and the xanthan gum can be quickly decomposed, so that the denitration granules are disintegrated to release the reducing agent, the manganese ore powder-based denitration catalyst and the powder denitration synergist.
Preferably, the preparation method of the manganese ore powder-based denitration catalyst in the denitration agent comprises the following steps: stirring and uniformly mixing 5-10 parts by mass of cerium oxide and 90-95 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 85-100 ℃, and roasting at 300-500 ℃ for 3 hours or more; and after cooling, ball milling is carried out again to obtain the manganese ore powder denitration catalyst loaded with the cerium powder, wherein the manganese ore powder denitration catalyst is 200 meshes.
In order to further improve the denitration efficiency of the manganese ore powder, cerium (Ce) is loaded on the manganese ore powder to form the cerium-loaded manganese ore powder-based catalyst. CeO (CeO) 2 Has higher oxygen capacity and excellent catalytic reduction performance, and Ce is added under the condition of oxidation or reduction 3+ And Ce 4+ There is a rapid transition between so as to trap or release O atoms, promoting the conversion of NO to NO 2 Thereby enhancing the denitration capability of the manganese ore powder.
The invention also provides a preparation method of the denitration agent, which comprises the following steps:
the method comprises the following steps: weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist in parts by weight, and mixing in a mixer;
step two: conveying the mixture to a disc granulator or a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
step three: conveying the granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-3.5 mm, cooling and packaging.
The invention also provides an application of the denitration agent in removing nitrogen oxides in flue gas, wherein the denitration agent is sprayed into the flue gas at 950-1100 ℃, and the denitration reaction temperature range is 100-1100 ℃.
The denitration agent has the denitration temperature range of 100-1050 ℃, and can continuously play a denitration role in the subsequent flue gas full cooling process after being sprayed into flue gas at 850-1050 ℃, so that NO in the flue gas is realized x The high-efficiency removal is realized; meanwhile, the denitrifying agent has the function of catalytically removing ammonia in the flue gas, so that the escape of ammonia can be reduced.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a denitration agent is a flue gas full-temperature denitration agent, and comprises the following components: 50-90 parts of organic amine reducing agent, 5-30 parts of denitration synergist and 5-20 parts of manganese ore powder-based denitration catalyst.
Preferably, the organic amine reducing agent comprises the following raw materials: 50-80 parts of urea and 20-50 parts of hydroxymethyl urea.
Preferably, the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde under the conditions that the pH value is 7.5-8.0 and the heating temperature is 70-85 ℃, wherein the molar ratio of the urea to the formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
Preferably, the denitration synergist comprises the following raw materials: 20-40 parts of powdery sodium bicarbonate and 60-80 parts of 200-mesh magnesium ore powder.
It should be noted that the flue gas full-temperature denitration agent is injected into the flue gas at 850-1050 ℃ in the form of solid mixture to remove NO in the flue gas x And removing. In a compounded denitrifying agentThe mixture of urea and hydroxymethyl urea is used as a reducing agent, and the solid reducing agent is disintegrated in high-temperature flue gas to release NH 3 Removing NO in the smoke by SNCR mode x . The thermal decomposition of methylol urea can also generate OH active group, which can promote NH 3 And the NO is reduced to react, so that the denitration reaction efficiency is improved. The denitration synergist contains sodium bicarbonate, and can promote generation of OH active groups and NH after being sprayed into flue gas at 850-1050 DEG C 3 The reduction of NO greatly improves the denitration reaction efficiency, widens the denitration reaction temperature window and enables NH 3 The reactivity of the denitration by SNCR mode is reduced to 600 ℃.
The flue gas full-temperature denitration agent comprises denitration synergist magnesium ore powder, wherein magnesium oxide in the magnesium ore powder has an oxygen defect structure surface, has strong catalytic capability on dissociation of NO in incineration flue gas, and can promote NO to generate N 2 Thereby further increasing the denitration effect of the full-temperature denitration agent in the range of 100-300 ℃. In order to ensure high catalytic denitration efficiency of the magnesium ore powder, the invention requires that the particle size of the magnesium ore powder is 200 meshes. Meanwhile, the magnesium mineral powder has a moisture-proof function, can prevent the reducing agent from caking, and can improve the fluidity of the full-temperature denitration agent in the injection process.
Preferably, the manganese ore powder-based denitration catalyst is cerium-loaded manganese ore powder, the particle size of the manganese ore powder is 200 meshes, and the manganese content is more than 30%.
It should be noted that the flue gas full-temperature denitration agent comprises a manganese ore powder-based denitration catalyst, and can remove NO in flue gas in an SCR mode at the temperature reduction stage of 600-100 DEG C x . The manganese ore powder contains various variable valence state manganese oxides, electrons on valence layer electron d orbit of manganese element are in a half-full state, and NO and NH can be adsorbed simultaneously 3 And promote electron transfer, thereby realizing efficient denitration. Manganese oxide in manganese ore powder has strong NH adsorption capacity 3 Ability to convert NH in the absence of NO 3 And (3) oxidizing to realize efficient deamination, thereby reducing ammonia escape. In order to ensure high efficiency of catalytic denitration and deamination of manganese ore powder, the invention requires that in the manganese ore powder-based denitration catalyst, the particle size of the manganese ore powder is 200 meshes, and the manganese content is more than 30%.
Preferably, the preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 5-10 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring with 90-95 parts by mass of manganese ore powder to form slurry, fully mixing uniformly, drying at 85-100 ℃, and roasting at 300-500 ℃ for 3 hours or more; and after cooling, ball milling is carried out again to 200 meshes, so as to obtain the cerium-loaded manganese ore powder denitration catalyst.
It should be noted that, in order to further improve the denitration efficiency of the manganese ore powder, cerium (Ce) is loaded on the manganese ore powder to form the cerium-loaded manganese ore powder-based catalyst. CeO (CeO) 2 Has higher oxygen capacity and excellent catalytic reduction performance, and Ce is oxidized or reduced 3+ And Ce 4+ There is a rapid transition between so as to trap or release O atoms, promoting the conversion of NO to NO 2 Thereby enhancing the denitration capability of the manganese ore powder.
The invention also provides a preparation method of the flue gas full-temperature denitration agent, which comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, uniformly mixing in a mixer, and sealing and packaging.
The invention also provides application of the denitration agent in removing nitrogen oxides in flue gas, wherein the denitration temperature of the denitration agent is 100-1050 ℃, and the denitration agent is sprayed into the flue gas at 850-1050 ℃.
The granular composite denitration agent is prepared by adopting the reducing agent, the manganese ore powder-based denitration catalyst and the organic binder as initial raw materials, so that the granular composite denitration agent has the following beneficial effects:
1. the granular composite denitration agent obtained by the invention can continuously play a denitration role in the subsequent full temperature reduction process of flue gas after being sprayed into the flue gas with the temperature of 950-1100 ℃, has a wide denitration reaction window and high denitration efficiency, and simultaneously has a catalytic deamination function, so that the escape of ammonia can be reduced to the maximum extent.
2. The granular composite denitration agent has good material fluidity and stable denitration effect in the storage and use processes.
3. The granular composite denitration agent is suitable for denitration of industrial incineration flue gas of industrial coal-fired boilers, industrial kilns, municipal solid waste incineration, solid waste incineration and the like, and is wide in application field.
Because the granular composite denitration agent is prepared by adopting the reducing agent containing urea and hydroxymethyl urea and the manganese ore powder-based denitration catalyst as the initial raw materials, the granular composite denitration agent has the following beneficial effects:
1. the flue gas full-temperature denitration agent obtained by the invention is injected into the flue gas with the temperature of 850-1050 ℃ in the form of solid mixture to remove NO in the flue gas x And removing. In the compounded denitrifier, the mixture of urea and hydroxymethyl urea is used as a reducing agent, and the solid reducing agent disintegrates and releases NH in high-temperature flue gas 3 Removing NO in the smoke by SNCR method x . The thermal decomposition of methylol urea can also generate OH active group, which can promote NH 3 And the NO is reduced to react, so that the denitration reaction efficiency is improved. The denitration synergist contains sodium bicarbonate, and can promote generation of OH active groups and NH after being sprayed into flue gas at 850-1050 DEG C 3 The reduction of NO greatly improves the denitration reaction efficiency, widens the denitration reaction temperature window and reduces the reaction activity of NH3 denitration to 600 ℃ in an SNCR mode.
2. The flue gas full-temperature denitration agent comprises a manganese ore powder-based denitration catalyst, and can remove NO in flue gas in an SCR (selective catalytic reduction) mode at the temperature reduction stage of 600-100 DEG C x . The manganese ore powder contains various variable valence state manganese oxides, electrons on valence layer electron d orbitals of manganese elements are in a half-full state, NO and NH3 can be adsorbed simultaneously, electron transfer is promoted, and therefore efficient denitration is achieved. Manganese oxide in manganese ore powder has strong NH adsorption capacity 3 The ability, NH3 can also be oxidized under the condition of NO NO existence, realize high-efficient deamination, thus can reduce ammonia escape.
3. The flue gas full-temperature denitration agent is suitable for the incineration treatment of municipal solid waste, the incineration treatment of solid waste and the flue gas treatment of various industrial coal-fired boilers and industrial kilns, and has wide application fields.
Drawings
FIG. 1 is an infrared spectrum of urea and modified urea of the present invention;
FIG. 2 shows the specific surface area and the average pore diameter of the manganese ore powder-based denitration catalyst of the present invention;
FIG. 3 shows the denitration activity and sulfur resistance of the manganese ore powder-based denitration catalyst according to the present invention;
FIG. 4 is a graph showing the denitration efficiency of the full-temperature denitration agent for flue gas at 100-1050 ℃ and the catalytic deamination efficiency at 100-550 ℃ in example 7 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are either commercially available from conventional sources or are prepared in conventional manners.
Example 1:
the embodiment provides a granular composite denitration agent, which comprises the following components: 80 parts by mass of a reducing agent, 8 parts by mass of a manganese ore powder-based denitration catalyst, 10 parts by mass of a denitration synergist and 2 parts by mass of an organic binder. The reducing agent is a mixture of 50 parts by mass of urea and 50 parts by mass of ammonium chloride.
The denitration synergist comprises the following components: 50 parts by mass of powdery sodium bicarbonate and 50 parts by mass of 200-mesh magnesium ore powder.
The organic binder comprises the following components: 95 parts by mass of pregelatinized starch and 5 parts by mass of xanthan gum.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 10 parts by mass of cerium oxide and 90 parts by mass of manganese ore powder at room temperature, then adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 85 ℃, and then roasting at 500 ℃ for 3 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
step two, conveying the mixture to a disc granulator, preparing an aqueous solution from an organic binder, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-2.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of coal-fired boiler flue gas and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 2:
the embodiment provides a granular composite denitration agent, which comprises the following components: 70 parts by mass of a reducing agent, 10 parts by mass of a manganese ore powder-based denitration catalyst, 18.5 parts by mass of a denitration synergist and 1.5 parts by mass of an organic binder. The reducing agent was a mixture of 50 parts by mass of ammonium chloride and 50 parts by mass of melamine.
The organic binder comprises the following components: 94 parts by mass of pregelatinized starch and 6 parts by mass of xanthan gum.
The denitration synergist comprises the following components: 20 parts of powdery sodium bicarbonate and 80 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 5 parts by mass of cerium oxide and 95 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 90 ℃, and roasting at 400 ℃ for 4 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by weight, and mixing in a mixer;
conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-2.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of flue gas of a hazardous waste incinerator and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 3:
the embodiment provides a granular composite denitration agent, which comprises the following components: 65 parts by mass of a reducing agent, 12 parts by mass of a manganese ore powder-based denitration catalyst, 21.8 parts by mass of a denitration synergist and 1.2 parts by mass of an organic binder. The reducing agent is a mixture of 60 parts by mass of urea and 40 parts by mass of ammonium chloride.
The organic binder comprises the following components: 93 parts by mass of pregelatinized starch and 7 parts by mass of xanthan gum.
The denitration synergist comprises the following components: 30 parts by mass of powdery sodium bicarbonate and 70 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 8 parts by mass of cerium oxide and 92 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 95 ℃, and roasting at 350 ℃ for 4 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
conveying the mixture to a disc granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 2.0-3.0mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of coal-fired boiler flue gas and is sprayed into the flue gas with the temperature of 1050-1100 ℃ after being sprayed into a combustion chamber.
Example 4:
the embodiment provides a granular composite denitration agent, which comprises the following components: 60 parts by mass of a reducing agent, 15 parts by mass of a manganese ore powder-based denitration catalyst, 24 parts by mass of a denitration synergist and 1 part by mass of an organic binder. The reducing agent was a mixture of 60 parts by mass of urea and 40 parts by mass of melamine.
The organic binder comprises the following components: 92 parts by mass of pregelatinized starch and 8 parts by mass of xanthan gum.
The denitration synergist comprises the following components: 25 parts by mass of powdery sodium bicarbonate and 75 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 6 parts by mass of cerium oxide and 94 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 100 ℃, and roasting at 300 ℃ for 5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 2.0-3.0mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of flue gas of an urban domestic garbage incinerator and is sprayed into the flue gas at 950-1000 ℃ after being sprayed into a combustion chamber.
Example 5:
the embodiment provides a granular composite denitration agent, which comprises the following components: 55 parts by mass of a reducing agent, 18 parts by mass of a manganese ore powder-based denitration catalyst, 26.2 parts by mass of a denitration synergist and 0.8 part by mass of an organic binder. The reducing agent is urea.
The organic binder comprises the following components: 91 parts by mass of pregelatinized starch and 9 parts by mass of xanthan gum.
The denitration synergist comprises the following components: 35 parts by mass of powdery sodium bicarbonate and 65 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 7 parts by mass of cerium oxide and 93 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain a slurry, fully and uniformly mixing, drying at 90 ℃, and roasting at 450 ℃ for 3.5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
step two, conveying the mixture to a disc granulator, preparing an aqueous solution from an organic binder, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 2.5-3.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of flue gas of an urban domestic garbage incinerator and is sprayed into the flue gas at 950-1000 ℃ after being sprayed into a combustion chamber.
Example 6:
the embodiment provides a granular composite denitration agent, which comprises the following components: 50 parts by mass of a reducing agent, 20 parts by mass of a manganese ore powder-based denitration catalyst, 29.5 parts by mass of a denitration synergist and 0.5 part by mass of an organic binder. The reducing agent is a mixture of 50 parts by mass of urea, 25 parts by mass of ammonium chloride and 25 parts by mass of melamine.
The organic binder comprises the following components: 90 parts by mass of pregelatinized starch and 10 parts by mass of xanthan gum.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: at room temperature, 7.5 parts by mass of cerium oxide and 92.5 parts by mass of manganese ore powder are uniformly stirred, then 1M dilute sulfuric acid solution is added for mixing and stirring to form slurry, the slurry is fully and uniformly mixed, the mixture is dried at 90 ℃, and then the mixture is roasted at 400 ℃ for 3.5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
conveying the mixture to a rotary drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 2.5-3.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas at 1050-1100 ℃ after being sprayed into a combustion chamber.
Example 7:
the preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 5-10 parts by mass of cerium zirconium oxide, 90-95 parts by mass of manganese ore powder and 8-15 parts by mass of strontium barium sulfate at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring to obtain slurry, fully and uniformly mixing, drying at 85-100 ℃, and roasting at 300-500 ℃ for 3 hours or more; and after cooling, ball milling is carried out again to obtain the manganese ore powder denitration catalyst loaded with the cerium powder, wherein the manganese ore powder denitration catalyst is 200 meshes. According to the preparation method of the manganese ore powder-based denitration catalyst, the specific surface area and the average pore diameter of the manganese ore powder-based denitration catalyst are improved by adding strontium barium sulfate, so that more NH is exposed to the manganese ore powder-based denitration catalyst 3 The adsorption sites and the active sites enhance the denitration capability of the manganese ore powder and can reduce the escape of ammonia. In the preparation method of the manganese ore powder-based denitration catalyst, the strontium barium sulfate is added, so that the sulfur resistance of the manganese ore powder-based denitration catalyst can be improved. Preferably, the specific surface area of the manganese ore powder-based denitration catalyst is more than 80cm 2 (ii)/g, the average pore diameter is larger than 15nm.
The embodiment provides a granular composite denitration agent, which comprises the following components: 80 parts by mass of a reducing agent, 8 parts by mass of a manganese ore powder-based denitration catalyst, 10 parts by mass of a denitration synergist and 2 parts by mass of an organic binder. The reducing agent is a mixture of 50 parts by mass of urea and 50 parts by mass of ammonium chloride.
The denitration synergist comprises the following components: 50 parts by mass of powdery sodium bicarbonate and 50 parts by mass of 200-mesh magnesium ore powder.
The organic binder comprises the following components: 95 parts by mass of pregelatinized starch and 5 parts by mass of xanthan gum.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: at room temperature, 10 parts by mass of cerium oxide, 90 parts by mass of manganese ore powder and 12 parts by mass of strontium barium sulfate are uniformly stirred, then 1M dilute sulfuric acid solution is added for mixing and stirring to form slurry, the slurry is fully and uniformly mixed, the mixture is dried at the temperature of 85 ℃, and then the mixture is roasted for 3 hours at the temperature of 500 ℃; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by mass, and mixing in a mixer;
step two, conveying the mixture to a disc granulator, preparing an aqueous solution from an organic binder, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-2.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of coal-fired boiler flue gas, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 8:
the preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 5-10 parts by mass of cerium zirconium oxide and 90-95 parts by mass of manganese ore powder at room temperature, adding 1M of dilute sulfuric acid solution, mixing and stirring, wherein the dilute sulfuric acid solution contains 0.1-0.3M of mucic acid and is in a slurry state, fully and uniformly mixing, drying at 85-100 ℃, and roasting at 300-500 ℃ for 3 hours or more; and after cooling, ball milling is carried out again to 200 meshes, so as to obtain the cerium-loaded manganese ore powder denitration catalyst. Preparation method of manganese ore powder-based denitration catalystIn the method, the dilute sulfuric acid solution containing the mucic acid is mixed and stirred, so that the specific surface area and the average pore diameter of the manganese ore powder-based denitration catalyst can be improved, and more NH is exposed to the manganese ore powder-based denitration catalyst 3 Adsorption sites and active sites enhance the denitration capability of the manganese ore powder and reduce ammonia escape. Preferably, the specific surface area of the manganese ore powder-based denitration catalyst is more than 80cm 2 (ii)/g, the average pore diameter is larger than 15nm.
The embodiment provides a granular composite denitration agent, which comprises the following components: 80 parts of reducing agent, 8 parts of manganese ore powder-based denitration catalyst, 10 parts of denitration synergist and 2 parts of organic binder. The reducing agent is a mixture of 50 parts by mass of urea and 50 parts by mass of ammonium chloride.
The denitration synergist comprises the following components: 50 parts by mass of powdery sodium bicarbonate and 50 parts by mass of 200-mesh magnesium ore powder.
The organic binder comprises the following components: 95 parts by mass of pregelatinized starch and 5 parts by mass of xanthan gum.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 10 parts by mass of cerium oxide and 90 parts by mass of manganese ore powder at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring, wherein the dilute sulfuric acid solution contains 0.2M mucic acid and is in a slurry state, fully and uniformly mixing, drying at 85 ℃, and roasting at 500 ℃ for 3 hours; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by weight, and mixing in a mixer;
conveying the mixture to a disc granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-2.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of coal-fired boiler flue gas, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 9:
the preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 5-10 parts by mass of cerium zirconium oxide, 90-95 parts by mass of manganese ore powder and 8-15 parts by mass of strontium barium sulfate at room temperature, adding 1M dilute sulfuric acid solution, mixing and stirring, wherein the dilute sulfuric acid solution contains 0.1-0.3M of mucic acid, is in a slurry state, is fully and uniformly mixed, is dried at the temperature of 85-100 ℃, and is roasted at the temperature of 300-500 ℃ for 3 hours or more; and after cooling, ball milling is carried out again to obtain the manganese ore powder denitration catalyst loaded with the cerium powder, wherein the manganese ore powder denitration catalyst is 200 meshes. The manganese ore powder-based denitration catalyst prepared by the preparation method of the manganese ore powder-based denitration catalyst has higher specific surface area and average pore diameter, thereby having higher denitration capability and reducing ammonia escape and sulfur resistance. Preferably, the specific surface area of the manganese ore powder-based denitration catalyst is more than 80cm 2 G, average pore diameter is larger than 15nm.
The embodiment provides a granular composite denitration agent, which comprises the following components: 80 parts by mass of a reducing agent, 8 parts by mass of a manganese ore powder-based denitration catalyst, 10 parts by mass of a denitration synergist and 2 parts by mass of an organic binder. The reducing agent is a mixture of 50 parts by mass of urea and 50 parts by mass of ammonium chloride.
The denitration synergist comprises the following components: 50 parts by mass of powdery sodium bicarbonate and 50 parts by mass of 200-mesh magnesium ore powder.
The organic binder comprises the following components: 95 parts by mass of pregelatinized starch and 5 parts by mass of xanthan gum.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: stirring and uniformly mixing 10 parts by mass of cerium oxide, 90 parts by mass of manganese ore powder and 12 parts by mass of strontium barium sulfate at room temperature, then adding 1M dilute sulfuric acid solution, mixing and stirring, wherein the dilute sulfuric acid solution contains 0.2M mucic acid and is in a slurry state, fully and uniformly mixing, drying at 85 ℃, and then roasting for 3 hours at 500 ℃; after cooling, the mixture is ball milled again to 200 meshes.
The granular composite denitration agent is prepared by the following method:
weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to parts by weight, and mixing in a mixer;
step two, conveying the mixture to a disc granulator, preparing an aqueous solution from an organic binder, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
and step three, conveying the produced granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-2.5mm, cooling and packaging.
The granular composite denitration agent prepared by the embodiment is used for denitration of coal-fired boiler flue gas, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 10:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 50 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH of 8.0 and heating temperature of 70 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 10 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture and 90 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 85 ℃, and then roasting at 500 ℃ for 3 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 11:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 80 parts by mass of an organic amine reducing agent, 10 parts by mass of a denitration synergist and 10 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 60 parts by mass of urea, 40 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH 7.9 and heating temperature of 75 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 20 parts of powdery sodium bicarbonate and 80 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 5 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture with 95 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 90 ℃, and roasting at 400 ℃ for 4 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 12:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 60 parts by mass of an organic amine reducing agent, 25 parts by mass of a denitration synergist and 15 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 70 parts by mass of urea and 30 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH 7.8 and heating temperature of 80 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding, and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 30 parts by mass of powdery sodium bicarbonate and 70 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 8 parts by mass of cerium nitrate hexahydrate in water at room temperature, mixing and stirring with 92 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 95 ℃, and then roasting at 350 ℃ for 4 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas at 900-1000 ℃ after being sprayed into a combustion chamber.
Example 13:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 70 parts by mass of an organic amine reducing agent, 10 parts by mass of a denitration synergist and 20 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 80 parts by mass of urea and 20 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH 7.7 and heating temperature of 75 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 25 parts by mass of powdery sodium bicarbonate and 75 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 6 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture with 94 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 100 ℃, and roasting at 300 ℃ for 5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for flue gas denitration of municipal solid waste incineration facilities, and is sprayed into flue gas at 950-1000 ℃ in a combustion chamber.
Example 14:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 75 parts by mass of an organic amine reducing agent, 13 parts by mass of a denitration synergist and 12 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 65 parts by mass of urea, 35 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH 7.6 and heating temperature of 80 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 32 parts by mass of powdery sodium bicarbonate and 68 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 7.5 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture with 92.5 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 90 ℃, and then roasting at 400 ℃ for 3.5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of household garbage incineration facilities, and is sprayed into the flue gas with the temperature of 850-950 ℃ after being sprayed into a combustion chamber.
Example 15:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 50 parts by mass of an organic amine reducing agent, 30 parts by mass of a denitration synergist and 20 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 75 parts by mass of urea, 25 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH 7.5 and heating temperature of 85 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 35 parts by mass of powdery sodium bicarbonate and 65 parts by mass of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 7 parts by mass of cerium nitrate hexahydrate in water at room temperature, mixing and stirring with 93 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 90 ℃, and then roasting at 450 ℃ for 3.5 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a hazardous waste incinerator and is sprayed into the flue gas at 900-1000 ℃ after being sprayed into a combustion chamber.
Example 16:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 50 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH of 8.0 and heating temperature of 70 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: the same as in example 7.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 17:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 50 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH of 8.0 and heating temperature of 70 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: the same as in example 8.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 18:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 50 parts by mass of methylol urea; the preparation method of the hydroxymethyl urea comprises the following steps: prepared by reacting urea and formaldehyde at the conditions of pH of 8.0 and heating temperature of 70 ℃, wherein the molar ratio of urea to formaldehyde is 1; drying the reaction product, grinding and sieving with a 100-mesh sieve.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: the same as in example 9.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 19:
a flue gas full-temperature denitration agent comprises the following components: 50-90 parts of organic amine reducing agent, 5-30 parts of denitration synergist and 5-20 parts of manganese ore powder-based denitration catalyst. Wherein, the organic amine reducing agent comprises the following raw materials: 50-80 parts of urea and 20-50 parts of mixture, wherein the mixture is hydroxymethyl urea and/or modified urea, and the modified urea is triethanolamine maleate modified urea. Preferably, when the mixture is hydroxymethyl urea and modified urea, the dosage ratio of hydroxymethyl urea to modified urea is 1. The mixture of urea, hydroxymethyl urea and/or modified urea is used as a reducing agent, OH active groups can be generated, and the denitration efficiency is further improved. The preparation method of the modified urea comprises the following steps:
adding p-toluenesulfonic acid and maleic anhydride into triethanolamine, wherein the molar ratio of the triethanolamine to the maleic anhydride is 1.8-1.2, the p-toluenesulfonic acid is 1-5% of the total mass of the triethanolamine and the maleic anhydride, and stirring and reacting at 100-120 ℃ for 2-6h to prepare triethanolamine maleate;
adding triethanolamine maleate into molten urea, wherein the molar ratio of urea to triethanolamine maleate is 1.7-1.2, stirring for reaction for 10-60s, cooling to room temperature, grinding, and sieving to obtain modified urea.
The embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 25 parts by mass of methylol urea and 25 parts by mass of modified urea; wherein, the preparation method of the hydroxymethyl urea is the same as that of the embodiment 10, and the preparation method of the modified urea comprises the following steps: adding p-toluenesulfonic acid and maleic anhydride into triethanolamine, wherein the molar ratio of the triethanolamine to the maleic anhydride is 1, the p-toluenesulfonic acid accounts for 2% of the total mass of the triethanolamine and the maleic anhydride, and stirring and reacting at 110 ℃ for 5 hours to obtain triethanolamine maleate; adding triethanolamine maleate into molten urea, stirring and reacting for 60s, wherein the molar ratio of the urea to the triethanolamine maleate is 1. Mixing urea and modified urea with potassium bromide, tablettingAnd (5) infrared spectrum characterization to obtain an infrared spectrogram shown in figure 1. As can be seen from FIG. 1, the modified urea has an IR spectrum ranging from 3100 cm to 3600cm, compared with the IR spectrum of urea -1 The intensity of the internal peak is enhanced because of the simultaneous presence of-OH and-NH 2 At 2970cm -1 Asymmetric stretching vibration of methylene appears at 2850cm -1 The symmetric stretching vibration peak of C-H in methylene appears at 1780-1740cm -1 The symmetric stretching vibration peak of C = O in acid anhydride does not appear at 1715cm -1 The symmetric stretching vibration peak of C = O in ester carbonyl appears at 1660cm -1 The peak of C = O stretching vibration in amide is strengthened at 1625cm -1 The peak reinforcement of the stretching vibration with C = C appears at 1290cm -1 At and 1060cm -1 The stretching vibration peak of C-O in alcohol appears, which indicates that the modified urea is successfully prepared.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 10 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture and 90 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 85 ℃, and then roasting at 500 ℃ for 3 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 20:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 25 parts by mass of methylol urea and 25 parts by mass of modified urea; the preparation method of methylol urea was the same as in example 10, and the preparation method of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 7.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 21:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 25 parts by mass of methylol urea and 25 parts by mass of modified urea; the preparation method of methylol urea was the same as in example 10, and the preparation method of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 8.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 22:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea, 25 parts by mass of methylol urea and 25 parts by mass of modified urea; the preparation method of methylol urea was the same as in example 10, and the preparation method of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 9.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 23:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea and 50 parts by mass of modified urea; the process for the preparation of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst comprises the following steps: dissolving 10 parts by mass of cerous nitrate hexahydrate in water at room temperature, mixing and stirring the mixture and 90 parts by mass of manganese ore powder to form slurry, fully and uniformly mixing, drying at 85 ℃, and then roasting at 500 ℃ for 3 hours; after cooling, the mixture is ball milled again to 200 meshes.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 24:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea and 50 parts by mass of modified urea; the process for the preparation of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 7.
The preparation method of the flue gas full-temperature denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler and is sprayed into the flue gas at 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 25:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea and 50 parts by mass of modified urea; the preparation of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 8.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Example 26:
the embodiment provides a flue gas full-temperature denitration agent, which comprises the following components: 90 parts by mass of an organic amine reducing agent, 5 parts by mass of a denitration synergist and 5 parts by mass of a manganese ore powder-based denitration catalyst.
The organic amine reducing agent comprises the following components: 50 parts by mass of urea and 50 parts by mass of modified urea; the preparation of modified urea was the same as in example 19.
The denitration synergist comprises the following components: 40 parts of powdery sodium bicarbonate and 60 parts of 200-mesh magnesium ore powder.
The preparation method of the manganese ore powder-based denitration catalyst is the same as that of example 9.
The preparation method of the full-temperature flue gas denitration agent comprises the following steps: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, and uniformly mixing in a mixer.
The flue gas full-temperature denitration agent prepared by the embodiment is used for denitration of flue gas of a coal-fired boiler, and is sprayed into the flue gas with the temperature of 1000-1050 ℃ after being sprayed into a combustion chamber.
Test example 1:
the specific surface area and the average pore diameter of the manganese ore powder-based denitration catalyst samples prepared in examples 1 to 9 were measured by a full-automatic physical adsorption apparatus, about 0.1g of the sample was pretreated at 400 ℃ for 3 hours under vacuum, and then N was performed in a liquid nitrogen environment at-196 ℃ 2 And (3) adsorption-desorption, wherein the specific surface area of the manganese ore powder-based denitration catalyst sample is calculated by a BET method, the average pore diameter of the manganese ore powder-based denitration catalyst sample is calculated by a BJH model, and the calculation result is shown in figure 2.
As can be seen from FIG. 2, the specific surface areas of the manganese ore powder-based denitration catalysts prepared in examples 1 to 9 of the present invention were more than 50cm 2 A specific surface area of the manganese ore powder-based denitration catalyst prepared in examples 7 to 9 of more than 80cm 2 G, average pore diameter is larger than 15nm. It can also be seen that the specific surface area and the average pore size of the manganese ore powder-based denitration catalysts prepared in examples 7 to 9 are larger than those of the manganese ore powder-based denitration catalyst prepared in example 1, which indicates that the addition of strontium barium sulfate and/or mucic acid in the preparation method of the manganese ore powder-based denitration catalyst can increase the specific surface area and the average pore size of the manganese ore powder-based denitration catalyst.
Test example 2:
the denitration performance of the manganese ore powder-based denitration catalyst samples prepared in examples 1 to 9 was measured by using a flue gas denitration catalyst activity evaluation apparatus, which was composed of three parts:
the gas distribution system simulates the environment of flue gas, and the simulated flue gas comprises 0.03 percent of NO and 0.03 percent of NH 3 、5% O 2 And Ar is balance gas, the total flow is 200mL/min;
the reaction system consists of a reaction furnace, a thermocouple and a temperature controller, the dosage of the catalyst is 0.5 g/time, and reaction gas passes through the catalyst layer for 0.5h at normal temperature before each experiment so as to ensure that the reaction gas is in an adsorption saturation state;
and the detection system is used for detecting the concentration of the nitrogen oxide on line by the analyzer.
The temperature rising mode selected in the test is that the temperature is raised to 300 ℃ from normal temperature at the speed of 10 ℃/min, the temperature is kept for 1h, and the air speed of the gas is 20000h -1 . Denitration activity of manganese ore powder-based denitration catalyst is expressed by NO x Conversion is expressed as NO x Conversion = (1-C) NOx,out / C NOx,in ) X 100%, wherein C NOx,in For simulating the mass concentration of the flue gas inlet, C NOx,out Calculating the NO of the manganese ore powder-based denitration catalyst to simulate the outlet mass concentration of the flue gas x The conversion is shown as a in FIG. 3. The sulfur resistance test of the manganese ore powder-based denitration catalyst was also performed in this test example, and 0.02% SO was added to the simulated flue gas 2 Keeping NO of the manganese ore powder-based denitration catalyst for 6 hours under the condition of keeping other conditions unchanged x The conversion, results are shown in b in FIG. 3.
As can be seen from FIG. 3, the NO of the manganese ore powder-based denitration catalysts prepared in examples 7 to 9 of the present invention x The conversion rate was higher than that of the manganese ore powder-based denitration catalyst prepared in example 1, which indicates that the addition of strontium barium carbonate and/or mucic acid in the preparation method of the manganese ore powder-based denitration catalyst can improve the denitration ability of the manganese ore powder-based denitration catalyst. As can be seen from FIG. 3, with SO 2 In addition, NO of the denitration efficiency after 6 hours was achieved by using the manganese ore powder-based denitration catalyst prepared in examples 1 to 9 of the present invention x The conversion rate was decreased, however, NO of the manganese ore powder-based denitration catalysts prepared in examples 7 and 9 of the present invention was reduced x The reduction rate of the conversion rate is lower than that of the manganese ore powder-based denitration prepared in the examples 1 and 8The catalyst shows that the addition of strontium barium acid in the preparation method of the manganese ore powder-based denitration catalyst can improve the sulfur resistance of the manganese ore powder-based denitration catalyst.
Test example 3:
the denitration agents prepared in examples 1 to 26 are applied to an industrial field, and NO in the chimney gas of an incineration facility is monitored on line in real time x And NH 3 Concentration change of NO in stack gas without using denitrifier x The hour-average concentration of (a) is an initial concentration to use NO in the stack gas when the denitrifier is used x The obtained average concentration in hours was the concentration after treatment, and the denitration effect of the prepared denitration agent was evaluated, and the denitration effect results of the particulate composite denitration agents prepared in examples 1 to 9 are shown in table 1, and the denitration effect results of the full-temperature denitration agents for flue gas prepared in examples 10 to 26 are shown in table 2.
TABLE 1
As can be seen from table 1, the granular composite denitration agent obtained in examples 1 to 9 of the present invention has a high denitration efficiency after being injected into industrial incineration flue gas of an industrial coal-fired boiler, an industrial kiln, municipal solid waste incineration, and the like, and the denitration agent minimizes ammonia escape. The granular composite denitration agent obtained by the invention solves the problems in the background technology and has wide application value. As can be seen from table 1, the denitration rates of the particulate composite denitration agents obtained in examples 7 to 9 of the present invention are higher than the denitration rate of the particulate composite denitration agent obtained in example 1, wherein the denitration rates of the particulate composite denitration agents obtained in examples 7 and 8 of the present invention are not lower than 96%, and the denitration rate of the particulate composite denitration agent obtained in example 9 is not lower than 97.5%, which indicates that the denitration effects of the particulate composite denitration agents obtained in examples 7 to 9 of the present invention are better than the denitration effects of the particulate composite denitration agent obtained in example 1. It can also be seen from table 1 that NH in the flue gas after the treatment of the particulate composite denitration agent obtained in examples 7 and 8 of the present invention 3 The concentration is lower than that of the granular composite denitration agent obtained in example 1, which shows the comparisonThe granular composite denitration agent obtained in example 1 and the granular composite denitration agents obtained in examples 7 to 9 of the invention can further reduce ammonia escape.
TABLE 2
FIG. 4 is a denitration efficiency curve of a flue gas full-temperature denitration agent at 100-1050 ℃ and a catalytic deamination efficiency curve at 100-550 ℃ in example 7 of the present invention. As can be seen from the table 1 and the figure 4, the flue gas full-temperature denitration agent obtained by the invention can continuously play a denitration role in the subsequent flue gas full-cooling process after being sprayed into the flue gas with the temperature of 850-1050 ℃, so that NO in the flue gas is realized x The high-efficiency removal is realized; meanwhile, the denitrifying agent has the function of catalytically removing ammonia in the flue gas, so that the escape of ammonia can be reduced. Table 1 also shows that the denitration efficiency of the flue gas full-temperature denitration agent obtained in example 19 and example 23 is greater than 95%, and the denitration efficiency of the flue gas full-temperature denitration agent obtained in example 15 and example 16 is greater than the denitration efficiency of the flue gas full-temperature denitration agent obtained in example 10, which indicates that the denitration efficiency of the flue gas full-temperature denitration agent can be further improved by using a mixture of urea, methylol urea and/or modified urea as a reducing agent. As can be seen from table 1, the denitration rate of the particulate composite denitration agent obtained in example 18 of the present invention is higher than that of the particulate composite denitration agent obtained in example 10, the denitration rate of the particulate composite denitration agent obtained in example 22 is higher than that of the particulate composite denitration agent obtained in example 19, and the denitration rate of the particulate composite denitration agent obtained in example 26 is higher than that of the particulate composite denitration agent obtained in example 23, where the denitration rate of the particulate composite denitration agent obtained in example 18 is higher than 95%, and the denitration rates of the particulate composite denitration agents obtained in examples 22 and 26 of the present invention are higher than 98%, which indicates that the denitration capabilities of the manganese ore powder-based denitration catalysts for the particulate composite denitration agents of examples 18, 22 and 26 of the present invention are better. By table 1It can be seen that the particulate composite denitration agent obtained in example 18 of the present invention treats NH in the stack gas 3 The concentration of the particulate composite denitration agent is lower than that of the particulate composite denitration agent obtained in example 10, and NH in the chimney gas treated by the particulate composite denitration agent obtained in example 22 3 The concentration of the NH in the chimney gas treated by the granular composite denitration agent obtained in example 26 is lower than that of the granular composite denitration agent obtained in example 19 3 The concentration of the manganese ore powder-based denitration catalyst is lower than that of the granular composite denitration agent obtained in example 23, which indicates that the use of the manganese ore powder-based denitration catalyst for the granular composite denitration agents in examples 18, 22 and 26 of the present invention can reduce ammonia slip.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A denitration agent is a granular composite denitration agent, and the granular composite denitration agent comprises the following components: 50-80 parts of reducing agent, 8-20 parts of manganese ore powder-based denitration catalyst, 10-30 parts of denitration synergist and 0.5-2 parts of organic binder.
2. The denitration agent according to claim 1, wherein the reducing agent is prepared from the following raw materials: one or more of powdered urea, powdered ammonium chloride, and powdered melamine.
3. The denitrifier according to claim 1, wherein the manganese ore powder-based denitration catalyst is cerium-supported manganese ore powder, the particle size of the manganese ore powder is 200 meshes, and the manganese content is more than 40%.
4. The method of preparing the denitration agent of claim 1, comprising:
the method comprises the following steps: weighing a powdery reducing agent, a manganese ore powder-based denitration catalyst and a denitration synergist according to the mass parts, and mixing in a mixer;
step two: conveying the mixture to a disc granulator or a drum granulator, preparing an organic binder into an aqueous solution, spraying the aqueous solution onto the surface of the mixture by high-pressure spraying, and carrying out rolling granulation;
step three: conveying the granules to a drying cylinder for drying, sieving and screening the granules with the diameter of 1.5-3.5 mm, cooling and packaging.
5. The use of the denitrifier according to claim 1 in the removal of nitrogen oxides from flue gases, wherein the denitrifier is sprayed into flue gases at 950-1100 ℃, and the denitration reaction temperature ranges from 100-1100 ℃.
6. The denitration agent is a flue gas full-temperature denitration agent and is characterized by comprising the following components in parts by mass: 50-90 parts of organic amine reducing agent, 5-30 parts of denitration synergist and 5-20 parts of manganese ore powder-based denitration catalyst.
7. The denitrifier according to claim 6, wherein the organic amine reducing agent comprises the following raw materials: 50-80 parts of urea and 20-50 parts of hydroxymethyl urea.
8. The denitrifier according to claim 6, wherein the manganese ore powder-based denitration catalyst is cerium-loaded manganese ore powder, the particle size of the manganese ore powder is 200 meshes, and the manganese content is more than 30%.
9. The method of preparing the denitration agent of claim 6, comprising: directly mixing the organic amine reducing agent, the denitration synergist and the manganese ore powder-based denitration catalyst, uniformly mixing in a mixer, and then sealing and packaging.
10. The use of the denitrifier according to claim 6 for removing nitrogen oxides from flue gas, wherein the denitrifier is injected into the flue gas at 850-1050 ℃, and the denitrifier has a denitration temperature in the range of 100-1050 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116212631A (en) * | 2022-12-30 | 2023-06-06 | 嘉兴沃特泰科环保科技股份有限公司 | High-temperature SO removal for waste incineration flue gas 2 Synergistic catalytic NOx removal method |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4824815A (en) * | 1985-06-11 | 1989-04-25 | Exxon Research And Engineering Company | Cracking catalysts containing strontium carbonate |
| EP0333833A1 (en) * | 1987-09-23 | 1989-09-27 | Fuel Tech, Inc. | Process for the reduction of nitrogen oxides in an effluent |
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| US20150306578A1 (en) * | 2014-04-24 | 2015-10-29 | Jifei Jia | Method of preparing high activity hydrotreating catalysts |
| CN105618032A (en) * | 2016-01-19 | 2016-06-01 | 中国建筑材料科学研究总院 | Supported manganese based low-temperature denitration catalyst and preparation method thereof |
| CN106861431A (en) * | 2017-04-21 | 2017-06-20 | 广东龙鼎环境科技工程有限公司 | Quadruple effect denitrfying agent composition and its method of denitration |
| CN111545040A (en) * | 2020-04-10 | 2020-08-18 | 佛山华清智业环保科技有限公司 | Composite denitration agent and preparation method thereof |
| CN111992035A (en) * | 2020-08-13 | 2020-11-27 | 青岛惠城环保科技股份有限公司 | High-fluidity efficient denitration agent and preparation method thereof |
| CN112427033A (en) * | 2020-11-17 | 2021-03-02 | 北京科技大学 | Method for preparing low-temperature denitration catalyst by utilizing manganese ore |
| CN112495373A (en) * | 2020-12-10 | 2021-03-16 | 重庆大学 | Manganese-containing soil low-temperature denitration catalyst and preparation method thereof |
| CN112569965A (en) * | 2020-12-23 | 2021-03-30 | 内蒙古工业大学 | Double-transition metal hierarchical pore catalyst and preparation method and application thereof |
| CN112915751A (en) * | 2020-06-22 | 2021-06-08 | 北京中科润宇环保科技股份有限公司 | Preparation method of high-molecular solid powder denitration agent for flue gas denitration |
-
2022
- 2022-08-29 CN CN202211037215.1A patent/CN115501748B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4824815A (en) * | 1985-06-11 | 1989-04-25 | Exxon Research And Engineering Company | Cracking catalysts containing strontium carbonate |
| EP0333833A1 (en) * | 1987-09-23 | 1989-09-27 | Fuel Tech, Inc. | Process for the reduction of nitrogen oxides in an effluent |
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| US20150306578A1 (en) * | 2014-04-24 | 2015-10-29 | Jifei Jia | Method of preparing high activity hydrotreating catalysts |
| CN105618032A (en) * | 2016-01-19 | 2016-06-01 | 中国建筑材料科学研究总院 | Supported manganese based low-temperature denitration catalyst and preparation method thereof |
| CN106861431A (en) * | 2017-04-21 | 2017-06-20 | 广东龙鼎环境科技工程有限公司 | Quadruple effect denitrfying agent composition and its method of denitration |
| CN111545040A (en) * | 2020-04-10 | 2020-08-18 | 佛山华清智业环保科技有限公司 | Composite denitration agent and preparation method thereof |
| CN112915751A (en) * | 2020-06-22 | 2021-06-08 | 北京中科润宇环保科技股份有限公司 | Preparation method of high-molecular solid powder denitration agent for flue gas denitration |
| CN111992035A (en) * | 2020-08-13 | 2020-11-27 | 青岛惠城环保科技股份有限公司 | High-fluidity efficient denitration agent and preparation method thereof |
| CN112427033A (en) * | 2020-11-17 | 2021-03-02 | 北京科技大学 | Method for preparing low-temperature denitration catalyst by utilizing manganese ore |
| CN112495373A (en) * | 2020-12-10 | 2021-03-16 | 重庆大学 | Manganese-containing soil low-temperature denitration catalyst and preparation method thereof |
| CN112569965A (en) * | 2020-12-23 | 2021-03-30 | 内蒙古工业大学 | Double-transition metal hierarchical pore catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王涛等: "天然锰矿负载CeO2低温NH3-SCR脱硝性能" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116212631A (en) * | 2022-12-30 | 2023-06-06 | 嘉兴沃特泰科环保科技股份有限公司 | High-temperature SO removal for waste incineration flue gas 2 Synergistic catalytic NOx removal method |
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