CN116651176A - Ammonia-free denitration agent for biomass boiler and preparation method thereof - Google Patents
Ammonia-free denitration agent for biomass boiler and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000007800 oxidant agent Substances 0.000 claims abstract description 34
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000002250 absorbent Substances 0.000 claims abstract description 13
- 230000002745 absorbent Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000012875 nonionic emulsifier Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000032798 delamination Effects 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 71
- 238000012544 monitoring process Methods 0.000 abstract description 11
- 239000000779 smoke Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010413 mother solution Substances 0.000 abstract description 5
- 239000012895 dilution Substances 0.000 abstract description 3
- 238000010790 dilution Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 239000003546 flue gas Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 229910002089 NOx Inorganic materials 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- 239000004202 carbamide Substances 0.000 description 9
- 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 8
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 229950008882 polysorbate Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229940068968 polysorbate 80 Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses an ammonia-free denitration agent for a biomass boiler and a preparation method thereof, wherein the preparation raw materials comprise the following components in percentage by mass: 13-18% of oxidant, 0.5-2% of solubilizer, 0.5-1% of dispersant, 15-19% of absorbent, 8-15% of activated carbon slurry and the balance of water. 5. The denitration agent can be doped to effectively reduce the monitoring values of the nitrogen oxides at the smoke inlet and the nitrogen oxides at the smoke outlet, and the finished product has the effect of reducing the nitrogen oxides both in the mother solution and after dilution, and has the advantages of simple use method, low cost, convenient use, great economic value and wide application prospect.
Description
Technical Field
The invention relates to the field of B01D53/60, in particular to an ammonia-free denitration agent for a biomass boiler and a preparation method thereof.
Background
Along with the continuous transformation and upgrading of the energy structures at home and abroad, the renewable energy duty ratio is continuously improved in the world energy structure, and the biomass is the only renewable energy source which can be directly used as fuel at present, and meanwhile, the biomass is convenient to store and stable in application.
CN110252051B discloses a method for dedusting, desulfurizing and denitrating boiler flue gas and removing dioxin, wherein flue gas with the temperature of 250-350 ℃ is led out from the boiler, bicarbonate and reducing agent are sprayed into the flue gas, and then the flue gas enters a denitration compound dust removal device for denitration, dioxin removal and dust removal. CN113144897a provides a dry-process denitration agent and an application method thereof, wherein the dry-process denitration agent comprises an oxidant, urea, a catalyst, an organic accelerator, a drying agent and the like, and can achieve denitration efficiency of 99% when used at a temperature of 600-900 ℃, and the dry-process denitration agent has the advantages of simple use method, low cost, convenient use, great economic value and wide application prospect.
However, biomass fuels are generally high in volatile matter, high in water content, low in carbon content, low in calorific value, low in sulfur content and ash content, high in combustion speed, easy to ignite and burn out and poor in combustion stability. The concentration of smoke dust and SOx generated by biomass fuel is low, but the ash melting point is low, the ash often contains higher K, na and other alkali metals, and meanwhile, the problems of corrosion, coking and the like are easy to occur possibly along with chlorine. Compared with a coal-fired boiler, the fly ash in the flue gas of the biomass boiler has higher alkali metal content and humidity and strong adhesiveness. Meanwhile, the load fluctuation of the biomass boiler is larger, the combustion is unstable, the temperature difference in the boiler is large, and the initial nitrogen oxide emission fluctuation is larger. Therefore, the problems of fly ash utilization, ammonia escape utilization and the like after combustion are also considered seriously when the biomass power plant performs denitration treatment.
Disclosure of Invention
Aiming at the problems, the invention discloses an ammonia-free denitration agent for a biomass boiler, which comprises the following raw materials in percentage by mass: 13-18% of oxidant, 0.5-2% of solubilizer, 0.5-1% of dispersant, 15-19% of absorbent, 8-15% of activated carbon slurry and the balance of water.
In one embodiment, the oxidizing agent is a primary inorganic oxidizing agent and/or a primary organic oxidizing agent.
Preferably, the oxidant is a combination of a primary inorganic oxidant and a primary organic oxidant, and the mass ratio is (10-30): 1.
the primary inorganic oxidant comprises one or a combination of several of potassium permanganate, sodium perchlorate and sodium chlorate; potassium permanganate is preferred.
The primary organic oxidizer includes, but is not limited to, one or more of peroxyacetic acid, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, perbenzoic acid, performic acid; preferably peracetic acid.
In one embodiment, the solubilizing agent is selected from one or more of cationic solubilizing agents, anionic solubilizing agents, nonionic solubilizing agents, zwitterionic solubilizing agents.
Preferably, the solubilizer is a nonionic solubilizer.
Further preferably, the nonionic solubilizer comprises one or a combination of several of polysorbate, polyethylene glycol and polyoxyethylene fatty acid.
More preferably, the solubilizing agent is polysorbate.
In one embodiment, the dispersant is an anionic organic dispersant and/or a nonionic organic dispersant.
The anionic organic dispersants include, but are not limited to, alkyl naphthalene sulfonates, carboxylates, alkylbenzene sulfonates, sulfate salts, and the like.
The nonionic organic dispersants include, but are not limited to, polycarboxylates, poly (meth) acrylic acid derivatives, nonylphenol polyoxyethylene ethers, and the like.
Preferably, the dispersant is a sulfate salt.
Further preferably, the sulfate salt is sodium dodecyl sulfate.
In one embodiment, the absorbent is selected from one or a combination of several of calcium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the absorbent is sodium carbonate.
Further preferably, the sodium carbonate has an average particle size of 100 to 3000 mesh.
In one embodiment, the activated carbon slurry is prepared from the following raw materials in percentage by mass: 0.2-3% of emulsifying agent, 1-10% of active carbon and the balance of deionized water.
In one embodiment, the emulsifier is a cationic emulsifier and/or a nonionic emulsifier.
Preferably, the emulsifier is a combination of a cationic emulsifier and a nonionic emulsifier, and the mass ratio is (0.5-3): 1.
further preferably, the cationic emulsifier is cetyl trimethylammonium bromide; the nonionic emulsifier is selected from one or more of polyacrylamide, polyethylene glycol and polyethylene glycol monostearate.
More preferably, the nonionic emulsifier is polyethylene glycol, the average molecular weight of the polyethylene glycol is 300-800, and polyethylene glycol-400 and polyethylene glycol-600 can be cited.
In one embodiment, the activated carbon is a micron-sized activated carbon.
Preferably, the micron-sized activated carbon is 10-200 microns.
Further preferably, the micron-sized activated carbon has an iodine value of greater than 600.
In one embodiment, the method for preparing the activated carbon slurry comprises the steps of: the emulsifier was dissolved in half of the water until it was completely dissolved. Adding active carbon into the aqueous solution, stirring for 60-180 min, adding the rest water, emulsifying for 0.5-2 h by a shearing emulsifying machine, and standing to prevent layering.
The oxidant in the ammonia-free denitration agent mainly acts as follows: firstly, an oxygen source is provided, so that the oxygen source can rapidly release oxygen to react with nitric oxide at high temperature to produce nitrogen dioxide; secondly, the oxidizing agent is directly reacted with nitric oxide to generate nitrogen dioxide, and the primary inorganic oxidizing agent and the primary organic oxidizing agent are combined, so that the safety of a system and sufficient oxygen supply can be ensured, the process that the absorbing agent converts nitrogen dioxide into stable nitrate through physical and chemical adsorption can be promoted, and the dispersion of the absorbing agent in the system can be improved by adding a small amount of organic oxidizing agent, so that the nanoscale absorbing agent can absorb and convert nitrogen dioxide into nitrate more efficiently, and the NOx in tail gas can be removed efficiently. The emulsifier is the combination of a cationic emulsifier and a nonionic emulsifier, and the active carbon slurry prepared from the micron active carbon can capture and adsorb nitrogen, nitric oxide and nitrogen dioxide more efficiently through physical adsorption so that the active carbon slurry can be more fully contacted with the ammonia-free denitration agent. The dispersant can further increase the solubility of the oxidant and the absorbent, and improve the conversion efficiency of NOx into nitrate. Finally, the generated nitrate particles can be captured in a dust collection link, so that the aim of denitration is fulfilled.
The invention also discloses a preparation method of the ammonia-free denitration agent, which comprises the following steps: fully stirring the solubilizer, the absorbent and the water, then adding the dispersing agent and the activated carbon slurry into the mixture, emulsifying the mixture for 1 to 3 hours by using a shearing emulsifying machine, standing the mixture to prevent delamination, continuously adding the oxidant into the system, and fully and uniformly stirring the mixture.
Advantageous effects
1. The combination of the primary inorganic oxidant and the primary organic oxidant not only can ensure the safety of the system and enough oxygen supply, but also can promote the process that the absorber converts nitrogen dioxide into stable nitrate through physical and chemical adsorption.
2. The nanoscale absorbent can absorb and convert nitrogen dioxide into nitrate more efficiently, so that the NOx in the tail gas can be removed efficiently.
3. The emulsifier is the combination of a cationic emulsifier and a nonionic emulsifier, and the active carbon slurry prepared from the micron active carbon can capture and adsorb nitrogen, nitric oxide and nitrogen dioxide more efficiently through physical adsorption so that the active carbon slurry can be more fully contacted with the ammonia-free denitration agent.
4. The dispersant can further increase the solubility of the oxidant and the absorbent, and improve the conversion efficiency of NOx into nitrate. Finally, the generated nitrate particles can be captured in a dust collection link, so that the aim of denitration is fulfilled.
5. The denitration agent can be doped to effectively reduce the monitoring values of the nitrogen oxides at the smoke inlet and the nitrogen oxides at the smoke outlet, and the finished product has the effect of reducing the nitrogen oxides both in the mother solution and after dilution, and has the advantages of simple use method, low cost, convenient use, great economic value and wide application prospect.
Detailed Description
The embodiment discloses an ammonia-free denitration agent for a biomass boiler, which comprises the following preparation raw materials in percentage by mass: 15% of oxidant, 1% of solubilizer, 0.8% of dispersing agent, 17% of absorbent, 10% of activated carbon slurry and the balance of water.
The oxidant is a combination of potassium permanganate and peracetic acid, and the mass ratio is 20:1.
the solubilizer is polysorbate-80.
The dispersing agent is sodium dodecyl sulfate.
The absorbent is sodium carbonate, and is purchased from Teng Zhan Shing commercial Co Ltd in Tangshan, the grade of the product is industrial grade, and the granularity is 400 meshes.
The active carbon slurry is prepared from the following raw materials in percentage by mass: 1.8% of emulsifying agent, 8.2% of active carbon and the balance of deionized water.
The emulsifier is a combination of cetyl trimethyl ammonium bromide and polyethylene glycol-400, and the mass ratio is 1:1.
the activated carbon is micron-sized activated carbon, is purchased from the company of the Ministry of water treatment materials of the Feng Xiang Fu, and has an average particle size of 75 microns (200 meshes) and an iodine value of 650-1000.
The preparation method of the activated carbon slurry comprises the following steps: the emulsifier was dissolved in half of the water until it was completely dissolved. Adding active carbon into the aqueous solution, stirring for 90min, adding the rest water, emulsifying for 1 hr with a shearing emulsifying machine, and standing to prevent delamination.
On the other hand, the embodiment discloses a preparation method of the ammonia-free denitration agent, which comprises the steps of fully stirring a solubilizer, an absorbent and water, adding a dispersing agent and active carbon slurry into the mixture, emulsifying the mixture for 2 hours by using a shearing emulsifying machine, standing the mixture to prevent layering, continuously adding an oxidant into the system, and fully and uniformly stirring the mixture.
Performance testing
1. The test method comprises the following steps: the design principle of the denitration agent is that the denitration agent is added at the outlet flue of the air preheater, and the denitration agent is fully contacted and reacted with nitrogen oxides in the flue gas through atomization and spraying. And (3) observing the change of the emission value of the nitrogen oxides, and gradually reducing the using amount of SNCR denitration urea under the condition of ensuring that the environmental protection emission reaches the standard.
2. Test temporary equipment installation:
the factory side needs to provide a 304 stainless steel atomizing spray gun; one gear metering pump for test, a liquid pipeline fitting and other mounting auxiliary materials. The compressed air pipeline is connected to the vicinity of the placement point of the spray gun at the outlet of the air preheater, and the diameter of the compressed air pipeline is DN 25; the method is characterized in that the method is matched with a factory to implement field installation work and electrify and communicate compressed air.
3. The test steps are as follows:
the denitration agent is transported to a designated position.
And connecting a compressed air pipe with the gas end of the spray gun, connecting a liquid outlet pipe of the pump with the liquid end of the spray gun, and starting the pump and the compressed air for debugging so as to achieve the optimal atomization state.
The spray gun is arranged on the south side of the east flue of the air preheater outlet, holes are needed to be drilled in advance, and pipelines are welded, so that the spray gun is convenient to place and fix.
Under the condition of normal production and relatively stable emission of nitrogen oxides in the flue, statistics of blank period data is carried out, and the NOx monitoring value at the inlet end of the flue gas is 72mg/Nm 3 The NOx monitoring value at the outlet end is 43mg/Nm 3 The urea dosage is 845kg/h. Starting a mother liquor test 10:07, starting a denitration agent pump flow 253kg/h, gradually descending the NOx at the smoke inlet end about 5 minutes, and recording that the monitoring value of the NOx at the smoke inlet end after 10 minutes of reaction is 42mg/Nm 3 The NOx monitoring value at the outlet end is 27mg/Nm 3 The urea dosage is 820kg/h. Manual urea consumption reduction is 100kg/h, continuous observation is continued for ten minutes, and the NOx monitoring value is basically stabilized at 42mg/Nm 3 And (3) continuing the test to gradually reduce the dosage of the denitration agent, so that the minimum dosage of the denitration agent for monitoring the qualified emission of NOx at the outlet end is 111kg/h, the dosage of urea is 690kg/h, and the denitration agent is stable for a period of time.
According to the test of diluting the finished product in a ratio of 1:1, the minimum usage amount of the denitration agent is 253kg/h (the usage amount of the combined mother liquor is 126.5 kg/h), and the nitrogen oxide value of the flue gas inlet can be reduced to 50mg/Nm 3 And right and left, replacing the back-end SCR system. Reducing ureaThe dosage is 105kg/h. (the fluctuation of the detection of the nitrogen oxide value at the flue gas inlet during the test is larger and is 30 mg/Nm) 3 Left and right amplitude. ) The monitoring data are similar in the cases of 380kg/h and 253kg/h of the finished denitration agent. The nitrogen oxide does not obviously decrease in a large extent when the flow of the denitration agent is increased.
Test data:
conclusion of the test
1. The using amount of the denitration agent mother liquor is 253kg/h, the using amount of urea is reduced by 135kg/h, and the nitrogen oxide value at the flue gas inlet can be reduced to below 50 to replace a rear-end SCR system. The using amount of the denitration agent mother liquor is 110kg/h, the using amount of urea is reduced by 155kg/h, the nitrogen oxide value at a flue gas outlet can be reduced to below 50, and the rear-end SCR system is assisted.
2. The minimum usage amount of 253kg/h (the usage amount of the combined mother solution is 126.5 kg/h) of the denitration agent mother solution after dilution according to the proportion of 1:1 can reduce the nitrogen oxide value of the flue gas inlet to 50mg/Nm 3 And right and left, replacing the back-end SCR system. The urea consumption is reduced by 105kg/h. (the fluctuation of the detection of the nitrogen oxide value at the flue gas inlet during the test is larger and is 30 mg/Nm) 3 Left and right amplitude. )
3. The blending of the denitration agent can effectively reduce the monitoring value of the nitrogen oxides at the smoke inlet and the nitrogen oxides at the smoke outlet, and the finished product has the effect of reducing the nitrogen oxides no matter the mother solution or the diluted finished product.
4. The fluctuation range of the nitrogen oxide monitoring value of the flue gas inlet is large during the test, the analysis of reasons can be overlarge with the sectional area of the flue, the atomization effect of the single spray gun can not achieve full coverage, and unreacted flue gas can escape. The test effect can be improved by increasing the total coverage of the spray gun to the coverage surface.
Claims (10)
1. The ammonia-free denitration agent for the biomass boiler is characterized by comprising the following preparation raw materials in percentage by mass: 13-18% of oxidant, 0.5-2% of solubilizer, 0.5-1% of dispersant, 15-19% of absorbent, 8-15% of activated carbon slurry and the balance of water.
2. The ammonia-free denitration agent according to claim 1, wherein the oxidizing agent is a primary inorganic oxidizing agent and/or a primary organic oxidizing agent.
3. The ammonia-free denitration agent according to claim 2, wherein the oxidant is a combination of a primary inorganic oxidant and a primary organic oxidant, and the mass ratio is (10-30): 1.
4. the ammonia-free denitration agent according to claim 3, wherein the primary inorganic oxidant is selected from one or a combination of several of potassium permanganate, sodium perchlorate and sodium chlorate; the primary organic oxidant is selected from one or more of peroxyacetic acid, dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, perbenzoic acid and performic acid.
5. The ammonia-free denitration agent according to claim 1, wherein the solubilizing agent is one or more selected from the group consisting of cationic solubilizing agents, anionic solubilizing agents, nonionic solubilizing agents, and zwitterionic solubilizing agents.
6. The ammonia-free denitration agent according to claim 1, wherein the raw materials for preparing the activated carbon slurry comprise, in mass percent: 0.2-3% of emulsifying agent, 1-10% of active carbon and the balance of deionized water.
7. The ammonia-free denitration agent according to claim 6, wherein the emulsifier is a cationic emulsifier and/or a nonionic emulsifier.
8. The ammonia-free denitration agent according to claim 7, wherein the activated carbon is a micron-sized activated carbon; the average particle size of the micron-sized activated carbon is 10-200 microns.
9. The ammonia-free denitration agent according to any one of claims 6 to 8, characterized by the preparation method of the activated carbon slurry comprising the steps of: dissolving the emulsifier in half of water until it is completely dissolved; adding active carbon into the aqueous solution, stirring for 60-180 min, adding the rest water, emulsifying for 0.5-2 h by a shearing emulsifying machine, and standing to prevent layering.
10. A method of preparing the ammonia-free denitration agent according to claim 9, comprising the steps of: fully stirring the solubilizer, the absorbent and the water, then adding the dispersing agent and the activated carbon slurry into the mixture, emulsifying the mixture for 1 to 3 hours by using a shearing emulsifying machine, standing the mixture to prevent delamination, continuously adding the oxidant into the system, and fully and uniformly stirring the mixture.
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