CN111249894A - Method for simultaneously desulfurizing and denitrifying flue gas by using solid ammonium salt - Google Patents
Method for simultaneously desulfurizing and denitrifying flue gas by using solid ammonium salt Download PDFInfo
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- 239000003546 flue gas Substances 0.000 title claims abstract description 113
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 83
- 239000007787 solid Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 38
- 230000023556 desulfurization Effects 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 11
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 29
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- 239000000428 dust Substances 0.000 description 21
- 230000008569 process Effects 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910002089 NOx Inorganic materials 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000002250 absorbent Substances 0.000 description 9
- 230000002745 absorbent Effects 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000009102 absorption Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 238000005507 spraying Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 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 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
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- 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 relates to a method for simultaneously desulfurizing and denitrifying flue gas by using solid ammonium salt. The method comprises the following steps: preparing solid ammonium salt into fine powder, wherein the solid ammonium salt is a single component or a mixture of the single component and the mixture, and the main component of the ammonium sulfate or the ammonium sulfite is ammonium sulfate or ammonium sulfite; the invention relates to a dry-method flue gas purification system, which is characterized in that powdery solid ammonium salt is mixed with flue gas at the temperature of 80-240 ℃ in a flue or a closed gas reactor, the mixed powdery ammonium salt reacts with sulfur in the flue gas to generate ammonium bisulfate or ammonium bisulfite, and simultaneously reacts with nitrate in the flue gas to generate nitrogen or nitrate solid.
Description
Technical Field
The invention relates to a method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt, namely a dry method technique for simultaneously desulfurizing and denitrating flue gas by using reactants in a reactor.
Background
The flue gas simultaneous desulfurization and denitrification technology comprises the following steps: with the stricter NOx emission control standard, the desulfurization and denitrification integrated technology is increasingly receiving attention. Although the independent flue gas FGD and SCR desulfurization and denitrification technologies can achieve respective ideal removal rates, when the flue gas passes through the SCR reactor, 0.02-2% of SO2 in the flue gas is oxidized into SO3 and reacts with free CaO and ammonia to generate CaSO 34And ammonium salts, which tend to cause fouling of the catalyst surface, thereby reducing the SCR denitration rate, while increasing the potential for plugging and corrosion in gas/gas heat exchangers (GGH). Thus, flue gas desulfurization and denitrationThe integrated process technology is gradually becoming a hot point of research and a trend of application. The integrated technology for flue gas desulfurization and denitration is still in research and industrial demonstration stages at present, can realize desulfurization and denitration simultaneously in the same set of system, and has the advantages of simple equipment, small occupied area, low capital investment, convenient operation and management, low production cost and the like.
The research progress of the flue gas desulfurization and denitration integrated technology of the coal-fired power plant is mainly introduced below, and the application prospect of the flue gas desulfurization and denitration integrated technology in China is analyzed and predicted.
Firstly, an Activated Carbon (AC) method: the activated carbon method is characterized in that the desulfurization and the denitrification are carried out simultaneously, and chloride, fluoride and heavy metal in the flue gas can be removed. Therefore, although the number of denitration systems using the activated carbon denitration process is not large, the activated carbon denitration process is attracting attention. The working principle is as follows: reacting NH3The NOx is reduced to generate N by the catalytic action of the activated carbon through the activated carbon filler layer together with the dedusted flue gas2And H2O，SO2Then the sulfuric acid is absorbed by the activated carbon, and further chemical raw materials such as sulfuric acid are generated for recycling.
Second, copper oxide CuO method: CuO is used as an active component to simultaneously remove SO in flue gas2The technique of/NOx, in which CuO/Al is used, has been studied more intensively2O3And CuO/SiO2Mainly comprises the following steps. The CuO content is 4-6%, and is in the temperature range of 300-400 ℃ with the SO in the flue gas2Reaction to form CuSO4Reduction of NO by SCR processXHas high catalytic activity. Absorb saturated CuSO4By CH in general4The gas is reduced to release SO2Can be used for preparing acid and reducing to obtain metallic copper or Cu2S is oxidized by flue gas or air, and the generated CuO is reused in the absorption process. The copper absorption reduction process is proposed by Shell company in the 60 th 20 th century, but after more than 30 years of research, no industrialization report is available so far, and the main reasons are that: in the continuous absorption, reduction and oxidation processes, the physical and chemical properties of CuO gradually decrease, and the CuO loses its effect after multiple cycles.
Thirdly, SNOx process: work of SNOx technologyThe principle is that NOx is removed by an ammonia reduction method, SO2 is oxidized into SO3 by an oxidation method, and then sulfuric acid is prepared. Exhaust gas enters NOXCatalytic reactor, in the presence of ammonia, NOXIs catalytically reduced to nitrogen and water. In the 2 nd stage catalytic reactor, SO2Is oxidized to generate SO3A gas. Because the desulfurization reactor is located the rear portion of denitration reactor, consequently, the trace ammonia that leaks from denitration reactor can obtain make full use of in the desulfurization section, guarantees that the residual ammonia volume is very little in the flue gas after the purification.
Fourthly, NOXSO process: the NOXSO technology is developed by cooperation of Pittsburgh energy center (PETC) of the U.S. department of energy and NOXSO company, and is a dry absorption technology capable of removing SO in flue gas simultaneously2And NOX. The flue gas enters an absorbent fluidized bed, SO2And NOXAdsorbed therein with a high specific surface area and containing Na2CO3On an aluminum absorbent; after the absorbent reaches a certain absorption saturation degree, the absorbent is moved into a regenerator for heating regeneration, and the absorbed NO is regeneratedXReleasing; rich in NOXThe hot air is returned to the combustion chamber of the boiler for recycling the flue gas. Adsorbed SO2React with methane at high temperature to generate high-concentration SO2And H2S gas, the absorbent of the process is Al impregnated with sodium carbonate2O3Round ball (1.6mm), the treatment process includes the steps of absorption, regeneration, etc.
Fifthly, a DESONOX/REDOX process: NOXRemoving CO and hydrocarbon substances by ammonia catalytic reduction method, and oxidizing CO and hydrocarbon substances into CO2And water, SO2Conversion to SO3Then sulfuric acid is prepared. In which NO is removed by ammonia selective catalytic reductionXVarious catalysts can be used, e.g. V2O5/TiO2、Fe2O3Zeolites, and the like. DESONOX requires a reaction temperature of 400-460 deg.C, REDOX requires a reaction temperature of 320-500 deg.C. The CO and hydrocarbon removing process can use noble metal or non-noble metal as catalyst. SO (SO)2The oxidation catalyst is developed by Degussa company, is particularly suitable for treating dust-containing flue gas, has better activity on low-concentration SO2, and has the optimal operation temperature of 400-450 ℃.
Sixthly, SNRB (SOx-NOx-ROx-BOx) process: the SNRB method is performed by the U.S. Barbock-Wilcoxs (B)&W) company, and the process uses a high-temperature bag-type dust remover and can simultaneously remove sulfur, nitrogen and dust. Spraying calcium base or sodium base into flue gas for desulfurization, and spraying ammonia and high-temperature catalyst into a high-temperature ceramic fiber bag for denitration. The method is characterized in that: the high-temperature bag-type dust collector is utilized to achieve the purposes of simultaneously desulfurizing, denitrating and dedusting. SO in flue gas2Calcium base or sodium base is sprayed in the flue in front of the bag-type dust remover, and the calcium base or sodium base is removed by using a filter layer on the outer surface of the cloth.
Seventhly, Lurgi CFB method: lurgi GmbH developed the use of a Circulating Fluidized Bed (CFB) for SO removal2Process for NOx. In the integrated process, the CFB reactor is operated at 385 ℃, slaked lime is used as an absorbent for desulfurization, and the absorbed product is mainly CaSO4(anhydrous) and about 10% CaSO3. The denitration reaction uses ammonia as a reducing agent to carry out selective catalytic reduction reaction, and the catalyst is an active fine powder compound FeSO47H2O。
Eighthly, a urea method: the process for purifying the flue gas by the urea is jointly developed by units such as the Russian Mendeleev chemical process academy and the like, and can simultaneously remove SO2And NOx, SO2The removal rate of the catalyst is close to 100 percent, and the removal rate of NOx is more than 95 percent. The pH value of the absorption liquid adopted by the process is 5-9, no corrosion effect exists, and SO is generated2NOx removal rate and NOx and SO in flue gas2The concentration of the tail gas is irrelevant, the tail gas can be directly discharged, and the absorption liquid can be treated to recover ammonium sulfate.
Ninthly, a hearth limestone/urea spraying process: the lime (stone)/urea spraying, desulfurizing and denitrating integrated process for furnace cavity is characterized by that the calcium spraying and selective non-catalytic reduction (SNCR) of furnace cavity are combined together, at the same time the SO in the flue gas can be removed2/NOx。
Application prospect analysis
1. And (3) utilization of sulfur and nitrate resources: sulfur resource comprehensive utilization type desulfurization process, such as SNOx and NOxSO technology, because the desulfurization by-product is sulfur element, such as sulfur, concentrated sulfuric acid and liquid SO2Has high market value, stable demand and wide application, and is used in the southwest of ChinaThe high-sulfur coal power plant and the power plants near the city with insufficient market demand of the desulfurized gypsum and limited stacking of desulfurized byproducts have better application prospect.
2. In the aspect of the transformation of the existing unit: the existing unit, especially the unit with middle and low parameters in the 'two control areas', has short residual service life, less annual operation time, limited equipment modification site, and low requirement (not more than 50%) for desulfurization rate, and the pipeline calcium spraying technology is a simple and easy environmental protection measure, can achieve the purpose of desulfurization and denitrification at the same time, and is expected to have better development prospect in China.
3. The occupied area of the facility is as follows: the SOx-NOx-ROx-BOx simultaneous desulfurization, denitrification and dust removal technology has the advantages of better comprehensive economic benefits than the technologies of desulfurization, denitrification and dust removal, simpler system and less occupied area, and has quite high competitiveness once a substantial breakthrough is made in engineering technology.
4. Economic aspects of the absorbent: the cost of the absorbent and the replacement cost are considerable proportions of the operating cost, and therefore, the price, recyclability, adsorption performance, catalytic performance, whether poisoning or deactivation occurs, and the like, of the absorbent should be fully considered. The activated carbon method and the NOxSO method have a great advantage in terms of the economical efficiency of use of the adsorbent.
Disclosure of Invention
1. A method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt is characterized by comprising the following steps:
(1) preparing solid ammonium salt into powder with the granularity of 50-1000 meshes;
(2) mixing powdery ammonium salt with flue gas in a flue or a reactor;
(3) the powdery ammonium salt and sulfur and nitrate in the flue gas undergo a desulfurization and denitrification chemical reaction to reduce the content of the sulfur and the nitrate in the flue gas;
(4) after the reaction is finished, the solid ammonium salt for desulfurization and denitrification is treated, partially or completely recycled, and is continuously used for desulfurization and denitrification reaction;
2. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the solid ammonium salt in the step (1) refers to a single component or a mixture of the two, the main component of which is ammonium sulfate or ammonium sulfite;
3. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the temperature of the flue gas in the step (2) is 80-240 ℃;
4. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the reactor in the step (2) is a closed reaction vessel;
5. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the powdery ammonium salt in the step (3) chemically reacts with sulfur in the flue gas to generate solid ammonia bisulfite or ammonium bisulfate;
6. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the powdery ammonium salt in the step (3) and the nitrate in the flue gas are subjected to chemical reaction to generate nitrogen or nitrate solid;
on the basis of the technical scheme, the invention can be further improved as follows:
further, a gas deflector can be added into the flue in the step (2) to enhance the mixing effect of the flue gas and the ammonium salt powder;
further, a gas necking and expanding structure can be added into the flue in the step (2) to enhance the mixing effect of the flue gas and the ammonium salt powder;
further, in the step (3), the solid ammonium salt can adsorb and remove part of heavy metal compounds in the flue gas besides desulfurization and denitrification;
further, in the step (3), the solid ammonium salt can also perform chemical reaction with other sulfides and nitrogen oxides in the flue gas besides desulfurization and denitrification;
further, sulfur and nitrate in the flue gas in the step (3), wherein the sulfur mainly refers to sulfur dioxide and sulfur trioxide, and the nitrate mainly refers to nitric oxide and nitrogen dioxide;
the invention has the beneficial effects that: the invention can realize desulfurization and denitration in the same system, has the advantages of simple equipment, small floor area, low capital investment, convenient operation and management, low production cost and the like, does not consume water or pollute water, and particularly can greatly reduce the current industrial flue gas desulfurization and denitration cost because the ammonium salt used in the invention is ammonium sulfate or ammonium sulfite with lower price.
Drawings
FIG. 1 is a schematic flow chart of a system for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt and using a flue mixer without flue gas temperature regulation. In fig. 1: 101 flue gas, 102 solid ammonium salt, 103 dust remover, 104 centrifugal fan, 105 flue mixer, 106 crushing equipment, 107 venturi jet conveyor, 108 cloth bag dust remover, 109 powder conveyor, 110 solid ammonium salt regeneration equipment, 111 chimney, 112 ammonia gas and 113 solid waste.
FIG. 2 is a schematic flow chart of a system for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt and using a gas-solid reactor to regulate the temperature of the flue gas. In fig. 2: 201 solid ammonium salt, 202 flue gas, 203 air, 204 crushing equipment, 205 powder conveyor 1, 206 dust remover, 207 air heat exchanger, 208 centrifugal fan, 209 gas-solid reactor, 210 bag dust remover, 211 powder conveyor 2, 212 solid ammonium salt regeneration equipment, 213 chimney, 214 ammonia gas and 215 solid waste.
FIG. 3 is a flue gas-solid mixing structure, and the flue gas and solid ammonium salt mixing effect is enhanced by reducing the diameter of the flue and expanding the diameter of the flue and then reducing the diameter of the flue. In fig. 3: 301 flue gas inlet, 302 flue, 303 solid ammonium salt inlet, 304 solid ammonium salt outlet, 305 flue reducing diameter 1, 306 flue expanding diameter, 307 flue reducing diameter 2, 308 flue gas outlet.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
FIG. 1 is a schematic flow chart of a system for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt and without flue gas temperature regulation by using a flue mixer according to the present invention; as shown in fig. 1, the method comprises the steps of:
step 1: ammonium sulfate and ammonium sulfite are mixed according to the mass ratio of 1: 1 and then ground into fine powder.
The mixing ratio shown in the figure I refers to the mass ratio (1: 1) of ammonium sulfate and ammonium sulfite, the mixed ammonium salt is sent to a crushing device 106 and is ground to 50 meshes to 1000 meshes so as to increase the specific surface area of the ammonium salt contacted with the flue gas; the fluidization effect of the solid ammonium salt with the granularity of more than 50 meshes is poor, and the manufacturing cost is high when the granularity of more than 1000 meshes.
Step 2: the finely ground solid ammonium salt 102 is fed into a flue mixer 105 through a venturi jet conveyor 107 to be mixed with the flue gas 101 containing sulfur and nitrate.
The flue gas 101 is flue gas containing sulfur and nitrate and having a temperature of 80-240 ℃, and if the temperature is lower than 80 ℃, water vapor in the flue gas is easy to condense and separate out, so that the solid ammonium salt 102 is dissolved and becomes viscous and adheres to the flue mixer 105, and the reactivity of the solid ammonium salt, particularly the denitrification reactivity, is reduced. If the flue gas temperature is higher than 240 ℃, the solid ammonium salt will melt rapidly and adhere to the flue or flue mixer 105 causing equipment failure. Therefore, if the flue gas temperature is not satisfactory, the flue gas temperature can be adjusted by mixing the air 203 and the air heat exchanger 207, and water can be sprayed in an emergency to ensure that the flue gas reaches the required temperature, so that the powdery ammonium salt is ensured not to be softened or melt and adhere to the pipeline. It is particularly emphasized that the method can be used for treating flue gas with other temperatures, but the temperature of the flue gas is adjusted to 80-240 ℃ by heat exchange before the reaction.
And step 3: the powdery ammonium salt 102 and the flue gas 101 are subjected to desulfurization and denitrification chemical reaction in the flue mixer 105 or the gas-solid reactor 209, so that sulfur and nitrate are removed from the flue gas, and the requirements of national flue gas emission standards on the concentration of sulfur and nitrate are met.
The main chemical equation of the desulfurization and denitrification chemical reaction of the powdery ammonium salt and the flue gas is as follows:
and (3) desulfurization reaction: (NH)4)2SO3+H2O+SO2＝2NH4HSO3
(NH4)2SO3+H2O+SO3＝NH4HSO3+NH4HSO4
(NH4)2SO4+H2O+SO2＝NH4HSO3+NH4HSO4
(NH4)2SO3+H2O+SO3＝2NH4HSO4
The main denitration reaction:
the ammonium sulfite reacts with the nitrate as follows
2NO+2(NH4)2SO3＝2(NH4)2SO4+N2
2NO2+4(NH4)2SO3＝4(NH4)2SO4+N2
Experiments show that the following reaction can occur between solid ammonium sulfate and nitre at the temperature of more than 80 ℃ under the condition of no liquid water
6NO2+8(NH4)2SO4＝8(NH4)HSO4+12H2O+7N2
6NO+4(NH4)2SO4＝4(NH4)HSO4+6H2O+5N2
The nitrogen monoxide, the nitrogen dioxide and the ammonium sulfate can also carry out heterogeneous reaction;
and 4, step 4: after the reaction, the solid ammonium salt for desulfurization and denitrification is treated by the solid ammonium salt regeneration equipment 110, and part or all of the solid ammonium salt is recycled and continuously used for desulfurization and denitrification reaction;
the chemical equation for solid ammonium salt treatment regeneration is as follows:
NH4HSO3+NH3＝(NH4)2SO3
NH4HSO4+NH3＝(NH4)2SO4
the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to the present invention is further described in detail by two examples.
Example 1-as in FIG. 1
The system is a simultaneous desulfurization and denitrification system using a flue mixer without flue gas temperature regulation, and is suitable for the flue gas temperature of 80-240 ℃ and the sulfur content of less than 500mg/M3The flue gas treatment.
Mixing solid ammonium salt 102 containing ammonium sulfate and ammonium sulfite with the mass ratio of 1: 1, grinding the mixture to 200 meshes by a grinding device 106, conveying the mixture into a flue mixer 105 by a Venturi injection conveyor 107, wherein a centrifugal fan 104 compresses part of flue gas 101 to provide power for the Venturi injection conveyor 107, simultaneously the pressurized flue gas 101 enters the flue mixer 105 after most of dust is removed by a dust remover 103, and the flue gas 101 and the powdery ammonium salt 102 have desulfurization and denitrification reactions, so that the content of sulfur and nitrate in the flue gas 101 is lower than the national flue gas emission standard. Then, the flue gas 101 enters a bag-type dust collector 108, the flue gas 101 is separated from the powdery ammonium salt 102 in the bag-type dust collector 108, the purified flue gas 101 is discharged into the atmosphere through a chimney 111, the reacted solid ammonium salt 102 separated by the bag-type dust collector 108 enters a solid ammonium salt regeneration device 110, the reacted ammonium salt is reduced to ammonium sulfate or ammonium sulfite, the part of the solid ammonium salt 102 returns to the crushing device 106 for recycling, and the ammonium salt which cannot be regenerated by the solid ammonium salt regeneration device 110 is discharged out of the system as solid waste.
Example 2-as in FIG. 2
The system is a desulfurization and denitrification system with a gas-solid reactor and flue gas temperature regulation, and is suitable for the flue gas with the sulfur content of more than 500mg/M3The flue gas treatment.
Mixing solid ammonium salt 201 containing ammonium sulfate and ammonium sulfite with the mass ratio of 1: 1, grinding the mixture to 200 meshes by a grinding device 204, conveying the mixture into a gas-solid reactor 209 by a powder conveyor 205, removing most dust from pressurized flue gas 202 by a dust remover 206, then feeding the flue gas into an air heat exchanger 207 to adjust the temperature to 160 ℃, if the temperature fluctuation of the flue gas 202 is large, directly mixing part of air 203 pressurized by a centrifugal fan 208, rapidly reducing the temperature of the flue gas 202, feeding the temperature-adjusted flue gas 202 into the gas-solid reactor 209 to perform desulfurization and denitrification reaction with the powder ammonium salt 201, and enabling the content of sulfur and nitrate in the flue gas 202 to be lower than the national flue gas emission standard. Then, the flue gas 202 enters a bag-type dust collector 210, the flue gas 202 is separated from the powdery ammonium salt 201 in the bag-type dust collector 210, the purified flue gas 202 is discharged into the atmosphere through a chimney 213, the reacted solid ammonium salt 201 separated by the bag-type dust collector 210 enters a solid ammonium salt regeneration device 212, the reacted solid ammonium salt 201 is reduced into ammonium sulfate or ammonium sulfite, the part of the solid ammonium salt 201 returns to a crushing device 204 for recycling, and the ammonium salt which cannot be regenerated by the solid ammonium salt regeneration device 212 is discharged out of the system as solid waste.
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 (6)
1. A method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt is characterized by comprising the following steps:
(1) preparing solid ammonium salt into powder with the granularity of 50-1000 meshes;
(2) mixing powdery ammonium salt with flue gas in a flue or a reactor;
(3) the powdery ammonium salt and sulfur and nitrate in the flue gas undergo a desulfurization and denitrification chemical reaction to reduce the content of the sulfur and the nitrate in the flue gas;
(4) after the reaction is finished, the solid ammonium salt for desulfurization and denitrification is treated, partially or completely recycled, and is continuously used for desulfurization and denitrification reaction;
2. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the solid ammonium salt in the step (1) refers to a single component or a mixture of the two, the main component of which is ammonium sulfate or ammonium sulfite;
3. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the temperature of the flue gas in the step (2) is 80-240 ℃;
4. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the reactor in the step (2) is a closed reaction vessel;
5. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the powdery ammonium salt in the step (3) chemically reacts with sulfur in the flue gas to generate solid ammonia bisulfite or ammonium bisulfate;
6. the method for simultaneously desulfurizing and denitrating flue gas by using solid ammonium salt according to claim 1, wherein the powdery ammonium salt in the step (3) chemically reacts with the nitrate in the flue gas to generate nitrogen or nitrate solid.
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