CN113797733A - Method and device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas - Google Patents
Method and device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas Download PDFInfo
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- CN113797733A CN113797733A CN202111076364.4A CN202111076364A CN113797733A CN 113797733 A CN113797733 A CN 113797733A CN 202111076364 A CN202111076364 A CN 202111076364A CN 113797733 A CN113797733 A CN 113797733A
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003546 flue gas Substances 0.000 title claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000010521 absorption reaction Methods 0.000 claims abstract description 43
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 30
- 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 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 34
- 239000012528 membrane Substances 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000003011 anion exchange membrane Substances 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 19
- 230000023556 desulfurization Effects 0.000 abstract description 19
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 239000007800 oxidant agent Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- -1 sulfate radicals Chemical class 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 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 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 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
- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
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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
- B01D53/77—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
- B01D53/60—Simultaneously removing sulfur oxides and 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
- B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
-
- 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
A method and a device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas are provided, the method takes ammonium sulfate as a flue gas absorption medium to react in an electrolytic reactor to prepare ammonium persulfate solution, the ammonium persulfate solution entering a spray system of an absorption tower is activated by high-temperature flue gas to be used for oxidizing and absorbing sulfur dioxide and nitrogen oxide in the flue gas, and the ammonium sulfate reduced by reaction can be extracted again to enter the electrolytic reactor, so that the purposes of circulation of an oxidant and efficient removal of the sulfur dioxide and the nitrogen oxide in the solution are realized. The device is simple, the occupied area is small, the condition is mild, and the operation cost is low; the method does not produce secondary pollution in desulfurization and denitrification, is environment-friendly and has wide pH adaptability; n, S element in the flue gas achieves the recycling of resources and has great industrial application potential.
Description
Technical Field
The invention belongs to the field of flue gas purification, and particularly relates to a method and a device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas.
Background
Very high concentrations of NOx and SO are produced during the combustion of fossil fuels2Is the main pollutant of air and causes a series of serious environmental problems, such as photochemical smog, eutrophication and ozone depletion. Therefore, the control of the emission of sulfur dioxide and nitrogen oxides generated after combustion into the atmosphere is of great significance. The prior desulfurization methods comprise wet ammonia desulfurization, dry desulfurization, semi-dry desulfurization and flue gas circulating fluidized bed desulfurization; as for the denitration method, selective catalytic reduction and selective non-catalytic reduction, the most applied flue gas desulfurization and denitration technologies mainly comprise limestone/lime-gypsum flue gas desulfurization and ammonia selective catalytic reduction technologies which can respectively remove dioxide and nitrogen oxide, and because the main component of NOx is NO (about 90%), the NO solubility is low, unlike SO2Thus, the removal is easy, and therefore, the simultaneous desulfurization and denitrification cannot be realized. At present, persulfate is used as an oxidizing agent to activate generated sulfate radicals (SO 4 ∙)-) A novel advanced oxidation technology capable of realizing synchronous and efficient desulfurization and denitrification with hydroxyl free radical (. OH) is gradually attracting attention of researchers, persulfate is ionized in water to generate persulfate ions S2O8 2-The molecule of the oxidant contains peroxy O-O, and the oxidant is a strong oxidizing oxidant. But because the persulfate is relatively stable, the reaction rate is relatively slow at normal temperature, and the removal effect on nitrogen oxides and sulfur oxides is not obvious. In the presence of light, heat, ultrasonic waves, hydrogen peroxide, transition metal ions (Fe)2+Etc.) under the same conditions, S2O8 2-Can be activated and decomposed into SO4∙-. Therefore, the persulfate technology activated by the waste heat of the high-temperature flue gas is adopted, and the activated free radicals and a feasible method for synchronous desulfurization and denitrification are adopted. CN103691279A discloses 'a system and a method for desulfurizing and denitrating sodium persulfate by using flue gas waste heat through high-temperature activation', the method mainly uses flue gasThe waste heat activates persulfate in a high-temperature activation reactor, so that active free radicals are generated to remove sulfur dioxide and nitrogen oxide in the flue gas. However, the method cannot regenerate the absorbent, and the generated active free radicals have instantaneity. CN204058604U discloses a device for preparing ammonium persulfate from ammonia and urea solution flue gas purification absorption liquid, which is characterized in that the method comprises the steps of crystallizing and purifying ammonium sulfate and ammonium bisulfite which are byproducts of ammonia/urea solution, preparing ammonium persulfate through desulfurization and denitrification absorption in an electrolytic reactor, and introducing SO in flue gas2And NOXAnd (4) removing. The method does not activate ammonium persulfate to generate active free radicals with stronger oxidizing property, and does not convert nitrate to cause pollution of nitrate in water. CN105381699A discloses a method and a device for desulfurization and denitration by combining hydrogen peroxide oxidation and an amino wet method. The active free radical generated by the method is single, the hydroxyl free radical is stable without sulfate radical, and the regeneration of the absorbent can not be achieved. CN103691278386A discloses a system and a method for strengthening ammonium persulfate of ammonium persulfate based on acousto-optic coupling, in the method, flue gas in a boiler is dedusted and then enters a temperature regulator, the flue gas is subjected to temperature regulation and then enters an acousto-optic coupling reactor, and an ammonium persulfate solution releases sulfate radical (SO) free radicals under the action of ultrasonic waves and ultraviolet light4∙-) And simultaneously, the sulfur dioxide and the nitrogen oxide in the flue gas are oxidized and removed. The method does not regenerate the oxidant of the absorption liquid, and does not consider that nitrate radical and nitrite radical in water are converted into raw materials of the electrolyte. CN110585909A discloses a method for purifying flue gas by desulfurization and denitrification simultaneously, which comprises the steps of spraying flue gas at 50-90 ℃ with ammonia absorption liquid, aerating and oxidizing the obtained solution to obtain ammonium sulfate solution; and heating the obtained flue gas for heat exchange, and then adding a catalyst to convert the nitrogen oxides into nitrogen. The method has complex process and causes catalyst poisoning.
Disclosure of Invention
The invention provides a method and a device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas, aiming at realizing the purpose of strengthening removal of sulfur dioxide and nitrogen oxide in the flue gas.
The technical scheme adopted by the invention is as follows:
a method for circularly purifying sulfur dioxide and nitrogen oxide in flue gas by using amino absorption liquid comprises the following steps: firstly, reaction absorption liquid enters a cathode chamber of an electrolytic reactor to convert nitrate radical and nitrite radical into NH4 +Then enters the anode chamber of the electrolytic reactor to convert sulfate radicals into S at the anode2O8 2-The solution containing ammonium persulfate obtained by electrolysis is pumped into the spraying atomization system of the absorption tower by using a circulating pump, and the high-temperature flue gas containing sulfur dioxide and nitrogen oxide is introduced from the bottom of the absorption tower, SO that heat exchange is realized in the process, the ammonium persulfate is activated to generate active free radicals with stronger oxidation, and SO in the flue gas is simultaneously used2And NOXAnd (4) removing by oxidation, wherein the solution after reaction enters a pipeline from the bottom and is circularly pumped into the electrolytic reactor again, so that the circulation of the process is realized. After multiple cycles, the high-concentration ammonium sulfate is further evaporated and crystallized to obtain the ammonium sulfate byproduct.
Preferably, the concentration of ammonium persulfate generated by electrolysis in the electrolysis reactor is 0.005-1 mol/L.
Preferably, the current density of the cathode and the anode of the electrolytic reactor is 0.5-10 mA/cm2And the electrolysis time is 0.5-8 h.
Preferably, the pH of the solution in the cathode chamber and the anode chamber of the electrolytic reactor is 2-5, the concentration of the ammonium sulfate solution in the cathode chamber is 0.5-3 mol/L, the concentration of the ammonium nitrate solution in the anode chamber is 0.0006-3 mol/L, and the concentration of the ammonium persulfate solution in the anode chamber is 0.005-1 mol/L. .
Preferably, the raw material liquid for electrolyzing the ammonium persulfate in the electrolysis reactor contains 1-3 mol/L ammonium sulfate.
Preferably, the current density of the cathode and the anode in the electrolytic reactor is 0.5-10 mA/cm2The electrolysis time is 2-8 h, and the pH value of the anode chamber is 2-5.
Preferably, the reduction reaction is carried out at the cathode of the electrolytic reactor to convert the nitric acid and nitrite ions into NH4 +The anode is oxidized to convert sulfate radical into S2O8 2-And finally, enabling the electrolysis product ammonium persulfate to flow into a spraying atomization system of the absorption tower by using a circulating pump.
A device for circularly purifying sulfur dioxide and nitrogen oxide in flue gas comprises an electrolytic reactor, a circulating pump, an absorption tower and an absorption liquid storage tank; the outlet of the electrolytic reactor is communicated with a spraying and atomizing system of the absorption tower through a pipeline, the flue gas enters from the bottom of the absorption tower, the inlet of the absorption liquid storage tank is communicated with the liquid outlet of the absorption tower, the outlet of the absorption liquid storage tank is connected with the inlet of the electrolytic reactor through a pipeline, and the pipeline is provided with a circulating pump.
Preferably, the flow rate of the circulating pump is 1-30L/min.
Preferably, the liquid inlet of the absorption column is in communication with the anode of the electrolysis cell.
Preferably, the electrolytic reactor comprises a cathode chamber and an anode chamber, wherein the cathode chamber solution is ammonium sulfate and ammonium nitrate, and the anode chamber solution is ammonium persulfate.
Preferably, the spraying and atomizing system is a stainless steel vortex nozzle with the diameter of 2.3-10 cm, and the nozzle is in a fan-shaped form.
Preferably, the anode of the electrolytic reactor is selected from one of pure platinum, titanium-based platinum and graphite electrodes, and the cathode is selected from one of copper-based polypyrrole-plated, titanium-based cobaltosic oxide-plated, titanium-based platinum dioxide-plated, copper-based bismuth-plated and titanium dioxide-plated electrodes.
Preferably, the cathode chamber and the anode chamber of the electrolytic reactor are separated by a diaphragm, and the diaphragm is one of a ceramic membrane, a perfluorosulfonic acid type cation exchange membrane and a quaternary ammonium type anion exchange membrane.
Preferably, the perfluorosulfonic acid type cation exchange membrane is an HDGN membrane, HDCMI membrane, HDNAF membrane or HDJCM membrane.
Preferably, the quaternary ammonium anion exchange membrane is an HDJAM membrane or an HDAMI membrane.
The principle is as follows: after the electrolyzed ammonium persulfate solution is subjected to flue gas desulfurization and denitration, the reaction product is a solution containing ammonium sulfate and ammonium nitrate, and the solution containing ammonium sulfate and ammonium nitrate is subjected to electrolysisAnd electrolyzing in the decomposition reactor to prepare ammonium persulfate solution. Oxidizing SO in flue gas by using ammonium persulfate as oxidant2And NOXNO in the flue gas is converted into a compound which is easier to dissolve and absorb, so that the aim of synchronously desulfurizing and denitrifying the flue gas based on an ammonia method is fulfilled. In addition, considering that the flue gas contains a large amount of high-temperature waste heat, in order to fully utilize the heat energy of the flue gas, the ammonium persulfate can be activated in the process of carrying out gas-liquid mass transfer by spraying in the absorption tower.
During the treatment process of the method, the partial chemical reactions involved are as follows:
the principle for preparing ammonium persulfate by electrolyzing ammonium sulfate and ammonium nitrate is as follows:
the electrolytic process has an ion reaction formula:
cathode:
anode:
persulfate activation reaction formula:
based on the amino absorption liquid NO removal reaction formula:
based on amino-group-absorbing liquids SO2Removing the reaction formula:
based on amino-group-absorbing liquids SO2The removal of NO in the presence of:
the invention has the following beneficial effects:
1) the raw materials of the ammonium persulfate produced by electrolysis in the electrolysis reactor are derived from the desulfurization and denitrification reaction product. In addition, SO in the flue gas is converted into SO by sulfate radicals generated by activating ammonium persulfate2And NOXAfter removal, it is itself reduced to ammonium sulfate, the same as the desulfurization by-product of the invention; meanwhile, nitrate radical and nitrite radical generated in the solution are converted into NH at cathode in the electrolytic bath4 +Conversion of sulphate to S at the anode2O8 2-Therefore, the method does not produce secondary pollution in the desulfurization and denitrification and is environment-friendly.
2) The method has good treatment effect on sulfur dioxide and nitrogen oxide in industrial flue gas, and byproducts of ammonium sulfate and ammonium nitrate can be used as electrolytic raw material liquid and also can be used as chemical fertilizer, so that N, S element in the flue gas is recycled, and economic cycle is realized.
3) The waste heat in the flue gas is fully utilized during persulfate activation, no additional substance or energy is needed for activation, the feasibility is high, the cost is low, and the industrial application potential is large.
Drawings
FIG. 1 is a schematic view of the apparatus and process of the present invention.
In the figure: 1-an electrolytic reactor, 2-a circulating pump, 3-an absorption tower and 4-an absorption liquid storage tank.
Fig. 2 is a schematic diagram of the reactions that mainly occur at the anode and cathode of the membrane electrode.
Detailed Description
The invention is described in more detail below with reference to the figures and the examples, but the scope of the invention is not limited to the description.
Example 1
The flue gas generated by a certain thermal power plant is circularly purified, wherein SO2、NOXRespectively at a concentration of 2635 mg/m3、383 mg/m3And the temperature of the flue gas entering the absorption tower is 85 ℃. The cathode chamber and the anode chamber of the electrolytic reactor take a perfluorinated sulfonic acid cation exchange membrane as a diaphragm to containUsing 1mol/L ammonium sulfate solution as anolyte, maintaining the pH of the anolyte at 2-3, selecting a titanium-based platinum-plated electrode as a cathode, selecting a titanium-based cobaltosic oxide-plated electrode as an anode, and controlling the current density of the cathode and the anode to be 8 mA/cm2The electrolysis time is 3.0 h, and the gas-to-liquid ratio of the flue gas desulfurization and denitrification liquid is 25L/m3The result of the system of the small-sized system for removing sulfur and nitrogen in the purified flue gas is that SO in the flue gas2And NOXAnd the removal efficiency can reach 99.8 percent and 51.6 percent respectively.
Example 2
Circularly purifying the sulfur dioxide and the nitrogen oxide in the flue gas generated by a certain coke-oven plant, wherein SO2、NOXRespectively at a concentration of 800 mg/m3、600 mg/m3And the temperature of the flue gas entering the absorption tower is 70 ℃. The cathode chamber and the anode chamber of the electrolytic reaction chamber use a perfluorinated sulfonic acid cation exchange membrane as a diaphragm, a solution containing 2 mol/L ammonium sulfate as an anolyte, the pH of the anolyte is maintained to be 2-3, a titanium-based platinum-plated electrode is used as a cathode, a titanium-based cobaltosic oxide-plated electrode is used as an anode, and the current densities of the cathode and the anode are both 10 mA/cm2The electrolysis time is 4.0 h, and the gas-liquid ratio of the flue gas denitration liquid is 25L/m3The result of the system of the small-sized system for removing sulfur and nitrogen in the purified flue gas is that SO in the flue gas2And NOXAnd the removal efficiency can reach 98.5 percent and 78.3 percent respectively.
Example 3
Circularly purifying the sulfur dioxide and the nitrogen oxide in the flue gas generated by a certain steel plant, wherein SO2、NOXRespectively at a concentration of 2457 mg/m3、300mg/m3The temperature of the flue gas entering the absorption tower is 85 ℃. The cathode chamber and the anode chamber of the electrolytic reactor use a perfluorinated sulfonic acid cation exchange membrane as a diaphragm, a solution containing 3 mol/L ammonium sulfate as an anolyte, the pH of the anolyte is maintained to be 2-3, a titanium-based platinum-plated electrode is used as a cathode, a titanium-based cobaltosic oxide-plated electrode is used as an anode, and the current densities of the cathode and the anode are both 10 mA/cm2The electrolysis time is 4.0 h, and the gas-liquid ratio of the flue gas denitration liquid is 25L/m3The result of the system of the small-sized system for removing sulfur and nitrogen in the purified flue gas is that SO in the flue gas2And NOXAnd the removal efficiency can reach 98.8 percent and 78.8 percent respectively.
Example 4
A method for circularly purifying sulfur dioxide and nitrogen oxides in flue gas by a circular electrolysis/advanced oxidation-ammonia process comprises the following steps: firstly, inputting high-temperature flue gas containing sulfur dioxide and nitric oxide to the bottom of an absorption tower; the solution containing ammonium persulfate obtained by electrolysis of the electrolysis reactor flows into a spraying and atomizing system of the absorption tower by using a cooling water circulating pump, the sprayed and atomized ammonium persulfate solution can be in gas-liquid contact in the absorption tower, so that indirect heat exchange is realized, and the ammonium persulfate is activated to generate active free radicals with strong oxidation; solution containing active free radicals as flue gas absorption liquid and SO in flue gas2And NOXContact reaction to remove SO in flue gas2And NOXRemoval by oxidation, SO2And NOXIs converted into SO with higher solubility3 2-、SO4 2-、NO2、NO2 -、NO3 -And (3) plasma products are generated, and the absorption liquid simultaneously contains ammonium sulfate and ammonium nitrate solution, and the solution flows into the absorption liquid storage tank to be used as a raw material liquid for electrolyzing the absorption liquid in the electrolytic reactor to produce ammonium persulfate.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. The utility model provides a device of sulfur dioxide and nitrogen oxide in circulation purification flue gas which characterized in that: comprises an electrolytic reactor (1), a circulating pump (2), an absorption tower (3) and an absorption liquid storage tank (4); the outlet of the electrolytic reactor (1) is communicated with a spraying atomization system of the absorption tower (3) through a pipeline, flue gas enters from the bottom of the absorption tower (3), the inlet of the absorption liquid storage tank (4) is communicated with the liquid outlet of the absorption tower (3), the outlet of the absorption liquid storage tank (4) is connected with the inlet of the electrolytic reactor (1) through a pipeline, and a circulating pump (2) is arranged on the pipeline.
2. The apparatus of claim 1, wherein: the electrolytic reactor (1) comprises a cathode chamber and an anode chamber, wherein the solution in the cathode chamber is ammonium sulfate and ammonium nitrate, and the solution in the anode chamber is ammonium persulfate.
3. The apparatus of claim 1, wherein: the flow rate in the circulating pump (2) is 1-30L/min.
4. The apparatus of claim 1, wherein: the spraying and atomizing system is a stainless steel vortex nozzle with the diameter of 2.3-10 cm, and the nozzle is in a fan-shaped form.
5. The apparatus of claim 1, wherein: the anode of the electrolytic reactor (1) is selected from one of pure platinum, titanium-based platinum plating and graphite electrode, and the cathode is selected from one of copper-based polypyrrole plating, titanium-based cobaltosic oxide plating, titanium-based platinum dioxide plating, copper-based bismuth plating and titanium dioxide plating electrode; the cathode chamber and the anode chamber of the electrolytic reactor (1) are separated by a diaphragm, and the diaphragm is one of a ceramic membrane, a perfluorosulfonic acid type cation exchange membrane and a quaternary ammonium type anion exchange membrane; the perfluorinated sulfonic acid type cation exchange membrane is an HDGN membrane, an HDCMI membrane, an HDNAF membrane or an HDJCM membrane; the quaternary ammonium type anion exchange membrane is an HDJAM membrane or an HDAMI membrane.
6. A method for circularly purifying sulfur dioxide and nitrogen oxide in flue gas is characterized by comprising the following steps: firstly, reaction absorption liquid enters a cathode chamber of an electrolytic reactor, nitrate radicals and nitrite radicals are converted into ammonium radicals, then the ammonium radicals enter an anode chamber of the electrolytic reactor, sulfate radicals are converted into sulfate radicals at an anode, the solution containing ammonium persulfate and obtained by electrolysis is pumped into a spraying atomization system of an absorption tower by a circulating pump, meanwhile, high-temperature flue gas containing sulfur dioxide and nitrogen oxide is introduced from the bottom of the absorption tower, heat exchange is realized in the process, the ammonium persulfate is activated to generate active free radicals with strong oxidation, and the active free radicals are activated to be used for generating strong oxidationSO in flue gas2And NOXAnd (4) removing by oxidation, wherein the solution after reaction enters a pipeline from the bottom and is circularly pumped into the electrolytic reactor again, so that the circulation of the process is realized.
7. The method of claim 5, wherein: the concentration of ammonium persulfate generated by electrolysis in the electrolysis reactor is 0.005-1 mol/L.
8. The method of claim 5, wherein: the current density of the cathode and the anode of the electrolytic reactor is 0.5-10 mA/cm2And the electrolysis time is 0.5-8 h.
9. The method of claim 5, wherein: the pH value of the solution in the cathode chamber and the anode chamber of the electrolytic reactor is 2-5, the concentration of the ammonium sulfate solution in the cathode chamber is 0.5-3 mol/L, the concentration of the ammonium nitrate solution in the anode chamber is 0.0006-3 mol/L, and the concentration of the ammonium persulfate solution in the anode chamber is 0.005-1 mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109012086A (en) * | 2018-07-19 | 2018-12-18 | 昆明理工大学 | The device and method of sulfur dioxide and nitrogen oxides in a kind of purifying smoke |
| CN112323097A (en) * | 2020-10-16 | 2021-02-05 | 昆明理工大学 | Method and system for removing sulfur dioxide in flue gas by zinc-ammonia complex coupling persulfate advanced oxidation technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012086A (en) * | 2018-07-19 | 2018-12-18 | 昆明理工大学 | The device and method of sulfur dioxide and nitrogen oxides in a kind of purifying smoke |
| CN112323097A (en) * | 2020-10-16 | 2021-02-05 | 昆明理工大学 | Method and system for removing sulfur dioxide in flue gas by zinc-ammonia complex coupling persulfate advanced oxidation technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931393A (en) * | 2022-07-26 | 2022-08-23 | 益佑科技(深圳)有限责任公司 | Multi-angle regulation type protective equipment for newborn radiation |
| CN114931393B (en) * | 2022-07-26 | 2022-11-15 | 汕头大学医学院第二附属医院 | Multi-angle regulation type protective equipment for newborn radiation |
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