CN115105944A - Hollow fiber membrane bed manganese method SOx/NOx control device - Google Patents
Hollow fiber membrane bed manganese method SOx/NOx control device Download PDFInfo
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- CN115105944A CN115105944A CN202210781458.XA CN202210781458A CN115105944A CN 115105944 A CN115105944 A CN 115105944A CN 202210781458 A CN202210781458 A CN 202210781458A CN 115105944 A CN115105944 A CN 115105944A
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- 239000012528 membrane Substances 0.000 title claims abstract description 77
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 55
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 49
- 239000011572 manganese Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 23
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 56
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003546 flue gas Substances 0.000 claims abstract description 31
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 21
- 230000023556 desulfurization Effects 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000011010 flushing procedure Methods 0.000 claims abstract description 9
- 238000007664 blowing Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 34
- 239000000428 dust Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229940099596 manganese sulfate Drugs 0.000 abstract description 8
- 239000011702 manganese sulphate Substances 0.000 abstract description 8
- 235000007079 manganese sulphate Nutrition 0.000 abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 239000000779 smoke Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 238000010926 purge Methods 0.000 abstract description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 229910052815 sulfur oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000010269 sulphur dioxide Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 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 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000668842 Lepidosaphes gloverii Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
- B01D53/565—Nitrogen oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
Abstract
A manganese desulfurization and denitrification device with a hollow fiber membrane bed consists of a dryer, a cyclone reactor, a hollow fiber membrane bed box body, an extraction or regeneration circulating treatment system and a manganese powder distribution and conveying device. Manganese oxide or manganese ore powder adsorbed on the surface of a hollow fiber membrane wire is used as a reaction bed to absorb sulfur oxide and nitrogen oxide in flue gas to generate manganese sulfate and manganese nitrate, the manganese sulfate and the manganese nitrate are generated, back flushing and forward purging are carried out, after powder cakes are dropped, the manganese oxide is fed into a circulation treatment system for absorbing the sulfur and the nitrogen oxide in the flue gas again through an extraction or regeneration circulation treatment system or a product is extracted or the manganese oxide is reduced. Because the specific surface area of the hollow fiber membrane is large, and manganese powder bridging can be formed between membrane filaments, manganese powder is fluffy and accumulated, the wind resistance is small, the manganese surface area is large, and the manganese powder can be fully contacted with smoke. Through blowback and blowing, old powder cakes are circularly removed in different bins, new manganese powder is replaced, and integrated desulfurization, denitrification and dust removal are realized. Can be used for flue gas treatment, manganese resource extraction and acid recovery.
Description
Technical Field
A hollow fiber membrane bed manganese method desulfurization and denitrification device. In particular to a technical scheme and a realization device for removing pollutants such as sulfur, nitrogen oxides and the like in flue gas by using a hollow fiber membrane as a reaction bed base and forming a fixed bed together with manganese oxide powder or manganese ore powder.
Background
The most common flue gas denitration technology at present is SCR, ammonia is sprayed into flue gas, nitrogen oxides are finally converted into nitrogen and water under the action of a catalyst, and the technology has the defects of high ammonia and catalyst consumption, high working temperature, high energy consumption and easiness in ammonia escape. The most common flue gas desulfurization technique at present is a lime absorption method, in which flue gas is mixed with calcium carbonate to generate calcium sulfate, which is then fixed. The disadvantage of this technique is that too much low value gypsum is produced, causing secondary pollution.
Generally, desulfurization and denitrification are carried out by two process links, and the flow and equipment are complicated. The development of a concise desulfurization and denitrification process is a continuous and striving goal in the industry.
A manganese-method desulfurization and denitrification technology is started to appear in the last 70 th century, and is mainly characterized in that manganese ore slurry or manganese oxide powder is used for filtering flue gas, nitrogen oxides in the flue gas react with manganese oxide to form manganese nitrate, and sulfur oxides in the flue gas react with manganese oxide to form manganese sulfate, so that the desulfurization and denitrification of the flue gas are realized. And then, washing with water and precipitating to dissolve out manganese nitrate and manganese sulfate, and taking out unreacted manganese oxide to return to the flue gas filtration link again. Adding alkaline substances such as ammonia, sodium hydroxide, lime and the like into the dissolved manganese nitrate and manganese sulfate solution to generate manganese hydroxide precipitate, taking out manganese oxide, and putting the manganese oxide into the flue gas absorption link again for recycling. Or ammonium sulfate, ammonium nitrate, sodium sulfate, sodium nitrate, calcium nitrate, gypsum, etc. are recovered.
Theoretically, this is a more perfect process, but has not been the mainstream engineering solution. The reason for this is mainly the lack of a suitable reaction bed, and the flue gas and manganese do not react sufficiently. For example, the process of treating flue gas by pyrolusite slurry can achieve two purposes, the flue gas is treated, manganese and acid are extracted, but reaction interfaces used in the current experimental engineering are a spray tower, a bubble tower, a turbulent ball tower and the like, manganese ore powder is insoluble in water, the spray tower is obviously not suitable, the specific gravity of the manganese ore slurry is very large, the bubble pressure is as high as 4-6 KP, the power consumption is huge, a mass transfer interface is very small, and a pipeline is easily blocked by mineral powder brought out by bubbles; the scheme of desulfurization and denitrification by adopting powdery manganese oxide mostly adopts a cyclone mixing reaction structure, and most gas molecules have no chance of directly or closely contacting powder particles due to the fact that the solid-gas ratio is very large, so that the treatment efficiency is very limited.
CN 106861410 a discloses "a flue gas deep desulfurization and denitration dry-type integrated method using manganese hydroxide as a circulating working medium", although the authors consider that a cyclone device is the main reaction interface, the inventors consider that the patent proposal actually proposes a bag-type dust collector as a reaction bed, and should be a beneficial suggestion. Although this is only one of the inventors' guesses, further improvements could be made based on this.
The CN 2021101203361 patent proposes a solution for treating flue gas with hollow fiber membrane as fixed bed, but it is attached to this fixed bed and is not a catalyst, but it is necessary to directly adsorb sulfur and nitrogen oxides in flue gas with the adsorbent, and make them react to produce manganese sulfate and manganese nitrate, and the catalyst mainly promotes its oxidation to produce carbon dioxide and water.
The technical problems and backgrounds faced by the present inventors are:
firstly, the filtration efficiency and precision of the bag-type dust remover are insufficient 1, the best bag-type dust remover at present can carry out 2-4 mg/m high-speed plantation of dust, and the common bag-type dust remover carries out 10-20 mg/m high-speed plantation. The hollow fiber membrane dust filter can easily achieve the filtering precision of 1ug/m and is improved by three orders of magnitude, and the inventor successfully applies the technology in 40000 m/h lead smoke dust removal engineering practice and passes test identification of southern China, the department of environmental protection (see non-ferrous metals in 2020, 12 months. P31). The improvement of the dust filtration precision means that the leaked pollutants loaded on the dust are greatly reduced, namely the reduction of the highly toxic substances such as dioxin, mercury, fluoride, cadmium and the like. 2. The volume of the hollow fiber membrane dust collector is only one sixth of that of the bag-type dust collector, which means that the volume is the same and the surface area can be six times larger. 3. The thickness of the hollow fiber membrane is 50-100 times of that of the cloth membrane, and the hollow fiber membrane has incomparable wear resistance and service life. 4. The distance between the membrane filaments of the hollow fiber membrane is short, the powdery reactant is easy to form 'bridges' between the membrane filaments to form a fluffy accumulation body, the volume of the reaction bed is greatly increased, and the point is incomparable with a bag-type dust collector. In short, only the hollow fiber dust scrubber is more suitable for manufacturing the powder fixed bed.
Secondly, an outstanding technical obstacle faced by the manganese-method integrated desulfurization and denitrification technology is that when manganese oxide simultaneously encounters two substances, namely nitrogen oxide and sulfur dioxide, the two gases compete for active sites on the surface of the manganese oxide substance, and the sulfur dioxide is more competitive and can react to generate manganese sulfide first. The formation of manganese sulfate hinders the contact of manganese with nitrogen oxides, and thus a problem arises in that the desulfurization effect and the denitration effect are not balanced.
And then, the bag-type dust collector and the hollow fiber membrane dust collector have a back flushing working condition, and the powder cake is not formed in time after back flushing, so that the filtering effect of the empty window period is the worst. The dust filtering efficiency of the outlet is saw-tooth wave-shaped in small scale and reduced in average filtering efficiency in long scale.
Disclosure of Invention
The invention aims to: 1. providing a hollow fiber membrane bed manganese method desulfurization and denitrification device; 2. the problem that the surface active positions of two gas competitive manganese oxide substances are unbalanced is solved; 3. the problem that the filtering effect is reduced in a filtering empty window period due to a back flushing working condition is solved; 4. the hollow fiber membrane bed is combined with a manganese extraction, manganese circulation and acid recovery system, and the processes of smoke treatment, manganese extraction, acid recovery and high-precision dust filtration are completed in one system.
To achieve these objects, the present application proposes the solution as follows:
the device for desulfurization and denitrification by the manganese method through the hollow fiber membrane bed comprises a pulse dryer, a cyclone drying reactor, a hollow fiber membrane bed box body, a fan, a manganese, acid and slag extraction or manganese oxide regeneration circulating treatment system, a manganese oxide or manganese ore powder distribution device and a manganese oxide or manganese ore powder conveying device; the method is characterized in that: the hollow fiber membrane bed box body is internally provided with a hollow fiber membrane filament array; in the membrane silk array, the interval between the surfaces of the membrane silks is less than 25 millimeters and more than 3 millimeters; the negative pressure air in the tube pass of the membrane wires adsorbs a layer of manganese oxide or manganese ore powder on the surfaces of the hollow fiber membrane wires to form powder cakes attached to the outer surfaces of the hollow fiber membrane wires, and the stacking thickness of the powder cakes on the outer surfaces of the membrane wires reaches the thickness of the powder cakes in contact with the powder cakes on the outer surfaces of the adjacent membrane wires to form a bridge between the powder cakes; the membrane filaments, the adsorbed powder cakes and manganese oxide or manganese ore powder participating in powder cake bridging form a hollow fiber membrane bed together.
The pulse dryer and the cyclone drying reactor have two functions, firstly, the heat carried by the flue gas is utilized to dry the powder sent from the manganese oxide or manganese ore powder distribution device and the manganese oxide or manganese ore powder conveying device, and the powder is heated to the temperature above the dew point; the second function is to form a cyclone fluidized bed to make the oxygen, sulfur and nitrogen oxides in the flue gas and the powdery absorbent perform primary reaction. And the powdery absorbent deposited by the cyclone drying reactor is conveyed and distributed again by a manganese oxide or manganese ore powder distribution device and a manganese oxide or manganese ore powder conveying device.
The manganese, acid and slag extraction or manganese oxide regeneration circulating treatment system is specifically arranged according to the specific application of the device. If the device is used, manganese ore powder is treated to obtain manganese sulfate and manganese nitrate; if the device is used, the manganese oxide is used as an intermediate material for recycling, so that the flue gas is treated; besides the treatment of flue gas, byproducts such as ammonium sulfate, ammonium nitrate, sulfuric acid and nitric acid are also expected to be obtained, and specific structures and flow paths can be set for specific requirements. Since these are readily available technologies and are not the focus of this application, they will not be described in detail here.
Furthermore, the hollow fiber membrane bed box body is divided into an upper bin and a lower bin, the upper bin is divided into a plurality of unit bins, each unit bin is communicated with a back-blowing gas tank through a respective angle valve, and each unit bin is communicated with an upper bin collecting pipe through a respective air door;
a flue gas inlet and a manganese oxide or manganese ore powder spraying port are arranged on the wall of the lower chamber of the hollow fiber membrane bed box body;
the lower chamber is provided with a partition plate, the lower chamber is divided into a plurality of compartments which are in one-to-one correspondence with the unit chambers of the upper chamber and are opened at the lower parts, the membrane wire tube pass air outlet is positioned in the unit chamber of the upper chamber, and the membrane wire shell pass is positioned in the compartment of the lower chamber; the compartments are all provided with a purging gas nozzle;
the lower chamber is provided with a clapboard, which aims to prevent the possible interference between chambers when the sub-chambers are blown back and blown forward, and prevent the powder cake on other film yarns which do not enter the back blowing period from being blown down. The lower part of the compartment is open, so that the powdery absorbent entering from the smoke inlet and the powder spraying port of the manganese oxide or manganese ore powder can reach the membrane filaments.
Furthermore, the hollow fiber membrane bed box body has two or more stages.
In order to solve the contention of sulfur and nitrogen for the surface active position of manganese oxide, the hollow fiber membrane bed box body is divided into two-stage or multi-stage design, in the first stage, sulfur oxides with stronger contention are firstly reacted, then the sulfur concentration is greatly reduced, and a room is left for the participation of nitrogen oxides and other smoke components in the subsequent hollow fiber membrane bed box body.
Furthermore, in the first-stage hollow fiber membrane fixed bed box body and the second-stage hollow fiber membrane bed box body, the time for removing the old pressed powder through back flushing and blowing does not occur simultaneously.
In order to solve the problem that the back flushing time in the two-stage hollow fiber membrane bed box body is staggered due to the filtering blank window period of back flushing, the filtering of the whole system is continuous all the time, the filtering blank window cannot occur, the sawtooth wave shape change of the filtering efficiency cannot occur, and the stable and extremely high filtering efficiency is maintained.
Drawings
FIG. 1 is a schematic diagram of an example of a hollow fiber membrane bed manganese desulfurization and denitrification device. In the figure, (1) a flue gas inlet; (2) spraying powder ports of manganese oxide or manganese ore powder; (3) a pulsed air flow dryer; (4) cyclone drying the reactor; (5) a cyclone dryer; (6) a first stage hollow fiber membrane bed box; (7) a second stage hollow fiber membrane bed box; (8) a reactant exhaust port; (9) a manganese, acid and slag extraction or manganese oxide regeneration circulating treatment system; (10) a manganese oxide or manganese ore powder outlet; (11) a manganese oxide or manganese ore powder distribution device; (12) and a manganese oxide or manganese ore powder conveying device.
FIG. 2 is a schematic view of an example of the hollow fiber membrane bed box. In the figure, (01) a flue gas inlet; (2) spraying a powder port for manganese oxide or manganese ore powder; (02) membrane silk; (03) a partition plate; (04) purging the air jet; (05) a unit cell; (06) a damper; (07) and an upper chamber manifold.
Since the blowback gas tank and the angle valve system are conventional, they are omitted from fig. 1 and 2 and are not shown.
Detailed Description
According to the scheme of the hollow fiber membrane bed manganese method desulfurization and denitrification device, a small-sized test bed is designed and manufactured. Ethanol production is carried out at test bench import wind rate 10m, 3000mg/m sulphur dioxide is added, and nitrogen monoxide 2000mg/m is mixed to simulate flue gas, temperature 140 ℃. The hollow fiber membrane is adopted, the surface area is 1 square meter, and 450 grams of 45 percent manganese ore powder is adsorbed. And (3) carrying out thin film dry distillation on the obtained product within 30 minutes, wherein the absorption conversion rate of sulfur dioxide is 98%, the absorption conversion rate of nitric oxide is more than 90%, and the concentration of outlet dust is 1 ug/m.
Because the specific surface area of the hollow fiber membrane is large, and manganese powder bridging can be formed between membrane filaments, the manganese powder is fluffy and accumulated, the wind resistance is small, the manganese volume is large, the surface area is large, and the manganese powder can be fully contacted with flue gas. And by back flushing and blowing, old powder cakes are circularly removed in different bins, and new manganese powder is replaced, so that integrated desulfurization, denitrification and dust removal are realized.
Can be used for flue gas treatment, manganese resource extraction and acid recovery.
Claims (4)
1. The device for desulfurization and denitrification by the manganese method through the hollow fiber membrane bed comprises a pulse dryer, a cyclone drying reactor, a hollow fiber membrane bed box body, a fan, a manganese, acid and slag extraction or manganese oxide regeneration circulating treatment system, a manganese oxide or manganese ore powder distribution device and a manganese oxide or manganese ore powder conveying device; the method is characterized in that: the hollow fiber membrane bed box body is internally provided with a hollow fiber membrane filament array; in the membrane silk array, the interval between the surfaces of the membrane silks is less than 25 millimeters and more than 3 millimeters; negative pressure air in the tube pass of the membrane wire adsorbs a layer of manganese oxide or manganese ore powder on the surface of the hollow fiber membrane wire to form a powder cake attached to the outer surface of the hollow fiber membrane wire; the powder cakes on the outer surfaces of the membrane yarns are stacked to the thickness of the powder cakes in contact with the powder cakes on the outer surfaces of the adjacent membrane yarns to form a bridge between the powder cakes; the membrane filaments, the adsorbed powder cakes and manganese oxide or manganese ore powder participating in powder cake bridging form a hollow fiber membrane bed together.
2. The hollow fiber membrane bed manganese method desulfurization and denitrification apparatus according to claim 1, characterized in that: the hollow fiber membrane bed box body is divided into an upper bin and a lower bin, the upper bin is divided into a plurality of unit bins, each unit bin is communicated with a back-blowing gas tank through a respective angle valve, and each unit bin is communicated with a collecting pipe of the upper bin through a respective air door;
the wall of the lower chamber of the hollow fiber membrane bed box body is provided with a flue gas inlet and a manganese oxide or manganese ore powder inlet;
the lower chamber is provided with a partition plate which divides the lower chamber into a plurality of compartments which are in one-to-one correspondence with the unit chambers of the upper chamber and are open at the lower sides, the air outlet end of the membrane filament tube pass is positioned in the unit chambers of the upper chamber, and the membrane filament shell pass is positioned in the compartments of the lower chamber; and the compartment is provided with a blowing air jet.
3. The hollow fiber membrane bed manganese method desulfurization and denitrification apparatus according to claim 1, characterized in that: the hollow fiber membrane bed box body has two or more stages.
4. The hollow fiber membrane bed manganese method desulfurization and denitrification apparatus according to claim 1, characterized in that: and the time for back flushing and blowing and removing old pressed powder in the first-stage hollow fiber membrane fixed bed box body and the second-stage hollow fiber membrane fixed bed box body is different.
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