CN103432878A - Integrated method for wet-process desulfurization, denitrification demercuration and dearsenification of complexing ferroporphyrin smoke based on supergravity - Google Patents
Integrated method for wet-process desulfurization, denitrification demercuration and dearsenification of complexing ferroporphyrin smoke based on supergravity Download PDFInfo
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- CN103432878A CN103432878A CN2013104051652A CN201310405165A CN103432878A CN 103432878 A CN103432878 A CN 103432878A CN 2013104051652 A CN2013104051652 A CN 2013104051652A CN 201310405165 A CN201310405165 A CN 201310405165A CN 103432878 A CN103432878 A CN 103432878A
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- desulfurization
- sulfide
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 134
- 230000023556 desulfurization Effects 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000000536 complexating effect Effects 0.000 title claims abstract description 36
- 239000000779 smoke Substances 0.000 title abstract description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 41
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002250 absorbent Substances 0.000 claims abstract description 35
- 230000002745 absorbent Effects 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005864 Sulphur Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 229910002089 NOx Inorganic materials 0.000 claims abstract description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 claims abstract description 4
- 239000003546 flue gas Substances 0.000 claims description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 40
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 34
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 29
- 229960001484 edetic acid Drugs 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 20
- 239000007792 gaseous phase Substances 0.000 claims description 20
- 238000012856 packing Methods 0.000 claims description 20
- 238000005987 sulfurization reaction Methods 0.000 claims description 20
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 13
- 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 claims description 11
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 11
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 10
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 9
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 abstract 4
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 231100000167 toxic agent Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000003245 coal Substances 0.000 description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 description 9
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- -1 iron filings Chemical compound 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
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- 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
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- Treating Waste Gases (AREA)
Abstract
The invention discloses an integrated method for wet-process desulfurization, denitrification demercuration and dearsenification of complexing ferroporphyrin smoke based on supergravity. The method comprises the following steps of firstly, absorbing SOx by utilizing inorganic sulfide, desulfurating, meanwhile, reacting inorganic sulfide with toxic heavy metals such as mercury and arsenic in the smoke so as to generate an insoluble vulcanized salt; utilizing a complexing ferroporphyrin to absorbing NOx by utilizing complexing ferroporphyrin for denitration; and regenerating ab absorber by utilizing inorganic sulfide as a reducing agent. The method provided by the invention has the advantages that a supergravity machine is adopted as gas-liquid mass transfer strengthening equipment, the method is beneficial to removal of toxicants such as SOx, NOx, mercury and arsenic, the regeneration efficiency of the absorbent is high, an absorption liquid is applied in a circulating manner, a reducing agent inorganic sulfide is oxidized so as to generate sulphur which can be recovered, sulphur is processed into a high quality sulphur product, and the secondary pollution is not generated; the process is simple, the absorption efficiency is high, the dust is thoroughly removed, the desulfurization degree is more than 99%, the denitration rate is more than 96%, and mercury and arsenic in the smoke are fully basically removed.
Description
Technical field
The present invention relates to industrial flue gas cleaning, refer to particularly the integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of a kind of hypergravity complexing.
Background technology
The pollution of acid rain and the harm caused thereof have become one of important environmental problem of paying close attention to various countries, the whole world.The country that coal is main energy sources be take in China, statistics according to investigations, the SO of China more than 90%
2, the NO more than 67%
x, the flue dust more than 70% discharge capacity all come from burning of coal.And the SO that coal combustion produces
2and NO
xthat industrial waste gas pollutes the main source of (acid rain harm).Nitrogen oxide also can form photochemical pollution, produce greenhouse effects, damage the ozone layer, human body is had the harm such as toxic action processed.Nitrogen oxide and oxysulfide also can be converted into PM2.5 and cause haze weather.
The whole world mercury total amount that is discharged in atmosphere in every year has more than 5000 ton, wherein approximately 4000 tons be artificial result, and the mercury emission of coal-fired process accounts for more than 30%.In China's raw coal, the mercury content excursion is at 0.1～5.5mg/Kg, average mercury content 0.22mg/Kg.Because the yearly consumption of China's fire coal is huge, the amount of annual coal fire discharged mercury and pollutant thereof is all very surprising, the current mercury emission of China has surpassed the U.S., and growth rate is very fast, human health and ecological environment have been formed to grave danger, and the discharge capacity of therefore controlling Mercury In Coal Combustion Flue Gas is significant.During coal combustion, the mercury major part enters atmosphere with flue gas, and what enter lime-ash only accounts for fraction, wherein accounts for 23.1%～26.9% in flying dust, accounts for 56.3%～69.7% in flue gas, and the mercury that enters lime-ash only accounts for 2% left and right.Therefore controlling coal-fired mercury pollution key is that the mercury of controlling in flue gas discharges in atmosphere.Stronger oxidant SO in flue gas
2, NO
2, Cl
2deng the simple substance that can obviously affect mercury metal and oxide existence form.Along with the increase of oxidant, also increased the oxide components of mercury, as HgCl
2, HgSO
4deng.
Mercury In Coal Combustion Flue Gas belongs to the trace level pollutant, wherein mainly contains three kinds of forms: gaseous elemental mercury, gaseous oxidation mercury, solid granulates mercury.Wherein gaseous elemental mercury is the main existence form of mercury in flue gas.Mercury in flue gas have the removed material impact of form to mercury.Affect the principal element that there is form in mercury in flue gas coal-fired kind, ignition temperature, smoke components etc. are arranged.Physics, the chemical property of mercury species differ greatly.As soluble in water as gaseous oxidation mercury, and easily by the particle in flue gas, adsorbed, therefore easily by wet desulphurization equipment or cleaner, removed, particle mercury is also easily removed by deduster, contrary atomic state mercury volatility is high, water-soluble low, is difficult to be desulfurized or cleaner is caught, and almost all discharges into the atmosphere, and mean residence time reaches half a year to two year in atmosphere, very easily in atmosphere, the conveying by long distance forms mercury pollution widely.Atomic state mercury is form the most rambunctious, is also the difficult point of coal-fired flue gas mercury removal.
At present, what industrial employing was more is selective catalytic reduction, adopt ammonia or urea to make reducing agent NO is reduced to nitrogen, as patent US Patent4,221,768, Swedish Patent8404840-4, US Patent4,101,238, US Patent4,048,112 disclosed method.But said method need be under higher temperature (350
right) just can carry out, and also the catalyst price is higher, and easily poisoning and deactivation can not be realized desulphurization denitration simultaneously.Japan Patent P1659565j (1976), P181759c (1976), P63100918, A2 (1988) removes NO when proposing
xand SO
2method adopt oxidant that NO is oxidized to NO soluble in water
2, as chloric acid, potassium permanganate, hydrogen peroxide, ozone etc., but liquid phase oxidation is former thereby fail to promote and come due to high in cost of production.The yellow phosphorus method that the Berkeley of California, USA university laboratory proposes (is shown in document Nature, 1990,343 (11): 151-153), can remove the NO in flue gas simultaneously
xand SO
2, but belong to the method for entirely abandoning.This method will consume a large amount of phosphor resources, and its toxicity is large, and operation requirements is higher.
Adopt Fe (II)-EDTA (EDTA means disodium ethylene diamine tetraacetate) to remove NO in waste gas.The reaction equation of Fe (II) EDTA and NO is as follows:
Fe(II)EDTA+NO→Fe(II)EDTA(NO) (1)
In nearly three ten years afterwards, many scholars have carried out comparatively systematic research to this reaction, but have not yet to see the industrialization report, and the greatest problem that affects the wet process complex denitration application is the cycle applications of absorption liquid.
The circulation regeneration method of absorption liquid mainly contains bioanalysis, improves the three major types such as absorbent absorbability and electrolysis, wherein to improve the absorbent absorbability, applies the most extensively.Fe (II) EDTA easily is oxidized to Fe (III) EDTA, and Fe (III) EDTA can not complexing NO, and absorption efficiency is descended rapidly.With the living things catalysis reducing process Fe (II) that regenerates, but this method will obtain large-scale application and also have many problems to need to solve at present just in the exploratory stage in the waste gas pollution control and treatment process.In the application of reducing agent, hydrazine and H
2s reduction Fe (III) EDTA, the assimilation effect of enhancing EDTA Fe, but due to H
2s and hydrazine are all poisonous, are difficult in industrial application.Someone adopts tannic acid, pyrogaelol and gallic acid to be the absorptive capacity that the second additive strengthens Fe (II) EDTA, NO in two hours
xremoval efficiency remain on 60～65% always, effectively improved the reduction effect of poly-phenol mixture.Also someone has reported dithionic acid sodium reduction Fe (III) EDTA, and reduction effect is better.Domestic scholars has been reported reducing/regenerating Fe (III) EDTA such as iron filings, malic acid, vitamin C, but that the key issue of this technology is operating cost is high, and the process route complexity, also need further research.
Summary of the invention
Purpose of the present invention will overcome the existing deficiency of prior art exactly, provides the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of a kind of hypergravity complexing integrated method.
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing of the present invention comprises the following steps:
1) by temperature be 40 ℃～120 ℃ and send into the desulfurization hypergravity machine containing SOx, NOx, mercury, arsenic flue gas, with be 0.1～5.0mol/L sulfide solution counter current contacting in desulfurization hypergravity machine rotor packing layer, desulfurization, demercuration, the dearsenification of the temperature that enters the desulfurization hypergravity machine concentration that is 0 ℃～40 ℃; Described sulfide is selected from vulcanized sodium, NaHS, ammonium sulfide, ammonium hydro sulfide, potassium sulfide or potassium bisulfide;
2) enter the denitration hypergravity machine with the reacted flue gas of sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 0 ℃～55 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, described absorbent contains complexing ferrous iron and sulfide reducing agent, the complexing agent of described complexing ferrous iron is selected from ethylenediamine tetra-acetic acid (EDTA), N-(2-ethoxy) ethylenediamine-N, N', the mixture of one or both in N'-triacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylene triamine pentacetic acid (DTPA) (DTPA), citric acid, described sulfide reducing agent is selected from vulcanized sodium, NaHS, ammonium sulfide, ammonium hydro sulfide, potassium sulfide or potassium bisulfide; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
In the present invention, in described absorbent, total Fe concentration is 0.01mol/L～0.5mol/L, and sulfide is 3:1～5:1 with the mol ratio of total Fe, and described complexing agent is 1.02:1～2:1 with the mol ratio of total Fe, and described total Fe refers to Fe
2+and Fe
3+sum.Described sulfide is preferably ammonium sulfide or ammonium hydro sulfide.
In the present invention, the complexing agent of described complexing ferrous iron is preferably the mixture of EDTA and citric acid, the mixture of HEDTA and citric acid, the mixture of the mixture of EDTA and HEDTA or NTA and DTPA.EDTA is 1:2～1:4 with citric acid mixing optimum weight ratio, and HEDTA is 1:3～1:6 with citric acid mixing optimum weight ratio, and EDTA is 1:1～1:3 with HEDTA mixing optimum weight ratio, and NTA is 1:1～1:3 with DTPA mixing optimum weight ratio.
Beneficial effect of the present invention is: first utilize inorganic sulphide to absorb SOx, in desulfurization simultaneously, the insoluble sulphurizing salt that becomes is given birth in inorganic sulphide and the toxic heavy metal reactions such as mercury in flue gas, arsenic, then utilizes the ferrous NOx of absorption of complexing denitration, and inorganic sulphide is as the reducing agent absorbent regeneration.The present invention adopts hypergravity machine as the gas-liquid mass transfer strengthening device, is conducive to removing of SOx, NOx, mercury, arsenic.
The present invention, in desulfurization, adopts inorganic sulphide to absorb SOx, not only can obtain sulphur, the heavy metals such as mercury, arsenic and lead is converted into to the insoluble sulfur compound simultaneously, and the sulphite of generation and thiosulfate can be for the production of the sulfide as reducing agent.
The present invention, in denitration, adopts cheap inorganic sulphide, Complexing Iron can not only be reduced to the complexing ferrous iron, and the NO of complexed absorption can be reduced to nitrogen, and the regeneration efficiency of absorbent is high, absorption liquid application capable of circulation.The product sulphur of the oxidized generation of reducing agent inorganic sulphide, can reclaim, and is processed as the high-quality sulfur product, can not produce secondary pollution.
Technique of the present invention is simple, and absorption efficiency is high, and desulfurization degree is more than 99%, and the denitration rate, more than 96%, can remove mercury and the arsenic in flue gas substantially fully.
The accompanying drawing explanation
Fig. 1 is the integrated process chart of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing of the present invention.
The specific embodiment
In order to explain better the present invention, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but they do not form restriction to the present invention.
The size of two hypergravity machines of the present invention's test: rotor interior diameter 250mm, rotor overall diameter 600mm, rotor height 100mm.
Embodiment 1
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by temperature after dedusting, be 120
flue gas is with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 600～1000ppmv, and NO concentration is 500～800ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3, oxygen concentration 2%v, flue gas is with by storage tank, through pump, to squeeze into temperature in the desulfurization hypergravity be 20
sodium sulfide solution is counter current contacting in hypergravity machine rotor packing layer, desulfurization, demercuration, dearsenification, and the volume ratio of flue gas and sodium sulfide solution is 100:1, the concentration of sodium sulfide solution is 0.1mol/L;
2) enter the denitration hypergravity machine with the reacted flue gas of sodium sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 20 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of vulcanized sodium, HEDTA complexing ferrous iron, and total Fe concentration is 0.01mol/L, the mol ratio 1.02:1 of HEDTA and total Fe, and vulcanized sodium is 5:1 with the mol ratio of total iron, the volume ratio of flue gas and absorbent is 100:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 5ppmv, and NO concentration is 7ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 2
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be 40
gas is with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 1400～2000ppmv, and NO concentration is 500～800ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3, oxygen concentration 3%v, flue gas is with by storage tank, through pump, to squeeze into temperature in the desulfurization hypergravity be 0
naHS aqueous solution counter current contacting in hypergravity machine rotor packing layer, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and the NaHS aqueous solution is 1000:1, the concentration of the NaHS aqueous solution is 1.0mol/L;
2) with the NaHS reactant aqueous solution after flue gas enter the denitration hypergravity machine from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 0 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of NaHS, EDTA complexing ferrous iron, and total Fe concentration is 0.5mol/L, the mol ratio 1.5:1 of EDTA and total Fe, and NaHS is 4:1 with the mol ratio of total iron, the volume ratio of flue gas and absorbent is 500:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 10ppmv, and NO concentration is 17ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 3
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be 80
gas is with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 1600～2400ppmv, and NO concentration is 500～800ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 5%v, flue gas with squeeze into ammonium sulfide solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 35 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and ammonium sulfide solution is 800:1, and the concentration of ammonium sulfide solution is 2.0mol/L;
2) enter the denitration hypergravity machine with the reacted flue gas of ammonium sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 55 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of ammonium sulfide, NTA complexing ferrous iron, and total Fe concentration is 0.3mol/L, the mol ratio 2:1 of NTA and total Fe, and ammonium sulfide is 3:1 with the mol ratio of total iron, the volume ratio of flue gas and absorbent is 1000:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 12ppmv, and NO concentration is 15ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 4
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be 60
flue gas is with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 600～1000ppmv, and NO concentration is 800～1200ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 6%v, flue gas with squeeze into ammonium hydro sulfide aqueous solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 40 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and the ammonium hydro sulfide aqueous solution is 800:1, and the concentration of the ammonium hydro sulfide aqueous solution is 3.0mol/L;
2) with the ammonium hydro sulfide reactant aqueous solution after flue gas enter the denitration hypergravity machine from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 45 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of ammonium hydro sulfide, DTPA complexing ferrous iron, and total Fe concentration is 0.3mol/L, the mol ratio 1.2:1 of DTPA and total Fe, and ammonium hydro sulfide is 5:1 with the mol ratio of total iron, the volume ratio of flue gas and absorbent is 800:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 6ppmv, and NO concentration is 20ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 5
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be that 75 ℃ of flue gases are with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 2300～3100ppmv, and NO concentration is 800～1200ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 6%v, flue gas with squeeze into potassium sulfide aqueous solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 30 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and potassium sulfide aqueous solution is 1000:1, and the concentration of potassium sulfide aqueous solution is 3.0mol/L;
2) enter the denitration hypergravity machine with the reacted flue gas of potassium sulfide aqueous solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 50 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of potassium sulfide, EDTA+ citric acid complex ferrous iron, total Fe concentration is 0.2mol/L, the mol ratio 1.2:1 of EDTA+ citric acid and total Fe, EDTA is 1:2 with citric acid mixing optimum weight ratio, potassium sulfide is 3:1 with the mol ratio of total iron, and the volume ratio of flue gas and absorbent is 800:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 6ppmv, and NO concentration is 10ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 6
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be that 90 ℃ of flue gases are with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 2300～3100ppmv, and NO concentration is 800～1200ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 7%v, flue gas with squeeze into potassium bisulfide aqueous solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 20 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and the potassium bisulfide aqueous solution is 1000:1, and the concentration of the potassium bisulfide aqueous solution is 5.0mol/L;
2) with the potassium bisulfide reactant aqueous solution after flue gas enter the denitration hypergravity machine from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 50 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of potassium bisulfide, HEDTA+ citric acid complex ferrous iron, total Fe concentration is 0.4mol/L, the mol ratio 1.2:1 of HEDTA+ citric acid and total Fe, HEDTA is 1:6 with citric acid mixing optimum weight ratio, potassium bisulfide is 3:1 with the mol ratio of total iron, and the volume ratio of flue gas and absorbent is 800:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 5ppmv, and NO concentration is 6ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 7
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be that 85 ℃ of flue gases are with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 2300～3100ppmv, and NO concentration is 1000～1500ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 7%v, flue gas with squeeze into sodium sulfide solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 25 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and sodium sulfide solution is 1000:1, and the concentration of sodium sulfide solution is 4.0mol/L;
2) enter the denitration hypergravity machine with the reacted flue gas of sodium sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 40 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of vulcanized sodium, EDTA+HEDTA complexing ferrous iron, total Fe concentration is 0.15mol/L, the mol ratio 1.25:1 of EDTA+HEDTA and total Fe, EDTA is 1:2 with HEDTA mixing optimum weight ratio, vulcanized sodium is 3:1 with the mol ratio of total iron, and the volume ratio of flue gas and absorbent is 800:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 7ppmv, and NO concentration is 8ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Embodiment 8
The integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing as shown in Figure 1, comprises the following steps:
1) by the temperature after dedusting, be that 50 ℃ of flue gases are with 400Nm
3the flow velocity of/h is sent into the desulfurization hypergravity machine, SO in flue gas
2concentration is 2300～3100ppmv, and NO concentration is 800～1200ppmv, arsenic content 6～20 μ g/Nm
3, mercury content 9～17 μ g/Nm
3oxygen concentration 8%v, flue gas with squeeze into potassium bisulfide aqueous solution counter current contacting in hypergravity machine rotor packing layer that in the desulfurization hypergravity, temperature is 35 ℃ by storage tank through pump, desulfurization, demercuration, dearsenification, the volume ratio of flue gas and the potassium bisulfide aqueous solution is 1000:1, and the concentration of the potassium bisulfide aqueous solution is 3.5mol/L;
2) enter the denitration hypergravity machine with the reacted flue gas of sodium sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 40 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, absorbent consists of vulcanized sodium, DTPA+NTA complexing ferrous iron, and total Fe concentration is 0.25mol/L, the mol ratio 1.3:1 of DTPA+NTA and total Fe, NTA is 1:3 with DTPA mixing optimum weight ratio, and vulcanized sodium is 3:1 with the mol ratio of total iron, and the volume ratio of flue gas and absorbent is 800:1; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system; Purified gas adopts infrared spectrometer to detect, SO in purified gas
2concentration is 5ppmv, and NO concentration is 8ppmv, adopts atomic absorption spectrography (AAS) to detect heavy metal, can't detect arsenic, mercury;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
(6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
Claims (3)
1. the integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing, is characterized in that, comprises the following steps:
1) by temperature be 40 ℃～120 ℃ and send into the desulfurization hypergravity machine containing SOx, NOx, mercury, arsenic flue gas, with be 0.1～5.0mol/L sulfide solution counter current contacting in desulfurization hypergravity machine rotor packing layer, desulfurization, demercuration, the dearsenification of the temperature that enters the desulfurization hypergravity machine concentration that is 0 ℃～40 ℃; Described sulfide is selected from vulcanized sodium, NaHS, ammonium sulfide, ammonium hydro sulfide, potassium sulfide or potassium bisulfide;
2) enter the denitration hypergravity machine with the reacted flue gas of sulfide solution from desulfurization hypergravity machine gaseous phase outlet, then with the temperature that enters the denitration hypergravity machine be 0 ℃～55 ℃ absorbent counter current contacting in denitration hypergravity machine rotor packing layer, reaction denitration; Wherein, described absorbent contains complexing ferrous iron and sulfide reducing agent, the complexing agent of described complexing ferrous iron is selected from ethylenediamine tetra-acetic acid, N-(2-ethoxy) ethylenediamine-N, N', the mixture of one or both in N'-triacetic acid, nitrilotriacetic acid, diethylene triamine pentacetic acid (DTPA), citric acid, described sulfide reducing agent is selected from vulcanized sodium, NaHS, ammonium sulfide, ammonium hydro sulfide, potassium sulfide or potassium bisulfide; Reacted purified gas enters demister from denitration hypergravity machine gaseous phase outlet, enters subsequently exhaust system;
3) from the desulfurization hypergravity machine, liquid out enters the desulfurization subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the desulfurization subsider;
4) clear liquid on desulfurization subsider top is extracted out and is sent to the desulfurization hypergravity machine, and with after supplementary sulfide on-line mixing, flowing to together the desulfurization hypergravity machine, Absorption Desulfurization is circulated;
5) from the denitration hypergravity machine, liquid out enters the denitration subsider after compensator, and sulphur wherein, insoluble sulfuration salt settling, to bottom, are reclaimed to solid after filter filters, and filtrate is returned the denitration subsider;
6) clear liquid on denitration subsider top is extracted out and is sent to the denitration hypergravity machine, with after supplementary sulfide reducing agent on-line mixing, flowing to together the denitration hypergravity machine, circulates and absorbs denitration.
2. the integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing according to claim 1, it is characterized in that: in described absorbent, total Fe concentration is 0.01mol/L～0.5mol/L, sulfide is 3:1～5:1 with the mol ratio of total Fe, described complexing agent is 1.02:1～2:1 with the mol ratio of total Fe, and described total Fe refers to Fe
2+and Fe
3+sum.
3. the integrated method of the ferrous smoke-gas wet desulfurization denitration demercuration arsenic of hypergravity complexing according to claim 1, it is characterized in that: the complexing agent of described complexing ferrous iron is selected from the mixture of ethylenediamine tetra-acetic acid and citric acid, N-(2-ethoxy) ethylenediamine-N, N', the mixture of N'-triacetic acid and citric acid, ethylenediamine tetra-acetic acid and N-(2-ethoxy) ethylenediamine-N, N', the mixture of the mixture of N'-triacetic acid or nitrilotriacetic acid and diethylene triamine pentacetic acid (DTPA).
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