CN109806741A - The low-temp desulfurization method of denitration of coke oven flue gas - Google Patents
The low-temp desulfurization method of denitration of coke oven flue gas Download PDFInfo
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- CN109806741A CN109806741A CN201811490524.8A CN201811490524A CN109806741A CN 109806741 A CN109806741 A CN 109806741A CN 201811490524 A CN201811490524 A CN 201811490524A CN 109806741 A CN109806741 A CN 109806741A
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- flue gas
- coke oven
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- 239000003546 flue gas Substances 0.000 title claims abstract description 99
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000571 coke Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 29
- 230000023556 desulfurization Effects 0.000 title claims abstract description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000007789 gas Substances 0.000 claims abstract description 58
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 33
- 230000008929 regeneration Effects 0.000 claims abstract description 21
- 238000011069 regeneration method Methods 0.000 claims abstract description 21
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims description 73
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- 239000003463 adsorbent Substances 0.000 claims description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002808 molecular sieve Substances 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 32
- 239000007921 spray Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 239000000779 smoke Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000001741 organic sulfur group Chemical group 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- -1 forms logistics H Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- 238000004781 supercooling Methods 0.000 claims description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical group [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000013081 microcrystal Substances 0.000 abstract description 16
- 238000004939 coking Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 37
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 25
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 20
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 239000002918 waste heat Substances 0.000 description 13
- 239000003517 fume Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000003795 desorption Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003034 coal gas Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc 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
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000605716 Desulfovibrio Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YTAHJIFKAKIKAV-XNMGPUDCSA-N [(1R)-3-morpholin-4-yl-1-phenylpropyl] N-[(3S)-2-oxo-5-phenyl-1,3-dihydro-1,4-benzodiazepin-3-yl]carbamate Chemical compound O=C1[C@H](N=C(C2=C(N1)C=CC=C2)C1=CC=CC=C1)NC(O[C@H](CCN1CCOCC1)C1=CC=CC=C1)=O YTAHJIFKAKIKAV-XNMGPUDCSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/30—Technologies for a more efficient combustion or heat usage
Landscapes
- Treating Waste Gases (AREA)
Abstract
The low-temp desulfurization method of denitration of coke oven flue gas.The present invention relates to a kind of method of coke oven flue gas desulphurization denitration, mainly solves the problem of that existing coke oven flue gas desulphurization denitration operating cost is high and generate secondary pollution.The present invention will enter the coke-stove gas or blast furnace gas of coke oven combustion by using the method that micro crystal material adsorbs, before entering coke oven, first remove sulfide, it burns again, again with the nitrogen oxides and sulfide in the method removing coke oven flue gas of absorption, nitrogen oxides in effluent and sulfide after regeneration carry out the technical solution of resource utilization through peroxidating, preferably solves above-mentioned technical problem, this method can be used in the industrial production of coking flue gas desulfurization and denitrification.
Description
Technical field
The invention belongs to desulphurization denitration technical fields, and in particular to a kind of desulfurization denitration method of coke oven flue gas.
Background technique
SO2And NOXIt is the important atmosphere pollution in China, excessive discharge will cause haze, acid rain and photochemical fog
Deng serious harm ecological environment and human health.The burning of fossil fuel is SO2And NOXMain source.Coal be China most
Important natural energy source, as the second largest coal field in China, carbonization of coal is one of industrial coal field primary pollution source, burnt
Kiln gas is the important pollution sources of atmosphere.
Current coke oven flue gas desulfuration field is using more for ammonia process, lime/lime stone method, Dual alkali, magnesium oxide method etc.
For the Wet Flue Gas Desulfurization Technique and semi-dry desulphurization technology of representative.Wet desulphurization absorption rate is high, but such as lime/lime
Stone-gypsum, Dual alkali contain small hydrophilic ionic in magnesium oxide method slurries, are taken out of by flue gas, and are emitted into big
In gas, while these particle surfaces are easily absorbing sulfur dioxide, sulfur trioxide, hydrogen chloride, hydrogen fluoride, nitrogen oxides, nocuousness
Organic matter and bacterium etc. cause atmosphere suspended particles (usually said PM100, PM10, PM2.5 etc.) content to dramatically increase,
And cause haze and atmospheric photochemical reaction phenomenon, cause serious environmental pollution.Sodium sulfite (potassium) method sulfur removal technology, Wei Er
Man-Luo Defa Desulfovibrio technique, organic acid-acylate buffer-solution method sulfur removal technology, regeneration steam energy consumption is big and regenerates
Rate is low, therefore it is big to industrialize difficulty.Ammonia corrosion is big in the ammonia process of desulfurization, the production process of equipment burn into and ammonia is caused to be high energy
Consumption, high pollution process.Semi-dry desulphurization equipment corrosion compared with wet desulphurization is small, spreads without obvious temperature drop, conducive to chimney exhaust,
But desulfuration efficiency is relatively low, reaction speed is slow.
The mainstream technology in coke oven flue gas denitration field is NH3SCR denitration, SCR technology use catalyst, and catalytic action makes
Reaction activity reduces.In coke-oven plant, since flue gas self-temperature is very low (200 DEG C ~ 300 DEG C), it need to be urged using low-temperature denitration
Agent carries out denitration reaction during this temperature, and need to spray into ammonia into flue gas and make reducing agent.
Individual desulphurization and denitration technique not only takes up a large area, but also invests, operating cost height.Simultaneous SO_2 and NO removal skill
Art, which has, reduces device configuration, saves space, material source is wide, and price is low, renewable the advantages that recycling.Wherein, with work
Property charcoal (coke) technology be representative dry desulfurization denitrification integral technology be the technology most to the heat energy utilization in flue gas.
Chinese patent 201410119747.9 recycles stack gases waste heat using stack gases waste-heat recovery device, reduces
The temperature of stack gases, the activated adoption ability having using coke and low-temperature denitration catalytic capability realize the de- of stack gases
Sulphur, denitration integration.The concrete operation step of the invention is that 1) stack gases first pass through waste gas residual heat recovery unit, and flue is useless
The waste heat of gas is recovered, and temperature is reduced to 100 DEG C ~ 150 DEG C, is subsequently entered in low-temperature SCR desulphurization denitration unit, in flue gas
SO2It by coke adsorbing and removing, is mixed by the flue gas of desulfurization with ammonia, take coke as the catalyst of SCR method, denitration reduction occurs
NO is completed in reactionXRemoving；2) coke in low-temperature SCR desulphurization denitration unit is supplied from by elevator and grader leveling blade
The coke feed unit of conveyer composition, the coke after denitration reduction reaction is expelled in coke main tank, periodically by outlet vehicle
It sends outside；3) flue gas of low-temperature SCR desulphurization denitration unit discharge is sent after gas cleaning unit dust separation to chimney, realizes flue
The qualified discharge of exhaust gas.The waste heat recycled in the waste gas residual heat recovery unit is sent in ammonia steaming device, is generated to coke-oven plant
Remained ammonia carries out ammonia still process processing, provides necessary ammonia for the denitration reduction reaction in low-temperature SCR desulphurization denitration unit.
Chinese patent 201810438291.0 discloses a kind of low-sulfur flue gas desulfurization and denitrification device.The device includes adsorption tower
And vibrating screen, adsorption tower are successively arranged the firstth area, the secondth area and third area along flue gas circulating direction, the firstth area is equipped with flue gas air inlet
Mouthful and positioned at smoke air inlet ammonia-spraying grid, third area is equipped with the gas outlet of flue gas, the active carbon flowed is equipped in the secondth area
Layer, active carbon layer are flowed into from the top entry of adsorption tower, outlet at bottom outflow；The connection of the outlet at bottom of vibrating screen and adsorption tower,
And it is connected by the top entry of conveying mechanism and adsorption tower.
Chinese patent CN201611269710.X discloses a kind of sintering flue gas ammonia charcoal combined desulfurization and denitration method, sintering
Flue gas is after the desulfurization of absorbing liquid containing ammonia again through activated carbon adsorption；Carbonaceous raw material, the gold that the active carbon is 2:1 ~ 5:1 by mass ratio
Belong to oxide source to roast to obtain in 850 ~ 1100 DEG C of countrysidies；The carbonaceous raw material is semicoke, or is the mixed of coal and biomass
Close material.In the present invention, the active carbon as made from by ammonia and the method for the invention is combined, can effective desulphurization denitration, also
Help reduce secondary pollution, reduction technique.
Document above is active carbon (coke) simultaneous SO_2 and NO removal, but can not all be detached from ammonia as this step of reducing agent denitration
Suddenly.Since coke oven flue flow field is uneven, temperature field is uneven, catalyst failure degree is uneven, the volume fraction of escape ammonia is difficult low
In design discipline.Escape ammonia is exceeded to will cause secondary pollution, and corrosion pipeline material, and there is danger in the use process of ammonia
Property, it is very important to the body harm of people.
In view of the above problems, not using ammonia, simultaneously the invention proposes the technology of molecular sieve adsorption simultaneous SO_2 and NO removal
Adsorb the SO in coke oven flue gas2And NOX, and be worth with certain recycling.
Summary of the invention
The technical problem to be solved by the present invention is to during existing coke-oven plant's Coke-oven flue gas governing, operating cost height is produced
The technical issues of raw secondary pollution, provides a kind of method of coke oven flue gas desulphurization denitration, which has process short, if
Standby with low investment, regeneration is simple, and low energy consumption, advantage without secondary pollution.
In order to solve the above technical problems, a kind of method that the present invention uses coke oven flue gas low-temp desulfurization denitration, including it is following
Step:
A) coke-stove gas or blast furnace gas for entering coke oven combustion first remove sulfide, then burn before entering coke oven；
B) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A
It is 180 ~ 320 DEG C；
C) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 120
~180℃；
D) flow B enters cooling tower, after supercooling, dedusting, forms flow C, the temperature of the flow C is 30 ~ 100 DEG C；
E) flow C enters the adsorption tower comprising crystallite adsorbent B, after adsorbing sulfide and nitrogen oxides, forms logistics D；
F) logistics D enters smoke stack emission after heating up；
G) adsorption tower after adsorbing sulfide and nitrogen oxides saturation in step e), with 100 ~ 10000m3The material flow A of/h regenerates,
Regenerated flue gas forms logistics E, wherein the temperature of the logistics E is 120 ~ 350 DEG C；
H) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F；
I) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G；
J) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters wastewater treatment
System or salt extraction system；
K) logistics H enters step the cooling tower in d).
In the above-mentioned technical solutions, preferred technical solution is that UTILIZATION OF VESIDUAL HEAT IN uses steam boiler in the step c),
The vapor (steam) temperature of production is 140 ~ 180 DEG C；Cooling tower in the step d) is spray column or heat exchanger types；Flow C
Temperature be 30 ~ 100 DEG C.
In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion,
Hydrogen sulfide content is 0 ~ 20 mg/m3, 0 ~ 20 mg/m of organic sulfur content3。
In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion,
Hydrogen sulfide content is 0 ~ 10 mg/m3, 0 ~ 10 mg/m of organic sulfur content3。
In the above-mentioned technical solutions, preferred technical solution is, into the coke-stove gas or blast furnace gas of coke oven combustion,
Hydrogen sulfide content is 0 ~ 5 mg/m3, 0 ~ 5mg/m of organic sulfur content3。
In above-mentioned technical proposal, preferred technical solution is that the temperature of the logistics D is 30 ~ 100 DEG C；Nitrogen oxides
Content is 1 ~ 200mg/m3, sulfide content is 0.1 ~ 100 mg/m3。
In above-mentioned technical proposal, preferred technical solution is that the heating mode of the logistics D is heated up using heated by gas
Mode or logistics D and material flow A heat exchange heating mode, for logistics D after heating up, temperature is 80 ~ 200 DEG C.
In above-mentioned technical proposal, preferred technical solution is, in step e), the quantity of adsorption tower is inhaled at least more than two
Attached bed operation temperature is 30 ~ 100 DEG C, and operating pressure is 0.1 ~ 20KPa.
In above-mentioned technical proposal, preferred technical solution is that the temperature of the material flow A is 200 ~ 300 DEG C；Nitrogen oxides
Content is 100-1000mg/m3, sulfide content is 40 ~ 3000 mg/m3。
In the above-mentioned technical solutions, preferred technical solution is, in step e), the quantity of adsorption tower at least more than two,
Adsorbent bed operation temperature is 30 ~ 100 DEG C, and operating pressure gauge pressure is 0.5 ~ 10Kpa.
In the above-mentioned technical solutions, preferred technical solution is the crystallite adsorbent A or the choosing of crystallite adsorbent B
From including X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecule
Sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/
β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β boiling
At least one of stone/Y zeolite or ZSM-5/Y zeolite/modenite.
In the above-mentioned technical solutions, preferred technical solution is that also containing in the crystallite adsorbent includes element week
At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in phase table.
In the above-mentioned technical solutions, preferred technical solution is that containing in the oxidation catalyst includes period of element
At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in table.
In the above-mentioned technical solutions, preferred technical solution is that the lye is sodium hydroxide solution, ammonium hydroxide, residue
At least one of ammonium hydroxide, sodium carbonate liquor, calcium hydroxide solution.
In the above-mentioned technical solutions, preferred technical solution is that denitrating catalyst described in step j) is selected from vanadium tungsten titanium
Catalyst, or selected from including the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth in the periodic table of elements
The above-mentioned crystallite adsorbent of at least one of race's element element.
In the above-mentioned technical solutions, preferred technical solution, it includes SSZ-13, TS- that the adsorbent of molecular sieve B, which is selected from,
1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, ZSM-5/ mercerising
Zeolite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y boiling
At least one of stone or ZSM-5/Y zeolite/modenite.
In the above-mentioned technical solutions, the silica alumina ratio of preferred technical solution, the molecular sieve is greater than 2.
In the above-mentioned technical solutions, preferred technical solution, the IIth element A is selected from magnesium and calcium in the periodic table of elements
At least one of；Ith B race element is selected from least one of copper, silver；IIIth B race element in lanthanum, cerium, yttrium at least
It is a kind of.
In the above-mentioned technical solutions, preferred technical solution, ZSM type molecular sieve is selected from packet in the adsorbent of molecular sieve
At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48 are included, wherein the silica alumina ratio of the molecular sieve is greater than 20.
In the above-mentioned technical solutions, preferred technical solution, adsorbent bed operation temperature are 0 ~ 100 DEG C, operating pressure 0.5
~ 10Kpa, gauge pressure.
In the above-mentioned technical solutions, preferred technical solution is passed through air, ozone, double water oxygen water in regeneration gas oxidizing tower
At least one of.
In the above-mentioned technical solutions, preferred technical solution first uses hot water after the adsorbent of molecular sieve adsorption saturation
It rinses, then with 100-300 DEG C of nitrogen regeneration.
It is known in the art, coal gas is purified using traditional handicraft, using desulfurizing tower again during gas purification process
It is middle to use iron oxide desulfurization；Naphthalene is taken off with active carbon using in de- naphthalene tower；Benzene is taken off with active carbon using debenzolizing tower again；3 are used altogether
Absorbing unit successively purifies coal gas.In device operation, device exit hydrogen sulfide, benzene and naphthalene are dense, influence production effect
Rate.Using method of the invention, have the advantages that (1), can be by benzene, naphthalene and hydrogen sulfide, organic sulfur using adsorbent of molecular sieve
It can thoroughly remove completely, solve the problems, such as line clogging.(2) adsorbent is subjected to multifunction, can desulfurization simultaneously, de- benzene,
De- naphthalene can carry out comprehensive purifying process simultaneously, reduce the quantity of adsorption tower in this way, reduce production in an adsorption tower
Cost.
Using technical solution of the present invention: the coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly enters after de- benzene
Comprehensive purifying tower, purifying column is interior to contain molecular sieve adsorbent, while removing the aromatic hydrocarbons and sulfide in coal gas, enters back into coke
Furnace burning.De- naphthalene tower exit hydrogen sulfide content is 0 mg/m3, naphthalene content is 0 mg/m3, tar content 0 carries in gas
Organic sulfur be also removed, sulfur dioxide in flue gas is emitted on 10m g/m3Hereinafter, device is stable.It is de- to reduce end desulfurization
The cost of nitre.
By adopting the above technical scheme, using crystallite adsorbent desulphurization denitration, crystallite adsorbent to gas cleaning handle just like
Lower advantage: the sulfur dioxide and nitrogen oxides in flue gas can be effectively adsorbed, discharge standard is made up to；High temperature resistant, structure are steady
It is fixed, iterative regenerable；It is high to adsorb precision, other than adsorb sulfur dioxide, can also dedusting simultaneously remove the harmful substances such as dioxin,
Make up to discharge standard；Crystallite adsorbent long service life, does not generate dangerous waste.By setting up adsorption tower in exhanst gas outlet, benefit
Sulfur dioxide, the nitrogen oxides in flue gas are adsorbed with System of Silica/Aluminum Microparticle hydrochlorate crystallite adsorbent, System of Silica/Aluminum Microparticle in adsorption tower
After hydrochlorate crystallite adsorbent adsorption saturation, crystallite adsorbent is regenerated by high-temperature flue gas, the nitrogen oxides and sulphur of desorption
Compound enters oxidizing tower, is oxidized to sulfur trioxide and nitrogen dioxide, and regenerated flue gas is absorbed with water spray, after effluent part neutralizes,
It is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column circulation.Entire treatment process process is short, equipment investment
It saves, regenerative operation is simple and reliable, and low energy consumption, flue gas emission nitrogen oxides≤50mg/m3, sulfur dioxide≤30mg/m3, dust content
Less than 5 mg/m3, achieve preferable technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of coke oven flue gas desulfurization denitration method of the invention.
1 is coke oven flue gas in Fig. 1, and 2 be waste heat steam boiler, and 3 be spray column, and 4 be heat exchanger, and 5 be electric fishing mist, and 6 be suction
Attached tower, 7 be blower, and 8 be heater, and 9 be denitrating tower, and 10 be oxidizing tower, and 11 be sedimentation basin, and 12 be cooling tower, and 13 be chimney.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I
1000~4000mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between；Object
Stream I enters comprehensive purifying tower, ZSM molecular sieve class adsorbent is contained in the comprehensive purifying tower, while removing in coal gas
Aromatic hydrocarbons and sulfide form logistics II, and benzene concentration is less than 1000mg/m in logistics II3, naphthalene concentration is less than 4 mg/m3, hydrogen sulfide is dense
Degree is less than 4mg/m3；Organic sulfur concentration is less than 4mg/m3；Logistics II enters coke oven combustion.
The flue gas of 16 240 DEG C of ten thousand steres, amount of nitrogen oxides 500mg/m3, sulfide content is 200 mg/m3, into
Enter waste heat boiler, generate steam, flue-gas temperature is reduced to 180 DEG C or so；180 DEG C of flue gas, to 50 DEG C, is sprayed by spraying cooling
Water drenching after effluent part neutralizes, removes biochemical system by being recycled；After flue gas after cooling passes through defogging equipment, into suction
Attached tower；Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3It is micro-
Brilliant material modenite；Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, enter
From after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3,
Sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, are automatically switched after adsorption saturation
Circular regeneration；Automatically switch within every 7 days a tower regeneration, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, desorption
Nitrogen oxides and sulfide be introduced into the denitrating tower containing ZSM-5 molecular sieve, in 300 DEG C of progress denitration reactions, nitrogen oxides
It is reduced into nitrogen, the gas after reaction enters back into oxidizing tower, and sulfide is oxidized to sulfur trioxide with vanadium series catalyst；Mixed gas
It after cooling, is absorbed with water spray, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 2]
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I
1000~4000mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between；Object
Stream I enters comprehensive purifying tower, ZSM molecular sieve class adsorbent is contained in the comprehensive purifying tower, while removing in coal gas
Aromatic hydrocarbons and sulfide form logistics II, and benzene concentration is less than 1000mg/m in logistics II3, naphthalene concentration is less than 4 mg/m3, hydrogen sulfide is dense
Degree is less than 4mg/m3；Organic sulfur concentration is less than 4mg/m3；Logistics II enters coke oven combustion.
Specific embodiment device process as shown in Fig. 1, the flue gas of 15 260 DEG C of ten thousand steres, nitrogen oxides contain
Amount is 400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 150 DEG C of steam are generated, flue-gas temperature is reduced to
120 DEG C or so；By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, is gone 120 DEG C of flue gas by being recycled
Biochemical system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 3 200m3Adsorption tower, two open it is one standby,
120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is diameter
It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100
DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Adsorption tower is built-in
Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again
It is raw, the adsorption tower 3000m of saturation3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, oxygen
It is melted into sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into department of biochemistry
Salt extraction workshop is united or goes, tail gas enters flue gas spray column.
[embodiment 3]
The coke-stove gas that coke oven comes out enters slightly de- benzene unit, slightly forms logistics I after de- benzene, wherein benzene concentration exists in logistics I
1000~3500mg/m3Between, naphthalene concentration is in 200~500mg/m3Between, concentration of hydrogen sulfide is in 100~500mg/m3Between；Object
Stream I enters comprehensive purifying tower, and the ZSM-5 molecular sieve class adsorbent containing zinc modification in the comprehensive purifying tower removes simultaneously
Fall the aromatic hydrocarbons and sulfide in coal gas, forms logistics II, benzene concentration is less than 60mg/m in logistics II3, naphthalene concentration is less than 1 mg/m3,
Concentration of hydrogen sulfide is less than 1mg/m3；Toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, naphthalene, anthracene, the concentration in Kun are less than 1 mg/m3；Vulcanization
Object is hydrogen sulfide, the concentration in sulfur dioxide, mercaptan, thioether, thiophene, methyl mercaptan, Dimethyl sulfide is less than 1 mg/m3, logistics
II, which enters coke oven, generates electricity.
Specific embodiment device process as shown in Fig. 1, the flue gas of 14 240 DEG C of ten thousand steres, nitrogen oxides contain
Amount is 450mg/m3, sulfide content is 200 mg/m3, into waste heat boiler, 160 DEG C of steam are generated, flue-gas temperature is reduced to
110 DEG C or so；By spraying cooling to 50 DEG C, shower water after effluent part neutralizes, is gone 110 DEG C of flue gas by being recycled
Biochemical system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 3 200m3Adsorption tower, two open it is one standby,
120m is loaded in each adsorption tower3Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is diameter
It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 110
DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.Adsorption tower is built-in
Desulphurization and denitration, dedusting crystallite adsorbent are filled out, after adsorption saturation, automatically switches circular regeneration with high-temperature flue gas；Automatically it cuts within every 7 days
Change a tower regeneration, the adsorption tower 3000m of saturation3240 DEG C of flue gases of/h are regenerated, the nitrogen oxides and sulfide of desorption
Into the denitrating tower for being introduced into the mordenite catalyst containing copper load, in 350 DEG C of progress denitration reactions, nitrogen oxides reduction
At nitrogen, the oxidizing tower containing vanadium series catalyst is entered back into, sulfur trioxide and nitrogen dioxide are oxidized to；After mixed gas cooling,
It is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas spray column.
[embodiment 4]
Specific embodiment device process as shown in Fig. 1, the flue gas of 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are
1000mg/m3, sulfide content is 500 mg/m3, into waste heat boiler, 10 tons of 165 DEG C of steam, flue-gas temperature are generated per hour
It is reduced to 120 DEG C or so；120 DEG C of flue gas is by spraying cooling to 40 DEG C, and by being recycled, effluent part neutralizes shower water
Afterwards, the salt extraction system that going produces；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 4 200m3Absorption
Tower, three open standby, a filling 120m in each adsorption tower3Micro crystal material amounts to 480 m3Micro crystal material SSZ-13 molecular sieve；Absorption
Tower specification is 4.8 meters of diameter, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, changed into from heat exchanger and hot fume
After heat, reach 100 DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/
m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, automatically switch circular regeneration after adsorption saturation；Every 7 days automatic
Switch a tower regeneration, the adsorption tower 2000m of saturation3The hot fume of/h is regenerated, the nitrogen oxides and sulfide of desorption
Into the oxidizing tower containing Cu-series catalyst, it is oxidized to sulfur trioxide and nitrogen dioxide；After mixed gas cooling, inhaled with water spray
It receives, after effluent part neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 5]
Specific embodiment device process as shown in Figure 1, the flue gas of 20 180 DEG C of ten thousand steres, amount of nitrogen oxides are
1000mg/m3, sulfide content is 500 mg/m3, into waste heat boiler, generate 150 DEG C of steam, flue gas cool-down is to 170 DEG C, cigarette
Gas enters spray column, and by spraying cooling to 40 DEG C, shower water is by being recycled, and after effluent part neutralizes, what going produced is mentioned
Salt system；After flue gas after cooling passes through defogging equipment, into adsorption tower；Using 4 200m3Adsorption tower, three open it is one standby, often
120m is loaded in a adsorption tower3Micro crystal material, amount to 480m3Micro crystal material copper ZSM-5 molecular sieve；Adsorption tower specification is diameter
It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100
DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 40mg/m3, sulfide content is 10 mg/m3.Adsorption tower is built-in
Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again
It is raw, the adsorption tower 3000m of saturation3180 DEG C of flue gases of/h are regenerated, and the nitrogen oxides and sulfide of desorption, which enter, contains copper
The oxidizing tower of series catalysts, is oxidized to sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, part is useless
After water neutralizes, being discharged into produces salt extraction workshop, and tail gas enters flue gas spray column.
[embodiment 6]
Specific embodiment device process as shown in Figure 1, the flue gas of 180 DEG C of 200,000 sides rice, amount of nitrogen oxides are
400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 170 DEG C of steam are generated, flue gas cool-down enters to 175 DEG C
For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled；Flue gas after cooling passes through
After defogging equipment, into adsorption tower；Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3Crystallite
Material amounts to 360 m3Micro crystal material, micro crystal material include the ZSM-5 molecular sieve of lanthanum and zinc modification；Adsorption tower specification is diameter
It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into smoke stack emission, nitrogen oxides in effluent content is
30mg/m3, sulfide content 5mg/m3.Desulphurization and denitration, dedusting crystallite adsorbent are loaded in adsorption tower, it is automatic after adsorption saturation
Switch circular regeneration；Automatically switch within every 7 days a tower regeneration, the adsorption tower 4000m of saturation3180 DEG C of the flue gas of/h carries out
Regeneration, the nitrogen oxides and sulfide of desorption enter oxidizing tower, are oxidized to sulfur trioxide and nitrogen dioxide at 250 DEG C；Gaseous mixture
It after body cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop, tail gas enters flue gas
Spray column.
[embodiment 7]
Specific embodiment device process as shown in Fig. 1, the flue gas of 18 240 DEG C of ten thousand steres, amount of nitrogen oxides are
400mg/m3, sulfide content is 100 mg/m3, into waste heat steam boiler, generate 145 DEG C of steam, flue gas cool-down to 160 DEG C,
By spraying cooling to 40 DEG C, shower water after effluent part neutralizes, removes biochemical system by being recycled；Flue gas after cooling
After defogging equipment, into adsorption tower；Using 3 200m3Adsorption tower, two open one standby, and 120m is loaded in each adsorption tower3
Micro crystal material amounts to 360 m3Micro crystal material ZSM-5 molecular sieve；Adsorption tower specification is 4.8 meters of diameter, 12.0 meters high；Flue gas removes
After desulfuration compound and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100 DEG C or more, into smoke stack emission, cigarette
Amount of nitrogen oxides is 50mg/m in gas3, sulfide content is 20 mg/m3.Desulphurization and denitration, dedusting crystallite are loaded in adsorption tower
Adsorbent automatically switches circular regeneration after adsorption saturation；Automatically switch within every 7 days a tower regeneration, the adsorption tower of saturation is used
3000m3The hot fume of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidizing tower, is oxidized to sulfur trioxide and two
Nitrogen oxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into biochemical system or goes to salt extraction workshop,
Tail gas enters flue gas spray column.
[embodiment 8]
Specific embodiment device process as shown in Fig. 1, the flue gas of 18 210 DEG C of ten thousand steres, amount of nitrogen oxides are
400mg/m3, sulfide content is 100 mg/m3, into waste heat boiler, 160 DEG C of steam are generated, flue gas cool-down passes through to 185 DEG C
For spraying cooling to 50 DEG C, shower water after effluent part neutralizes, goes to the salt extraction workshop of coking by being recycled；Cigarette after cooling
After gas passes through defogging equipment, into adsorption tower；Using 4 200m3Adsorption tower, three open one standby, filling in each adsorption tower
150m3Micro crystal material amounts to 600 m3Micro crystal material containing modenite and ZSM-5 molecular sieve；Adsorption tower specification is diameter
It is 4.8 meters, 12.0 meters high；After flue gas removes sulfide and nitrogen oxides, into from after heat exchanger and hot fume heat exchange, reach 100
DEG C or more, into smoke stack emission, nitrogen oxides in effluent content is 50mg/m3, sulfide content is 20 mg/m3.Adsorption tower is built-in
Desulphurization and denitration, dedusting crystallite adsorbent are filled out, automatically switches circular regeneration after adsorption saturation；One tower of automatic switchover in every 7 days is again
It is raw, the adsorption tower 4000m of saturation3240 DEG C of the flue gas of/h is regenerated, and the nitrogen oxides and sulfide of desorption enter oxidation
Tower is oxidized to sulfur trioxide and nitrogen dioxide；It after mixed gas cooling, is absorbed with water spray, after effluent part neutralizes, is discharged into life
Change system goes to salt extraction workshop, and tail gas enters flue gas spray column.
Claims (11)
1. a kind of method of coke oven flue gas low-temp desulfurization denitration, comprising the following steps:
A) coke-stove gas or blast furnace gas for entering coke oven combustion, before entering coke oven, first with the removing vulcanization of crystallite adsorbent A
Object enters back into coke oven combustion；
B) coke oven flue gas of coke oven flue is drawn sulfur compound and nitrogen oxides, is denoted as material flow A, the temperature of the material flow A
It is 180~320 DEG C；
C) material flow A carries out UTILIZATION OF VESIDUAL HEAT IN, produces steam, and the flue gas after cooling forms flow B, and the temperature of the flow B is 120
~180 DEG C；
D) flow B enters cooling tower, after supercooling, dedusting, forms flow C, the temperature of the flow C is 30~100 DEG C；
E) flow C enters the adsorption tower comprising crystallite adsorbent B, after adsorbing sulfide and nitrogen oxides, forms logistics D；
F) logistics D enters smoke stack emission after heating up；
G) adsorption tower after absorption sulfide and nitrogen oxides are saturated in step e), with 100~10000m3The material flow A of/h regenerates,
Regenerated flue gas forms logistics E, wherein the temperature of the logistics E is 120~350 DEG C；
H) logistics E enters the denitrating tower comprising denitrating catalyst, after catalysis reduction, forms logistics F；
I) logistics F enters the oxidizing tower comprising oxidation catalyst, after catalysis oxidation, forms logistics G；
J) logistics G enters regeneration tail gas desulfurizing tower, after water or lye spray, forms logistics H, spray liquid enters wastewater treatment
System or salt extraction system；
K) logistics H enters step the cooling tower in d).
2. the method for coke oven flue gas desulphurization denitration according to claim 1, it is characterised in that the temperature of the material flow A is
240~280 DEG C；Amount of nitrogen oxides is 100~1000mg/m3, sulfide content is 30~3000mg/m3。
3. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that into coke oven combustion
Coke-stove gas or blast furnace gas, hydrogen sulfide content are 0~20mg/m3, 0~20mg/m of organic sulfur content3。
4. UTILIZATION OF VESIDUAL HEAT IN uses steam boiler in step c) described in, and the vapor (steam) temperature of production is 140~180 DEG C；The step
It is rapid d) in cooling tower be spray column or heat exchanger types；The temperature of flow C is 30~100 DEG C.
5. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that the temperature of the logistics D
Degree is 30~100 DEG C；Amount of nitrogen oxides is 1~200mg/m3, sulfide content is 0.1~100mg/m3。
6. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that the liter of the logistics D
Warm mode is using heated by gas heating mode or logistics D and material flow A heat exchange heating mode, and after heating up, temperature is logistics D
80~200 DEG C.
7. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that in step e), adsorption tower
Quantity at least more than two, adsorbent bed operation temperature be 30~100 DEG C, operating pressure be 0.1~20KPa；The step
J) in, lye is at least one of sodium hydroxide solution, ammonium hydroxide, remained ammonia, sodium carbonate liquor, calcium hydroxide solution.
8. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that affiliated crystallite absorption
It includes X-type molecular sieve, Y type molecular sieve, A type molecular sieve, SSZ-13 molecular sieve, TS-1, Ti- that agent A or crystallite adsorbent B, which are selected from,
MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, MCM-22, MCM-49, MCM-56,
ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β boiling
Stone/modenite, ZSM-5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite.
9. according to the method for the coke oven flue gas low-temp desulfurization denitration that claim 7 is stated, it is characterised in that the crystallite adsorbent
In further include in the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element extremely
A kind of few element.
10. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that in the oxidation catalyst
Containing include in the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element extremely
A kind of few element.
11. the method for coke oven flue gas low-temp desulfurization denitration according to claim 1, it is characterised in that denitration described in step h)
Catalyst is selected from vanadium tungsten titanium catalyst, or selected from including the Ith A, II A, V A, I B, II B, III B, IV B, V in the periodic table of elements
B, the above-mentioned crystallite adsorbent of at least one of VI B, VII B or the VIIIth race's element element.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569603A (en) * | 2020-05-18 | 2020-08-25 | 中国华能集团有限公司 | Flue gas integrated desulfurization and denitrification method based on low-temperature adsorption principle |
| CN113209780A (en) * | 2021-05-17 | 2021-08-06 | 山东钢铁股份有限公司 | Purification treatment method for coke oven gas microcrystal adsorption regeneration tail gas |
| CN114570413A (en) * | 2020-12-02 | 2022-06-03 | 宁波中科远东催化工程技术有限公司 | Substance for desulfurization, preparation method and application thereof |
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2018
- 2018-12-07 CN CN201811490524.8A patent/CN109806741A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569603A (en) * | 2020-05-18 | 2020-08-25 | 中国华能集团有限公司 | Flue gas integrated desulfurization and denitrification method based on low-temperature adsorption principle |
| CN114570413A (en) * | 2020-12-02 | 2022-06-03 | 宁波中科远东催化工程技术有限公司 | Substance for desulfurization, preparation method and application thereof |
| CN114570413B (en) * | 2020-12-02 | 2024-03-12 | 宁波中科远东催化工程技术有限公司 | Material for desulfurization, preparation method and application thereof |
| CN113209780A (en) * | 2021-05-17 | 2021-08-06 | 山东钢铁股份有限公司 | Purification treatment method for coke oven gas microcrystal adsorption regeneration tail gas |
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