CN109019524A - A kind of recovery technology of sulfur of middle low concentration sour gas - Google Patents
A kind of recovery technology of sulfur of middle low concentration sour gas Download PDFInfo
- Publication number
- CN109019524A CN109019524A CN201811005747.0A CN201811005747A CN109019524A CN 109019524 A CN109019524 A CN 109019524A CN 201811005747 A CN201811005747 A CN 201811005747A CN 109019524 A CN109019524 A CN 109019524A
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- China
- Prior art keywords
- sulfur
- process gas
- sulphur
- gas
- reaction device
- Prior art date
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- Granted
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000011593 sulfur Substances 0.000 title claims abstract description 119
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 118
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000011084 recovery Methods 0.000 title claims abstract description 42
- 238000005516 engineering process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 153
- 239000007789 gas Substances 0.000 claims abstract description 126
- 230000008569 process Effects 0.000 claims abstract description 118
- 238000010521 absorption reaction Methods 0.000 claims abstract description 92
- 239000005864 Sulphur Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 30
- 230000009467 reduction Effects 0.000 claims abstract description 23
- 239000003245 coal Substances 0.000 claims abstract description 21
- 238000002485 combustion reaction Methods 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000010865 sewage Substances 0.000 claims abstract description 13
- 239000003517 fume Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- 239000002002 slurry Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000006722 reduction reaction Methods 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 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
- 239000000498 cooling water Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 10
- 235000010261 calcium sulphite Nutrition 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 239000002918 waste heat Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 239000013589 supplement Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000011944 chemoselective reduction Methods 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- JCXCVQBEOOXYNZ-UHFFFAOYSA-J dicalcium;carbonate;sulfate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]S([O-])(=O)=O JCXCVQBEOOXYNZ-UHFFFAOYSA-J 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 208000012839 conversion disease Diseases 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 10
- 210000000952 spleen Anatomy 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000007726 management method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000007763 Castanea pumila Nutrition 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 208000036119 Frailty Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000408782 Lepomis microlophus Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000009688 liquid atomisation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- -1 sour gas Hydrocarbon Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012384 transportation and delivery Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
Abstract
The present invention provides a kind of recovery technology of sulfur of middle low concentration sour gas, contains H for handling2The sour gas of S20-50v%, capital equipment is along acid gas stream to combustion furnace, twin-stage claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device, cyclic absorption unit and Molten sulphur slot including being sequentially connected in series；Cyclic absorption unit includes absorption tower, and circulating absorption solution is containing lye and/or calcic liquid, and main water quantity balance is the vapoury condensed water of Process Gas.Present invention process is in level-one claus reaction device by COS, CS2It is fully hydrolyzed, selective oxidation reaction device is by H2S is close to being totally converted, a small amount of SO2It is handled on absorption tower, realizes ultralow atmosphere discharge；Sulfur purity collected by condensed water or absorbing liquid is high；Circulating absorption solution and liquid concentration more than needed are low, are sent to sewage device, fire coal boiler fume wet desulphurization cell processing or are sent to coal-burning boiler as coal water drenching.
Description
Technical field
The present invention relates to a kind of recovery technology of sulfur, and in particular to a kind of recovery technology of sulfur of middle low concentration sour gas.
Background technique
During petrochemical industry, coal chemical industry, coal gas, most of sulphur contained by raw material would generally be converted to H2S, through separating
It is formed and contains H2The sour gas of S；Also often separation is formed containing H during natural gas purification processing2The sour gas of S.These sour gas are general
It is handled through recovery technology of sulfur, by H2S is converted into elemental sulfur as much as possible.
Sour gas sulfur recovery facility, during operation, the tail gas emptied through chimney, SO2Concentration is continuous monitoring
Project, emission request is more stringent in recent years, and such as " petroleum refining industry pollutant emission standard " (GB31570-2015) is provided
The SO of acid gas recovering device2Concentration of emission limit value is 400mg/m3, territorial development density is higher, resource environment carrying
Ability starts the region weakened or atmospheric environment capacity is smaller, ecological environment frailty, be easy to happen great environmental pollution problem and
Need to take the regional SO of special standby safeguard measure2Concentration of emission limit value is 100mg/m3.Because of H2S、COS、CS2It is main stench
Polluter, concentration of emission should reduce as far as possible.Some areas also execute more stringent discharge standard or according to emission behaviour
Carry out rewards and punishments.
A kind of sour gas recovery technology of sulfur of the prior art, capital equipment is along acid gas stream to including combustion furnace, two
Grade claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device, deep purifying unit, by sour gas institute
Sulfide hydrogen is substantially transitioned to sulphur and recycles, and Process Gas reaches discharge standard and empties through chimney later.Wherein selective hydrogenation
Reduction reactor is by SO contained by Process Gas2All reduction generate elemental sulfur and on a small quantity can be in selective oxidation reaction device below
The H of processing2Contained organic sulfur is converted elemental sulfur or H as far as possible by S2S；What selective oxidation reaction device was filled by introducing air
O2By H2S is substantially transitioned to elemental sulfur, and selective oxidation is elemental sulfur, and by-product is a small amount of SO2, the thinking of technology controlling and process be
Under the premise of guaranteeing simple substance Recovery ratio, with few production SO2For main target, to obtain higher H2S conversion ratio is appropriate low outlet
Gas H2S content is by-end, H in selective oxidation reaction device exit procedure gas2S content is usually SO2Several times of content with
On, to carry out in deep purifying unit by H2S is oxidized to the process of simple substance sulfur recovery, while by part SO2It disposes.
The activated carbon desulphurization agent as loaded alkali or iron oxide that dry method can be used in deep purifying unit carries out H2Absorption, the oxidation of S generates
Elemental sulfur is deposited on inner hole or the surface of active carbon particle, SO2Also substantially and H2S reaction generates elemental sulfur deposition；Evergreen chinquapin can also be used
The wet process such as glue method, iron salt method are by H2S, which is absorbed and aoxidized, generates elemental sulfur particle disperse in slurries, SO2Also basic absorption into
Enter slurries, small part and H2S reaction generates elemental sulfur, is largely converted to sulfate；The dry method, wet desulphurization all can be by mistakes
Journey gas is contained such as 3000mg/m3H2S processing is to such as 10 mg/m3Hereinafter, or even 5 mg/m3Hereinafter, SO2Content also can achieve
Discharge standard, this kind of processing residue H2The advantages of S method, is that sulphur yield is higher, but the activated carbon desulphurization agent of dry method penetrate after need
The elemental sulfur will be adsorbed by hot recycling, deposited purges and condenses collection, and desulfurizer regeneration is cumbersome, changes agent process
The problems such as there are the whereabouts of safety, health and waste desulfurizing agent and processing, wet process gained elemental sulfur need to divide from slurry
It separates out and, obtained sulphur is impure more, and quality is generally all poor；It is this selective oxidation reaction device to be worked off one's feeling vent one's spleen in a word
Middle low concentration H2S is converted into elemental sulfur and produces the process of sulphur, and the device is complicated, and process control needs are high, to selective hydrogenation
SO in reduction reactor2Conversion requirements it is higher, the control of preceding procedure technology is not proper, operation fluctuation or atmosphere when lower load
Discharge often cannot be up to standard, thus there are clearly disadvantageous.
Summary of the invention
To overcome above-mentioned technological deficiency, the present invention provides a kind of recovery technology of sulfur of middle low concentration sour gas, for locating
Reason contains H2The sour gas of S20-50v%, capital equipment are anti-to the combustion furnace including being sequentially connected in series, level-one Crouse along acid gas stream
Answer device, second level claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device, cyclic absorption unit；Burning
Furnace is attached to waste heat boiler, is respectively set before and after claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device
First to the 5th condenser and first to fourth heater；First to the 5th condenser is cold by the gaseous sulfur in Process Gas respectively
It coagulates for molten sulfur, the storage of molten sulfur influent sulphur slot；First to fourth heater respectively will be from first to fourth condenser overhead
Process Gas out is heated to required temperature and enters back into respective reaction device；
Wherein, Fe is loaded on level-one claus reaction device top2O3/Al2O3De-oxygen type catalyst for recovering sulfur, lower part filling
TiO2Base catalyst for recovering sulfur or pure TiO2Catalyst for recovering sulfur；The de-oxygen type catalyst for recovering sulfur is in addition to tool
There is claus reaction active, also by the O in Process Gas2By with H2S reaction generates elemental sulfur and removes；The TiO2Base sulphur
Recycle catalyst or pure TiO2Catalyst for recovering sulfur is in addition to active with claus reaction, also by COS, CS in Process Gas2It connects
It is bordering on and is completely converted into elemental sulfur or H2S, COS, CS2Total content≤10mg/m3；
Second level claus reaction device loads catalyst for recovering sulfur, under conditions of being lower than level-one claus reaction temperature, carries out
Further claus reaction conversion, the catalyst for recovering sulfur are TiO2Base catalyst for recovering sulfur, TiO2/Al2O3Sulphur
Recycle catalyst and Al2O3One or both of catalyst for recovering sulfur；In the second level claus reaction device exit procedure gas
H2S+SO2Content≤1.5v%；
Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Or CoO-MoO3/ TiO2-Al2O3Selective reduction SO2It urges
Agent utilizes the H generated in combustion furnace2By SO2Close to whole reduction, primary product is elemental sulfur, by-product H2S, not by simple substance
Sulphur is reduced to H2S；
Selective oxidation reaction device loads selective oxidation H2S catalyst is mended using before the reactor inlet by introducing air
The O entered2By H2For S close to being totally converted, selective oxidation is elemental sulfur, and by-product is a small amount of SO2；The selective oxidation reaction
H in device exit procedure gas2S content≤100mg/m3, SO2Content is H2Five times or more of S content；
Cyclic absorption unit includes absorption tower, and setting is for Process Gas, filler and/or the spray of circulating absorption solution distribution and contact in tower
Leaching, atomization component, the pH5-10 of circulating absorption solution, 20-50 DEG C of operation temperature, main water quantity balance is vapoury for Process Gas
Condensed water, circulating absorption solution maintain to operate normally outside liquid more than needed be sent to sewage device processing, or to be sent to fire coal boiler fume wet
Method desulfurization unit handles and as make-up water source, or is sent to coal-burning boiler as coal water drenching；Circulating absorption solution be containing lye and/
Or calcic liquid, wherein being to contain sulfurous acid by supplement sodium hydroxide, sodium carbonate or sodium bicarbonate maintenance absorbability containing lye
Sodium and/or metabisulfite solution, calcic liquid are to maintain containing for absorbability by supplement calcium oxide, calcium hydroxide, calcium carbonate superfine powder
Calcium sulfite and/or calcium sulfate slurries；When cyclic absorption unit uses calcic liquid, on absorption tower, the setting the 6th of Process Gas entrance is cold
Condenser, Process Gas are first cooled to 20-50 DEG C through the 6th condenser, and some vapor is condensed into water, contained sulphur droplet, powder and is caught
Collection forms the feed liquid containing sulphur powder, into absorption tower or its attached cyclic absorption liquid storage tank and matches again after feed liquid separation sulphur slurry
Calcium oxide, calcium hydroxide, calcium carbonate superfine powder is added to carry out cyclic absorption；
The recovery technology of sulfur includes the following steps:
1) enter combustion furnace after sour gas is mixed with aequum air and/or oxygen-enriched air to burn, the temperature control of combustion furnace
It makes the Process Gas that generates after 1050-1300 DEG C, burning and enters after waste heat boiler and be cooled to 260-350 DEG C, Process Gas is from waste heat
Boiler export enters the first condensate cooler and is cooled to 140-170 DEG C, after the condensation of the elemental sulfur that is generated in combustion furnace with process
Gas is segregated into Molten sulphur slot；
2) it is heated to 200-250 DEG C of required temperature from the Process Gas that the first condenser overhead comes out, into level-one claus reaction
Device carries out claus reaction and COS, CS2Hydrolysis；The temperature for controlling the reactor inlet gas makes catalyst reactor bed
Lower part reaches COS, CS2The temperature being fully hydrolyzed, wherein TiO2It is 320-350 DEG C when base catalyst for recovering sulfur, pure TiO2Sulphur
It is 300-350 DEG C when recycling catalyst；Exit procedure gas enters the second condenser and is cooled to 130-160 DEG C, makes the simple substance generated
Sulphur enters Molten sulphur slot after separating with Process Gas；
3) enter the progress gram of second level claus reaction device after being heated to 210-230 DEG C from the Process Gas that the second condenser overhead comes out
Louth reaction further generates elemental sulfur, and exit procedure gas enters third condenser and is cooled to 130-160 DEG C, makes the simple substance generated
Sulphur enters Molten sulphur slot after separating with Process Gas；
4) it is heated to 200-220 DEG C from the Process Gas that third condenser overhead comes out, into Chemoselective reduction device, SO2Choosing
Selecting property is reduced to elemental sulfur；The Process Gas come out from Chemoselective reduction device enters the 4th condenser and is cooled to 130-150 DEG C,
The elemental sulfur of generation enters Molten sulphur slot after separating with Process Gas；
5) from the 4th condenser overhead come out Process Gas fill into aequum air and mix after, be heated to 200-230 DEG C it is laggard
Selectable oxidation reactor, catalyst bed temperature of lower reach 220-280 DEG C, H2S selective oxidation is elemental sulfur, by-product
Object is SO2；The Process Gas come out from selective oxidation reaction device enters the 5th condenser and is cooled to 120-140 DEG C, the list of generation
Matter sulphur enters Molten sulphur slot after separating with Process Gas, and Process Gas is through optional molten sulfur trap trap sulfur mist and flows into liquid sulfur
After sulphur slot, into cyclic absorption cell processing；
6) Process Gas come out from the 5th condenser overhead or molten sulfur trap, into cyclic absorption cell processing after arranged through chimney
It is empty；Wherein cyclic absorption unit uses when containing lye, and the cooling of Process Gas, some vapor are condensed into water, contained sulphur droplet, powder
Grain and SO2、H2The trapping of S, all by containing lye circulated sprinkling or atomization absorption realize, lye by circulating cooling water management temperature,
Sulphur slurry or liquid more than needed are separated in lye cyclic process is being sent to sewage device processing or to be sent to fire coal boiler fume wet process de-
Sulphur slurry is separated before sulphur cell processing；When wherein cyclic absorption unit uses calcic liquid, Process Gas first passes through set the 6th
Condenser is cooled to 20-50 DEG C, and steam condensate of the gained containing sulphur powder separates the laggard circulating absorption tower of sulphur slurry.
In recovery technology of sulfur of the present invention, the level-one claus reaction device, second level claus reaction device, selective hydrogenation
The all preferred adiabatic reactor of reduction reactor, selective oxidation reaction device, by controlling the main reactant content in implication
And temperature, so that catalyst bed middle and lower part temperature is reached required reaction temperature using exothermic heat of reaction temperature rise.
In recovery technology of sulfur of the present invention, the SO of suitable control level-one claus reaction device entrance is answered2、H2S concentration, makes this
The catalyst bed temperature rise of level-one claus reaction device reaches such as 80-100 DEG C, and by controlling the reactor inlet temperature degree
At such as 210-250 DEG C, exothermic heat of reaction, which can be such that catalyst bed temperature of lower reaches, can make COS, CS2The temperature be fully hydrolyzed, converted
Degree, wherein in TiO2Base catalyst for recovering sulfur is 320-350 DEG C, in pure TiO2Base catalyst for recovering sulfur is 300-350 DEG C,
The level-one claus reaction device is worked off one's feeling vent one's spleen middle COS, CS2Total content can reach≤10mg/m3Level, this is one of this technique
Key, because being not easy to reach so high reaction bed temperature in rear process and being also equipped with the item that can be converted into elemental sulfur
Part；Some can be in lower temperature such as 250 DEG C hydrolysis COS, CS2Catalyst, including by such as alkaline-earth metal, transition metal, dilute
What soil metal oxide or salt were modified contains TiO2Catalyst hydrolyzes COS, CS2Activity and precision can achieve requirement, but one
As the service life far below the present invention used in TiO2Base catalyst for recovering sulfur, pure TiO2Catalyst for recovering sulfur；The TiO2Base sulphur
Sulphur recycles catalyst, contains TiO285m% or more, remaining is calcium sulfate binder, surface area 100-130m2/ g, pore volume 0.20-
0.35ml/g；The pure TiO2Catalyst for recovering sulfur contains TiO299m% or more, surface area 120-180m2/ g, pore volume 0.3-
0.5ml/g。
In recovery technology of sulfur of the present invention, the selective oxidation H2S catalyst, including Fe2O3/SiO2Or by alkaline earth gold
Category, rare earth metal, transition metal oxide modifying H2S catalyst for selective oxidation, wherein Fe2O3Content 3-10m%, alkaline earth
Metal oxide such as CaO 0-3m%, rare-earth oxide such as La2O3、CeO2, transition metal oxide such as Cr2O3And/or V2O5
Content 3-7m%；Catalyst average pore diameter 30nm or more is preferably 35nm or more, surface area such as 40-60m2/ g, pore volume are such as
0.5-0.6ml/g, the larger advantage of catalyst average pore diameter are not agglomerated in smaller diameter bore when bed temperature is lower
Liquid sulfur plug-hole or less cohesion plug-hole, to guarantee that the activity of catalyst and the extent of reaction meet the requirements.
In recovery technology of sulfur of the present invention, adiabatic reactor is can be used in selective oxidation reaction device, by controlling into implication
In less low H2S content such as 0.5-1.1v% and such as 200-230 DEG C of slightly higher temperature, make to be catalyzed using exothermic heat of reaction temperature rise
Agent bed temperature of lower reaches 220-280 DEG C, plays the reactivity worth of the catalyst at relatively high temperatures, makes H2S is close to complete
Portion's conversion also generates in addition to generating elemental sulfur and absorbs, handled to a small amount of SO up to standard easily in postorder circulation alkali liquor2, going out
Mouth reaction gas O2Content is lower than under conditions of 1v%, the catalyst performance stabilised, and the service life 5 years or more.The catalysis in the prior art
The usage of agent and reactor is to control 200-220 DEG C of bed temperature using appropriate low inlet temperature, in control SO2Production quantity
Under the premise of make H such as 90-95%2S conversion, mainly generates elemental sulfur, SO2Production quantity is smaller, reacts the H that works off one's feeling vent one's spleen2S concentration is far high
In SO2, postorder unit is mainly in such as activated carbon desulphurization agent adsorption treatment H2S or in slurries by H2S is oxidized to sulphur, wherein
The shortcomings that activated carbon desulphurization agent method is to need frequent hot recycling and unload useless agent when scrapping, fill the cumbersome of new agent, there is shut-down
Agent and solid waste problem are changed, by H in slurries2S be oxidized to the shortcomings that sulphur method be mainly produced sulphur quality it is lower.When
When selective oxidation entry process gas hydrogen sulfide content is lower than 0.5v%, H2The remaining content of S and generated SO2Content be easier control
Make required range.
In recovery technology of sulfur of the present invention, when cyclic absorption unit uses calcic liquid, exported in the 5th condenser Process Gas
With the 6th condenser of calcium liquid cyclic absorption unit process gas entrance setting, conventional shell-and-tube heat exchanger especially band can be used
The shell-and-tube heat exchanger of fin, process make shell side leave with rage, and cooling water walks tube side；During being cooled to 10-50 DEG C, contained by Process Gas
Most of steam can be condensed into water on heat-transfer surface, and sulphur droplet, sulphur steam entrained by Process Gas are condensed into sulphur powder entrance
Condensed water trapping, condensed water is also by the part SO in Process Gas2、H2S dissolution traps, gas bottom in and top out in heat exchanger, cooling water
Pipe is from top to bottom, to trap sulphur powder in the middle and lower part of cooling water pipe, condensed water compared with many places substantially, use up sulphur powder on the whole
Slurry outflow heat exchanger is formed possibly into condensed water, and is deposited under the surface deposition of top cooling water pipe as few as possible
Come, to keep heat exchanger effect；The plane of fin outside cooling water pipe is advisable with vertical direction installing, mitigates sulphur powder in fin
The deposition and cohesion on surface.Cooling water can be switched to 250 DEG C of superheated steams such as in tube side when efficiency is reduced and will changed by heat exchanger
Hot face sedimentary sulfur fusing, evaporation are removed, and during which postorder lye cyclic absorption can temporarily play the role of heat exchanger.6th is cold
Condenser can also have the structure except shell-and-tube heat exchanger, contain sulphur powder, SO as described above2、H2The condensate liquid of S as circulation fluid,
By spraying and/or being atomized, gas-liquid contact, Process Gas cooling, sulphur trapping and part SO are realized2、H2The solution absorption of S, condensation
The advantages of liquid is controlled by liquid-liquid heat exchanger to appropriate low temperature with cooling water, the condensation method is Process Gas head loss
Small, sulfur deposition influences condensation effect small.
In recovery technology of sulfur of the present invention, the condensate liquid containing sulphur powder, the separation containing sulphur powder in lye can pass through eddy flow
Sedimentation or natural subsidence are at the higher sulphur slurry of sulphur powder content；It is further separated by filtration, or uses steam after concentration accumulation
Molten sulfur will be sent to Molten sulphur slot after the fusing layering of contained sulphur powder by Pressurized-heated.Contain lye as described in trapping sulphur powder
Middle sodium sulphate, concentration of sodium sulfite are lower (being lower than 3m%, generally below 2m%), are practically free of in the 6th condenser condensate liquid
Sulfate, sulphite are all free of the solid state component other than sulphur powder, thus sulphur powder generated, separated sulphur out
Slurry is impure less, and all more clean, purity is much higher than the wet oxidation such as containing tannin extract, FeOOH etc molysite ingredient
Absorb H2Sulphur slurry or sulphur obtained by S.
In recovery technology of sulfur of the present invention, circulating absorption solution maintains sulfur acid sodium, sodium sulfite outside normal operation more than needed
Liquid or sulfur acid calcium, calcium sulfite slurries more than needed, are sent to sewage device processing, or be sent to fire coal boiler fume wet desulphurization unit
It handles and as make-up water source and raw material, or is sent to coal-burning boiler as coal water drenching, wherein sewage device, fire coal boiler fume
The facility condition of processing unit is more perfect, management controlled level it is higher, be easy to by the containing sulfate of the separated sulphur powder,
Sulfite solution or slurries handle the level to qualified discharge or recycling, and the requirement as coal water drenching is then more wide
Pine.Wherein sewage device, the facility condition of fire coal boiler fume processing unit are more perfect, and management controlled level is higher, are easy to
Containing sulfate, sulfite solution or the slurries of the separated sulphur powder are handled to the water to qualified discharge or recycling
It is flat.Wherein, the prevailing technology of the wet desulphurization of fire coal boiler fume is calcium carbonate-calcium sulfate method, calcium carbonate slurries spray or
SO contained by atomization absorption flue gas2, calcium sulfite is generated, also there is Sodium/Calcium Dual alkali wet desulphurization, using sodium hydroxide and/or pure
Alkali absorption SO2, add lime to generate calcium sulfite and regenerate alkali；Gained calcium sulfite is all sulfuric acid by the air oxidation blasted
Calcium, then by calcium sulfate separation, utilize.The sulfur acid sodium, sodium sulfite liquid more than needed to be sent to Sodium/Calcium Dual alkali wet desulphurization
It is advisable, and the slurries more than needed of sulfur acid calcium, calcium sulfite can be sent to calcium carbonate-calcium sulfate method or Sodium/Calcium Dual alkali wet desulphurization
It is any.The sulfur acid sodium, liquid and the sulfur acid calcium more than needed of sodium sulfite, calcium sulfite slurries more than needed, ingredient letter
It is single, it is practically free of organic ingredient, quantity is smaller, and easily in sewage device, flue-gas desulfurizing device processing, reason is it
The aqueous condensed water for steam in Process Gas, added alkali, calcium raw material it is all simple nontoxic.
In recovery technology of sulfur of the present invention, since the absorbing liquid more than needed is sent to sewage device processing, or it is sent to coal-fired pot
Kiln gas wet desulphurization cell processing and as make-up water source, or it is sent to coal-burning boiler as coal water drenching, it can be alkali or calcium
Inventory suitably relax i.e. using some higher inventory or concentration, make circulating absorption solution that there is higher absorbability,
It is preferential to guarantee to H if lye pH value can be higher2S、SO2Absorbability, guarantee atmosphere discharge concentration it is up to standard or lower, and
The utilization rate of alkali, calcium is not haggled over excessively；It need be not excessively and haggle over whether crystal of calcium sulfate situation is up to standard to meet user or downstream
The requirement of user, because the amount of absorbing liquid of the present invention and contained alkali, calcium concentration are typically well below fire coal boiler fume wet process
Liquid measure and concentration when desulfurization will not cause it significantly to influence.
Recovery technology of sulfur of the present invention is utilized in Process Gas by H2The condensed water that S aoxidizes sulphur institute processed by-product vapor is made
For the water source of cyclic absorption unit, special without water is supplemented and controls.Different H2Steam contained by the Process Gas of S content sour gas
Condensate liquid quantity situation in different condensation temperatures, as listed by the following table 1.Design conditions: H in sour gas2S and aequum air
Reaction is converted into sulphur, and air is not excessive；12kPa at 50 DEG C of the saturated vapour pressure of water, 7.4kPa at 40 DEG C；It is free of in sour gas
Hydrocarbon, ammonia etc. can generate the ingredient of water with air reaction；The unit volume when combustion furnace uses oxygen-enriched air or oxygen-enriched air+air
It is larger when the condensation water quantity ratio air of Process Gas.
Condensate liquid quantity situation of the steam contained by 1 Process Gas of table in different condensation temperatures
。
In recovery technology of sulfur of the present invention, selective oxidation reaction device exit procedure gas or cyclic absorption unit entry process
The SO of gas2, it is easy to control to 1000 mg/m3Within, it generally can control to 600 mg/m3Within, especially in sour gas condition
When fluctuating smaller；According to condensing capacity listed by table 1, sulfate, sulfite concentration are easy to control 2m% in circulating absorption solution
Within in addition 1m% within, even sulfur acid calcium, calcium sulfite slurries be also easier to long distance delivery；It is arranged from chimney top
It is less to enter salinity contained by the droplet of chimney and atmosphere out, light to the corrosion of chimney, the exhaust of chimney top has been not likely to produce
Color plume, low wind speeds chimney are nearby not easy the white powder that descends slowly and lightly in ground, and sulfate, sulfite concentration are remote in circulating absorption solution
Lower than existing alkaline process, calcium method, ammonia process technical treatment SO2Circulating absorption solution sulfite salt, sulfate 10m% or more it is highly concentrated
Degree is horizontal.Existing alkaline process, calcium method, ammonia process technical treatment SO2Circulating absorption solution in, due to contained sulphite, sulfate compared with
Height, general demister are poor to the trapping ability of 2.5 μm of diameter or less saliferous drops, sulphite containing higher concentration, sulfuric acid
The Process Gas of salt drop enters chimney and atmosphere, exists to chimney and corrodes, and the exhaust of chimney top is also easy to produce visible plume, low wind speed
When chimney nearby ground be easy the white powder that descends slowly and lightly.Selective oxidation reaction device exit procedure gas or cyclic absorption unit enter to make a slip of the tongue
The H of journey gas2S, since its content is far below SO2Content is easy to absorb processing to 10 required mg/m3Following content；H2S
Product in absorbing liquid is also easy in the processing of the absorbing liquid more than needed or is converted into innocuous substance such as sulfate.
In recovery technology of sulfur of the present invention, Process Gas after cyclic absorption can be warming up to through heat exchange as 75 DEG C or more again into
Chimney empties, and steam is unsaturated in Process Gas, does not generate condensate liquid substantially in chimney, mitigates to the corrosion of chimney, and the service life extends,
Chimney top end group does not originally have visible plume.
In recovery technology of sulfur of the present invention, it can use the cyclic absorption treated a small amount of Process Gas as purge gass purification
Treatment liquid sulphur slot and molten sulfur, and the acid gas storage tank before combustion furnace is returned to, by H contained in molten sulfur2S etc. is recycled.
First to fourth heater can be realized by modes such as mesohigh steam, conduction oil, fuel combustions, may be used also
It is implemented in combination with, described can more heat, the combination of heat exchange mode is realized with the first to the 5th condenser.
Process Gas outlet section in 5th condenser, it is settable by one or more layers stainless steel or the deflector of PTFE material
Or silk screen, filler trap molten sulfur droplet, and are collected as molten sulfur using the falling of the self gravity of molten sulfur.Second to the 4th condenser it
Setting molten sulfur mist eliminator may be selected afterwards, converged molten sulfur droplet in gas by mist eliminator, and returned using the self gravity of molten sulfur
It falls and is collected as molten sulfur, the mist component of catching of molten sulfur mist eliminator is stainless steel or the deflector or silk screen of PTFE material, filler.
Recovery technology of sulfur of the present invention does not set incinerator, and there is no the consumption of fuel, supply and cost problems.
Detailed description of the invention
Attached drawing 1 is a kind of process flow diagram of sour gas recovery technology of sulfur of the present invention.
Device numbering in Fig. 1 is successively are as follows: 1 combustion furnace, 2 waste heat boilers, 3 first condensers, 4 second condensers, 5 thirds
Condenser, 6 the 4th condensers, 7 the 5th condensers, 8 the 6th condensers, 9 primary heaters, 10 secondary heaters, 11 thirds add
Hot device, 12 the 4th heaters, 13 level-one claus reaction devices, 14 second level claus reaction devices, 15 selective hydrogenation reduction reactions
Device, 16 selective oxidation reaction devices, 17 absorbing liquid towers, 18 sulphur slurries knockout drums, 19 circulating pumps, 20 Molten sulphur slots, 21 cigarettes
Chimney, 22 adsorbent towers.
Specific embodiment
In the sour gas sulfur recovery facility of a set of 6000 tons/year of scales, some technological parameter experiments are carried out, to selection
Property oxidation reactor after the 5th condensator outlet Process Gas, done absorption processing experiment, so as to being illustrated to present invention process,
But the limitation to present invention process is not constituted.
The sulfur recovery facility, capital equipment are anti-to the combustion furnace including being sequentially connected in series, level-one Crouse along acid gas stream
Answer device, second level claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device, cyclic absorption unit；Burning
Furnace is attached to waste heat boiler, is respectively set before and after claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device
First to the 5th condenser and first to fourth heater；First to the 5th condenser is cold by the gaseous sulfur in Process Gas respectively
It coagulates for molten sulfur, the storage of molten sulfur influent sulphur slot；First to fourth heater respectively will be from first to fourth condenser overhead
Process Gas out is heated to required temperature and enters back into respective reaction device；Wherein, Fe is loaded on level-one claus reaction device top2O3/
Al2O3TiO is loaded in de-oxygen type catalyst for recovering sulfur, lower part2Base catalyst for recovering sulfur；Second level claus reaction device dress
Fill out TiO2Base catalyst for recovering sulfur；Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Selective reduction SO2Catalysis
Agent；Selective oxidation reaction device loads Fe2O3-CeO2-Cr2O3/SiO2Selective oxidation H2S catalyst.
In the normal process of the sulfur recovery facility, the 5th condensator outlet Process Gas is through work after selective oxidation reaction device
Property charcoal desulfurizing agent tower handle the emptying of laggard 90m chimney.Handled sour gas contains H during experiment2S30-40v%。
To verify present invention process, small-sized the 6th condenser and cyclic absorption unit experiment are set after the 5th condenser
Equipment, by Process Gas with 1.0-1.1m3/ min flow (measures) after the 6th condenser, is drawn by the 5th condensator outlet pipeline branch pipe
Enter the 6th condenser and cyclic absorption unit；Cyclic absorption unit includes transparent plastic absorption tower and absorbing liquid circulating pump,
Absorb the bottom of the tower is used as liquid storage tank is absorbed, and atomizer is arranged in absorption tower inner top, and absorption tower middle and upper part sky canister portion is divided into
Absorbing liquid can effectively be distributed, play abundant suction full of the atomization absorption space by absorbing liquid atomization absorption space, atomizer
Adduction；6th condenser is by circulating water cooling to 40 DEG C, and the condensate liquid of bottom leakage fluid dram discharge is through transparent plastic cylinder, sedimentation
Collect and flow into supplement water of the absorb the bottom of the tower as circulating absorption solution after sulphur slurry, exhaust outlet connection absorption tower middle and lower part incited somebody to action
Journey gas is sent into absorption tower；Exhaust outlet is set at the top of absorption tower, connects a NaOH/ activated carbon tower, process gas disposal heel row is entered existing
Field environment.The NaHCO of concentration 1m% is used respectively3Solution, ultra-fine CaCO3Slurries are as absorbing liquid.
Experiment the first stage main technologic parameters include:
1150 DEG C of furnace temperature or so, 350 DEG C of Process Gas temperature after waste heat boiler, the first condensator outlet Process Gas temperature
170 DEG C, H2S4v%, SO22.5v%, COS+CS20.5v%；
239 DEG C of degree of primary heater exit procedure temperature, 325 DEG C of temperature of lower of level-one claus reaction device catalyst bed, the
Two 150 DEG C of condensator outlet Process Gas temperature, H2S 1.4v%, SO20.7v%, COS+CS2≤5mg/m3；
210 DEG C of degree of secondary heater exit procedure temperature, 236 DEG C of temperature of lower of second level claus reaction device catalyst bed, the
Three 140 DEG C of condensator outlet Process Gas temperature, H2S0.6v%, SO20.3v%；
220 DEG C of temperature of third heater outlet Process Gas, selective hydrogenation reduction reactor catalyst bed temperature of lower 240
DEG C, the 4th 140 DEG C of condensator outlet Process Gas temperature, H2S0.5v%, SO2 ≤20mg/m3；
4th condensator outlet Process Gas fills into the desired amount of air and mixes into the 4th heater, exit procedure temperature degree 215
DEG C, 242 DEG C of temperature of lower of selective oxidation reaction device catalyst bed, the 4th 135 DEG C of condensator outlet Process Gas temperature,
H2S60-90mg/m3, SO2800-1000mg/m3, O20.4-0.8v%, CO2About 30v%, remaining is steam and N2；
6th 40 DEG C of condensator outlet temperature degree, bottom leakage fluid dram condensing liquid quantity about 125-130g/min；
Absorption tower absorbing liquid uses 1m%NaHCO3When solution, initial stage pH8 or so, work off one's feeling vent one's spleen H on absorption tower2S≤2mg/m3, SO2≤
10mg/m3；NaHCO is calculated according to processing tolerance and absorbing liquid amount3When consuming 80%, work off one's feeling vent one's spleen H on absorption tower2S≤5mg/m3, SO2
≤20mg/m3, COS+CS2≤6mg/m3；
Absorption tower absorbing liquid uses 1m%CaCO3When slurries, initial stage pH5.5 or so, work off one's feeling vent one's spleen H on absorption tower2S≤5mg/m3, SO2
≤20mg/m3；CaCO is calculated according to processing tolerance and absorbing liquid amount3When consuming 60%, work off one's feeling vent one's spleen H on absorption tower2S≤8mg/m3, SO2
≤30mg/m3, COS+CS2≤6mg/m3。
Experiment second stage main technologic parameters include:
1180 DEG C of furnace temperature or so, 350 DEG C of Process Gas temperature after waste heat boiler, the first condensator outlet Process Gas temperature
170 DEG C, H2S4.5v%, SO22.5v%, COS+CS20.5v%；
230 DEG C of degree of primary heater exit procedure temperature, 325 DEG C of temperature of lower of level-one claus reaction device catalyst bed, the
Two 150 DEG C of condensator outlet Process Gas temperature, H2S 1.6v%, SO20.7v%, COS+CS2≤5mg/m3；
205 DEG C of degree of secondary heater exit procedure temperature, 230 DEG C of temperature of lower of second level claus reaction device catalyst bed, the
Three 140 DEG C of condensator outlet Process Gas temperature, H2S0.7v%, SO20.2v%；
220 DEG C of temperature of third heater outlet Process Gas, selective hydrogenation reduction reactor catalyst bed temperature of lower 245
DEG C, the 4th 140 DEG C of condensator outlet Process Gas temperature, H2S0.6v%, SO2 ≤20mg/m3；
4th condensator outlet Process Gas fills into the desired amount of air and mixes into the 4th heater, exit procedure temperature degree 225
DEG C, 260 DEG C of temperature of lower of selective oxidation reaction device catalyst bed, the 4th 135 DEG C of condensator outlet Process Gas temperature,
H2S30-50mg/m3, SO21000-1200mg/m3, O20.8-1.3v%, CO2About 45v%, remaining is N2；
6th 40 DEG C of condensator outlet temperature degree, bottom leakage fluid dram condensing liquid quantity about 125-135g/min；
Absorption tower absorbing liquid uses 1m%NaHCO3When solution, initial stage pH8 or so, work off one's feeling vent one's spleen H on absorption tower2S≤2mg/m3, SO2≤
10mg/m3, COS+CS2≤4mg/m3；NaHCO is calculated according to processing tolerance and absorbing liquid amount3When consuming 80%, absorption tower outlet
Gas H2S≤5mg/m3, SO2≤25mg/m3, COS+CS2≤6mg/m3；
Absorption tower absorbing liquid uses 1m%CaCO3When slurries, initial stage pH5.5 or so, work off one's feeling vent one's spleen H on absorption tower2S≤3mg/m3, SO2
≤30mg/m3, COS+CS2≤6mg/m3；CaCO is calculated according to processing tolerance and absorbing liquid amount3When consuming 60%, absorption tower outlet
Gas H2S≤6mg/m3, SO2≤35mg/m3, COS+CS2≤6mg/m3。
In the experiment in two above stage, the condensate liquid of the 6th condenser bottom leakage fluid dram discharge is received in transparent plastic cylinder
Collection, sedimentation, bottom gained sulphur powder pulp color turn to be yellow, easily settled and filtering, supernatant clarification, and sulphur obtained by filtering is through simple water
Purity is higher than 99.5m% after washing drying, and color is purer.The quality condition of the sulphur slurry is preferable, when running up to certain amount
Pressurization, low-pressure steam fusing can be played through pump, the molten sulfur isolated directly is recycled into Molten sulphur slot.
Through place company sewage-treatment plant, coal-burning boiler device personnel to the 1m%NaHCO3Solution consumption 80%,
1m%CaCO3The absorption of containing sulfate, sulphite and a small amount of sulphurizing salt when slurry consumption 60% have more than needed liquid carry out it is inorganic at
Divide, the detailed detection of organic principle, it is believed that inorganic constituents is simple, content is low, organic ingredient is practically free of, relative to sewage treatment
The treating capacity or demand of device, fire coal boiler fume wet desulphurization unit or coal water drenching, recovery technology of sulfur of the present invention are used
Lifting rate when commercial plant is smaller, thus can be sent to sewage device processing discharge, can also be sent to fire coal boiler fume wet process
Desulfurization unit using, as coal water drenching utilize.
In the working off one's feeling vent one's spleen of absorption tower when recovery technology of sulfur of the present invention is used for commercial plant, SO2Content has reached ultralow
The requirement of discharge, H2S、COS、CS2Equal smell substances content is extremely low, also complies with emission request, can empty through chimney.
Claims (10)
1. a kind of recovery technology of sulfur of middle low concentration sour gas contains H for handling2The sour gas of S20-50v%, capital equipment edge
Acid gas stream to include be sequentially connected in series combustion furnace, level-one claus reaction device, second level claus reaction device, selective hydrogenation also
Former reactor, selective oxidation reaction device, cyclic absorption unit；Combustion furnace is attached to waste heat boiler, claus reaction device, selectivity
The first to the 5th condenser and first to fourth heating are respectively set before and after hydrogenation reduction device, selective oxidation reaction device
Device；Gaseous sulfur in Process Gas is condensed into molten sulfur, the storage of molten sulfur influent sulphur slot respectively by the first to the 5th condenser；The
The Process Gas come out from first to fourth condenser overhead is heated to required temperature respectively and enters back into phase by one to the 4th heater
Answer reactor；
Wherein, Fe is loaded on level-one claus reaction device top2O3/Al2O3De-oxygen type catalyst for recovering sulfur, lower part filling
TiO2Base catalyst for recovering sulfur or pure TiO2Catalyst for recovering sulfur；The de-oxygen type catalyst for recovering sulfur is in addition to tool
There is claus reaction active, also by the O in Process Gas2By with H2S reaction generates elemental sulfur and removes；The TiO2Base sulphur
Recycle catalyst or pure TiO2Catalyst for recovering sulfur is in addition to active with claus reaction, also by COS, CS in Process Gas2It connects
It is bordering on and is completely converted into elemental sulfur or H2S, COS, CS2Total content≤10mg/m3；
Second level claus reaction device loads catalyst for recovering sulfur, under conditions of being lower than level-one claus reaction temperature, carries out
Further claus reaction conversion, the catalyst for recovering sulfur are TiO2Base catalyst for recovering sulfur, TiO2/Al2O3Sulphur
Recycle catalyst and Al2O3One or both of catalyst for recovering sulfur；In the second level claus reaction device exit procedure gas
H2S+SO2Content≤1.5v%；
Selective hydrogenation reduction reactor loads CoO-MoO3/Al2O3Or CoO-MoO3/ TiO2-Al2O3Selective reduction SO2It urges
Agent utilizes the H generated in combustion furnace2By SO2Close to whole reduction, primary product is elemental sulfur；
Selective oxidation reaction device loads selective oxidation H2S catalyst is filled into using before the reactor inlet by introducing air
O2By H2For S close to being totally converted, selective oxidation is elemental sulfur, and by-product is a small amount of SO2；The selective oxidation reaction device
H in exit procedure gas2S content≤100mg/m3, SO2Content is H2Five times or more of S content；
Cyclic absorption unit includes absorption tower, and setting is for Process Gas, filler and/or the spray of circulating absorption solution distribution and contact in tower
Leaching, atomization component, the pH5-10 of circulating absorption solution, 20-50 DEG C of operation temperature, main water quantity balance is vapoury for Process Gas
Condensed water, circulating absorption solution maintain to operate normally outside liquid more than needed be sent to sewage device processing, or to be sent to fire coal boiler fume wet
Method desulfurization unit handles and as make-up water source, or is sent to coal-burning boiler as coal water drenching；Circulating absorption solution be containing lye and/
Or calcic liquid, wherein being to contain sulfurous acid by supplement sodium hydroxide, sodium carbonate or sodium bicarbonate maintenance absorbability containing lye
Sodium and/or metabisulfite solution, calcic liquid are to maintain containing for absorbability by supplement calcium oxide, calcium hydroxide, calcium carbonate superfine powder
Calcium sulfite and/or calcium sulfate slurries；When cyclic absorption unit uses calcic liquid, on absorption tower, the setting the 6th of Process Gas entrance is cold
Condenser, Process Gas are first cooled to 20-50 DEG C through the 6th condenser, and some vapor is condensed into water, contained sulphur droplet, powder and is caught
Collection forms the feed liquid containing sulphur powder, into absorption tower or its attached cyclic absorption liquid storage tank and matches again after feed liquid separation sulphur slurry
Calcium oxide, calcium hydroxide, calcium carbonate superfine powder is added to carry out cyclic absorption；
The recovery technology of sulfur includes lower step:
1) enter combustion furnace after sour gas is mixed with aequum air and/or oxygen-enriched air to burn, the temperature control of combustion furnace
It makes the Process Gas that generates after 1050-1300 DEG C, burning and enters after waste heat boiler and be cooled to 260-350 DEG C, Process Gas is from waste heat
Boiler export enters the first condensate cooler and is cooled to 140-170 DEG C, after the condensation of the elemental sulfur that is generated in combustion furnace with process
Gas is segregated into Molten sulphur slot；
2) it is heated to 210-250 DEG C of required temperature from the Process Gas that the first condenser overhead comes out, into level-one claus reaction
Device carries out claus reaction and COS, CS2Hydrolysis；Control the H of the reactor inlet gas2S、SO2Content and temperature make reactor
Middle catalyst bed lower part reaches COS, CS2The temperature being fully hydrolyzed, wherein TiO2It is 320-350 when base catalyst for recovering sulfur
DEG C, pure TiO2It is 300-350 DEG C when catalyst for recovering sulfur；Exit procedure gas enters the second condenser and is cooled to 130-160 DEG C,
Enter Molten sulphur slot after separating the elemental sulfur generated with Process Gas；
3) enter second level claus reaction device after being heated to 210-230 DEG C from the Process Gas that the second condenser overhead comes out；From two
The Process Gas that grade claus reaction device comes out enters third condenser and is cooled to 130-160 DEG C, makes the elemental sulfur generated and process
Enter Molten sulphur slot after gas separation；
4) it is heated to 200-220 DEG C from the Process Gas that third condenser overhead comes out, into Chemoselective reduction device；From selection
Property the Process Gas that comes out of reduction reactor enter the 4th condenser and be cooled to 130-150 DEG C, the elemental sulfur and Process Gas point of generation
Enter Molten sulphur slot from rear；
5) from the 4th condenser overhead come out Process Gas fill into aequum air and mix after, be heated to 200-230 DEG C it is laggard
Selectable oxidation reactor, catalyst bed temperature of lower reach 220-280 DEG C；The mistake come out from selective oxidation reaction device
Journey gas enters the 5th condenser and is cooled to 120-140 DEG C, and the elemental sulfur of generation enters Molten sulphur slot, mistake after separating with Process Gas
Journey gas is through optional molten sulfur trap trap sulfur mist and after flowing into liquid-state sulfur slot, into cyclic absorption cell processing；
6) Process Gas come out from the 5th condenser overhead or molten sulfur trap, into cyclic absorption cell processing after arranged through chimney
It is empty；Wherein cyclic absorption unit uses when containing lye, and the cooling of Process Gas, some vapor are condensed into water, contained sulphur droplet, powder
Grain and SO2、H2The trapping of S, all by containing lye circulated sprinkling or atomization absorption realize, lye by circulating cooling water management temperature,
Sulphur slurry or liquid more than needed are separated in lye cyclic process is being sent to sewage device processing or to be sent to fire coal boiler fume wet process de-
Sulphur slurry is separated before sulphur cell processing.
2. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that the level-one claus reaction device, second level
Claus reaction device, selective hydrogenation reduction reactor, selective oxidation reaction device are all adiabatic reactors.
3. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that the catalysis of level-one claus reaction device filling
In agent, the TiO2Base catalyst for recovering sulfur contains TiO285m% or more, remaining is calcium sulfate binder, surface area 100-130m2/
G, pore volume 0.20-0.35ml/g；The pure TiO2Catalyst for recovering sulfur contains TiO299m% or more, surface area 120-180m2/
G, pore volume 0.3-0.5ml/g.
4. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that the selective oxidation H2S catalyst with
SiO2For carrier, Fe2O33-10m%, CaO 0-3m%, La2O3+CeO2+Cr2O3+V2O53-7m%；Catalyst average pore diameter
30nm or more, surface area 40-60m2/ g, pore volume 0.5-0.6ml/g.
5. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that cyclic absorption unit uses calcic liquid when institute
In the 6th condenser being arranged, gas bottom in and top out, cooling water pipe from top to bottom, makes sulphur powder in cooling water pipe on the whole
Lower part, condensed water trap to form slurry outflow heat exchanger compared with many places.
6. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that condensation of the cyclic absorption unit containing sulphur powder
Liquid, the separation containing sulphur powder in lye, by rotational flow settlement or natural subsidence at the higher sulphur slurry of sulphur powder content；Sulphur
Slurry is further separated by filtration, or melts sulphur with steam Pressurized-heated after concentration accumulation, and molten sulfur is sent to liquid after layering
Sulphur slot.
7. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that circulating absorption solution maintains outside normal operation
Sulfur acid sodium, sodium sulfite liquid more than needed are sent to Sodium/Calcium Dual alkali wet desulphurization；Sulfur acid calcium, calcium sulfite slurries more than needed give
Toward calcium carbonate-calcium sulfate method or Sodium/Calcium Dual alkali wet desulphurization.
8. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that the raw material containing alkali feeds intake in circulating absorption solution
Amount or concentration are higher than 20% or more aequum, and the inventory or concentration of calcic raw material are higher than 40% or more aequum.
9. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that with the cyclic absorption, that treated is a small amount of
Process Gas returns to the acid gas storage tank before combustion furnace as purge gass purified treatment Molten sulphur slot and molten sulfur；And/or circulation
It absorbs treated Process Gas and is warming up to 75 DEG C or more again into chimney emptying through heat exchange.
10. the recovery technology of sulfur of sour gas described in claim 1, which is characterized in that first to fourth heater passes through
Mesohigh steam, conduction oil, fuel combustion mode are realized, and/or counterflow heat exchange reality is carried out in conjunction with the first to the 5th condenser
It is existing；And/or the 5th Process Gas outlet section in condenser, setting by one or more layers stainless steel or PTFE material deflector or
Silk screen, filler trap molten sulfur droplet, and are collected as molten sulfur using the falling of the self gravity of molten sulfur.
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