CN103693626B - A kind ofly carbonated hydrogen sulfide acid gas is utilized to prepare the method for Sodium sulfhydrate - Google Patents
A kind ofly carbonated hydrogen sulfide acid gas is utilized to prepare the method for Sodium sulfhydrate Download PDFInfo
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- CN103693626B CN103693626B CN201310697615.XA CN201310697615A CN103693626B CN 103693626 B CN103693626 B CN 103693626B CN 201310697615 A CN201310697615 A CN 201310697615A CN 103693626 B CN103693626 B CN 103693626B
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- acid gas
- hydrogen sulfide
- sodium
- decarburization
- sulfhydrate
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- 239000007789 gas Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 99
- 239000002253 acid Substances 0.000 title claims abstract description 74
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 66
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 title claims abstract description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 162
- 238000005261 decarburization Methods 0.000 claims abstract description 60
- 239000003513 alkali Substances 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 53
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 24
- 235000011089 carbon dioxide Nutrition 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 230000008020 evaporation Effects 0.000 claims abstract description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims abstract description 6
- 230000002441 reversible effect Effects 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 61
- 239000000243 solution Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010977 unit operation Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 14
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005262 decarbonization Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 sulfone amine Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 3
- 229940043276 diisopropanolamine Drugs 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JCVAWLVWQDNEGS-UHFFFAOYSA-N 1-(2-hydroxypropylamino)propan-2-ol;thiolane 1,1-dioxide;hydrate Chemical compound O.O=S1(=O)CCCC1.CC(O)CNCC(C)O JCVAWLVWQDNEGS-UHFFFAOYSA-N 0.000 description 1
- IUQJDHJVPLLKFL-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetate;dimethylazanium Chemical compound CNC.OC(=O)COC1=CC=C(Cl)C=C1Cl IUQJDHJVPLLKFL-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- HGYMTOSBDUVQSC-UHFFFAOYSA-N C(O)(O)=O.CC=C.[F] Chemical compound C(O)(O)=O.CC=C.[F] HGYMTOSBDUVQSC-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 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 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The present invention discloses and a kind ofly utilizes carbonated hydrogen sulfide acid gas to prepare the method for Sodium sulfhydrate, belongs to technical field of decarburization.First the hydrogen sulfide acid gas of the buffered soln containing sodium hydroxide and sodium bicarbonate and non-decarburization is carried out hybrid reaction and absorbs carbonic acid gas in acid gas and partial vulcanization hydrogen by the method, obtain decarburization rich solution, then decarburization rich solution is heated, make the Sodium sulfhydrate generation hydrolysis reaction in decarburization rich solution, change into sodium hydroxide, hydrolysis reaction generate sodium hydroxide and decarburization rich solution in free alkali and reaction of sodium bicarbonate generate sodium carbonate; Hydrogen sulfide acid gas after carbon dioxide removal is entered tubular-mix reactor, obtains the rich solution containing Sodium sulfhydrate with the reverse absorption of circulation alkali liquor, by the rich solution evaporation concentration containing Sodium sulfhydrate, the Sodium sulfhydrate product of obtained different grade.The inventive method can carbon dioxide removal from hydrogen sulfide acid gas effectively, and after utilizing decarburization, acid gas prepares the quality controllable adjustable of Sodium sulfhydrate goods.
Description
Technical field:
The invention belongs to technical field of decarburization, be specifically related to a kind ofly utilize carbonated hydrogen sulfide acid gas to prepare the method for Sodium sulfhydrate.
Background technology:
Domestic production Sodium sulfhydrate commonly uses the method for Sodium Sulphide (sodium Na) absorbing hydrogen sulphide.And the traditional preparation methods of sodium sulphite has coal reduction sodium sulfate, the barium sulphide by-product method of adopting, gas reduction sodium sulphate method, caustic soda absorbing hydrogen sulphide method etc.The basic skills of current domestic production industry Sodium sulfhydrate manufactures Sodium sulfhydrate with sodium sulfide solution absorbing hydrogen sulphide gas.And domestic production sodium sulphite adopts carbon reduction sodium sulphate method substantially, main raw material is saltcake and coal, and Technology is simple, but temperature of reaction is up to 900 ~ 1100 DEG C, therefore calcine coal reduction of mirabilite production production technology of sodium sulfide and there is high pollution, the problems such as high energy consumption.And iron content, be the principal element affecting sodium sulphite quality product containing sodium carbonate salt.
Utilize carbonated hydrogen sulfide acid gas to prepare Sodium sulfhydrate product, be that one both can Purge gas, the recycling economy technology of valuable components in tail gas can be made full use of again.
At chemical fields such as Coal Chemical Industry, petrochemical complex, gas chemical industry, chemical fertilizer industries, tail gas clean-up is the important technology of each class chemical process with being separated, wherein gas removal carbonic acid gas and hydrogen sulfide technology be separated at chemical fertilizer industry, flue gas, technique all widespread uses such as purified synthesis gas.And gas decarbonization technology and desulfurization technology are associated both at home and abroad, that is gas has decarburization function while desulfurization.Can be divided into dry desulfurization decarburization and wet desulphurization decarburization by technology category, dry method adopts solid adsorbent to be called pressure swing adsorption process, and wet method solution washing absorbs.Wet method is divided into again four kinds, as chemical-solvent method, and physical solvent process, physical-chemical solvent method, and direct translation method.Chemical-solvent method utilizes basic solution and acid gas component to react generate certain compound and separated from gas by acid gas component, as activated hot potash method, hydramine method (thanomin MEA process, diethanolamine DEA process, diglycolamine DGA method, diisopropanolamine (DIPA) DIPA method, methyldiethanolamine MDEA method and sterically hindered amines, mixing hydramine, formula alkanolamine solution etc.).Physical solvent process utilizes some solvent to H
2s, CO
2the method that acid gas component is separated by the difference of solubleness, as many glycol dimethyl ethers Selexol method, propene carbonate Fluor method, cold methanol Rectisol method.Physics-chemical method is that to have the solution of physics and chemistry method concurrently used in combination, conventional hydramine, physical solvent and water are mixed into physical chemistry solvent, typical physical-chemical method has sulfone amine Sulfinolifc1, comprise DIPA-tetramethylene sulfone (Sulfinol-D method, sulfone amine II method, MDEA-sulfolane process, Sulfinol-M method, sulfone amine III method, also have Amisol, Selefining, Selefinig, Optisol and Flexsorb mixing SE method in addition.Direct translation method is exactly wet oxidation process, or claims oxidation-reduction method, and be widely used in tail gas desulfurization and the decarburizations such as coke(oven)gas, water-gas, synthetic gas, what belong to this method has vanadium method, as ADA-NaVO
3method, tannin extract-NaVO
3method; Iron processes, as LO-Cat method, Sulferox method, EDTA complex iron, FD and iron alkaline process etc.
In existing decarburization technique, chemical fertilizer industry adopts the carbon rejection processes such as WATER-WASHING METHOD, Benfield method, propene carbonate method; Syngas for synthetic ammonia adopts the carbon rejection processes such as hot potash method-Padil method, NHD method, MDEA solution absorption method, sterically hindered ammonia process; Purified synthesis gas adopts low-temp methanol method, pressure swing adsorption process; Flue gas desulfurization decarburization adopts ammonia process.At petroleum chemical industry, generally adopt Kraus process process acid gas to produce sulphur so far, acid gas does not make carbonization treatment, and carbon dioxide gas enters environment with Claus tail gases, or enters environment after burning with tail gas.
It is hydrogen sulfide that petrochemical plant acid gas mainly forms, and in addition containing partial CO 2, acid gas Sodium sulfhydrate or sodium sulphite are most economical methods, but carbonic acid gas exists the quality of interference Sodium sulfhydrate or sodium sulphite, and therefore decarburization necessitates.Domestic acid gas Sodium sulfhydrate technique only has a set of acid gas decarbonization device, and technology is introduced from Japan, manages jointly with two Japan factories, and device is now located at three limited chemical companies of association of Shandong region.This device adopts the decarburization of hydramine method, device comprises alkanolamine solution cyclic absorption and alkanolamine solution cyclic regeneration two portions, alkanolamine solution energy absorbing carbon dioxide, also can absorbing hydrogen sulphide, there is no obvious absorption selectivity, therefore separate out carbonic acid gas and hydrogen sulfide during solvent reclamation and become secondary pollution source, resolution gas must carry out desulfurization process just can enter environment.In recent years environmental regulation promulgates strict emission standard to exhaust emissions, and Claus tail gases is adopted hydrotreatment by part refinery, and sulfur dioxide gas is reduced to stink damp, then reducing gas is returned solvent desulfurizer.Visible, hydramine method is traditional decarbonization, desulfuration technology, and for the acid gas occasion that there is hydrogen sulfide and carbonic acid gas simultaneously, MDEA solution can not wash rice separate hydrogen sulfide and carbonic acid gas clearly.The processing of refinery acid gas requires acid gas carbon dioxide removal before preparing Sodium sulfhydrate technique neutralizing treatment absorbing hydrogen sulphide.
Summary of the invention:
The present invention is directed to existing decarburization technique Problems existing, provide a kind of and utilize carbonated hydrogen sulfide acid gas to prepare the method for Sodium sulfhydrate.
Provided by the present inventionly a kind ofly utilize carbonated hydrogen sulfide acid gas to prepare the method for Sodium sulfhydrate, the method concrete steps are as follows:
(1) buffered soln and the hydrogen sulfide acid gas of non-decarburization are carried out the carbonic acid gas in the hydrogen sulfide acid gas of non-decarburization described in hybrid reaction absorption and partial vulcanization hydrogen, obtain the decarburization rich solution containing sodium bicarbonate and Sodium sulfhydrate;
Described buffered soln is the alkali lye containing sodium hydroxide and sodium bicarbonate; In described alkali lye, sodium bicarbonate comes from the absorption reaction of sodium hydroxide to the carbonic acid gas in the hydrogen sulfide acid gas of described non-decarburization, in described alkali lye, the mass concentration of sodium hydroxide is 10% ~ 40%, the pH value of described alkali lye is 8 ~ 12, the time of described hybrid reaction is 10 ~ 40 seconds, described hybrid reaction temperature is 50 ~ 100 DEG C, the internal circulating load of described alkali lye for described in non-decarburization hydrogen sulfide acid gas in 30 ~ 100 times of carbonic acid gas quality;
(2) heat the decarburization rich solution that described step (1) obtains, make the Sodium sulfhydrate generation hydrolysis reaction in decarburization rich solution, change into sodium hydroxide, and analyse release hydrogen sulfide return acid gas system; Free alkali in the sodium hydroxide that described hydrolysis reaction generates and described decarburization rich solution and reaction of sodium bicarbonate generate sodium carbonate; The final Formed acid sodium-salt of carbonic acid gas in the hydrogen sulfide acid gas of described non-decarburization is fixed, and obtains the hydrogen sulfide acid gas after carbon dioxide removal; And in the final sucked back acid gas of hydrogen sulfide that described hydrolysis reaction generates, enter and remove hydrogen sulfide and the unit operation preparing Sodium sulfhydrate; Described hydrolysising reacting temperature: 70 ~ 100 DEG C, described hydrolysis reaction pressure :-0.01 ~-0.09MPa;
(3) the hydrogen sulfide acid gas after the carbon dioxide removal described step (2) obtained enters tubular-mix reactor, obtains the rich solution containing Sodium sulfhydrate with the reverse absorption of circulation alkali liquor; This tubular-mix reactor relies on the injection of circulation alkali liquor to produce suction and is sucked by sulfide hydrogen acid gas, adopt gas-liquid conversed flowing contact reacts mode, add alkali continuous production Sodium sulfhydrate continuously, described circulation alkali liquor is the solution containing sodium hydroxide, the mass concentration of described circulation alkali liquor is 30% ~ 35%, the described gas-liquid conversed flowing catalytic time is 2 ~ 3 seconds, and described gas-liquid conversed flowing contact reacts temperature controls in 65 ~ 85 DEG C;
(4) the rich solution evaporation concentration containing Sodium sulfhydrate described step (3) obtained, the Sodium sulfhydrate product of obtained different grade, described evaporation concentration temperature is 35 ~ 60 DEG C, and the pressure of described evaporation concentration is normal pressure.
The inventive method comprises:
1, adopt alkaline buffer solution, control the absorption to hydrogen sulfide and the selective absorbing to carbonic acid gas.
2, thermolysis effect heating decarburization rich solution is adopted, Sodium sulfhydrate is hydrolyzed, Sodium sulfhydrate hydrolysis is analysed releasing hydrogen sulfide and is returned acid gas system, reaction of sodium bicarbonate in the sodium hydroxide that hydrolysis generates and the free alkali of solution and rich solution generates sodium carbonate, the final Formed acid sodium-salt of carbonic acid gas in acid gas is fixed, and in the final sucked back acid gas of hydrogen sulfide, continue the formation reaction participating in Sodium sulfhydrate.
3, adopt gas-liquid countercurrent method sodium hydroxide solution to absorb hydrogen sulfide in acid gas and produce Sodium sulfhydrate product.
The inventive method know-why is specific as follows:
1, adopt buffered soln to suppress and incur loss through delay the absorption of hydrogen sulfide.Hydrogen sulfide is different with carbonic acid gas two component dissolving course in the solution, after hydrogen sulfide is delivered to liquid phase from gas phase, the corresponding dividing potential drop that there is hydrogen sulfide on liquid level, the hydrogen sulfide molecule be dissolved in liquid phase dissociation can be transformed into ionic state by molecular state immediately, dividing potential drop corresponding on liquid level also disappears thereupon, and favourable its of rapid ionization process of hydrogen sulfide dissolves and absorb.Be expressed as with chemical equation:
Gas phase interface liquid phase
H
2SH
2SH
＋HS
－，
If solution has basic cpd or alkali ion, the sulphur hydrogen ion (HS in liquid phase
-) rapidly and basic ion be combined into salt.NaOH+H
++ HS
-==NaHS+H
++ OH
-, the solution absorption of the more large more favourable hydrogen sulfide of basicity.
But when the basicity in solution is little, and in solution, there is abundant bicarbonate radical (HCO
3 -) ion time, due to the difference of Acidity, bicarbonate ion is easy to sulphur hydrogen ion to cement out from molecules of salt.Chemistry is referred to as displacement.
Na-HS+H
++HCO
3 －==Na
++HCO
3 －+HS
－＋H
+，
↓
NaHS+H
++HCO
3 －==Na-HCO
3+H
2S↑，
When solution exists sufficient sodium bicarbonate component, or absorb dioxide solution when containing sufficient carbonic acid, the absorption of hydrogen sulfide is suppressed.
Sufficient carbonic acid or bicarbonate ion is had to exist in order to make solution, be necessary for absorption process and the sufficient time is provided, compensate carbonic acid gas in the time of dissolving and dissociation processes generation hydration reaction consumes, provide and meet the basicity condition that carbon dioxide absorption reaction generates sodium bicarbonate.
2, thermolysis is adopted to make decarburization absorption liquid remove hydrogen sulfide.When concentration of hydrogen sulfide in acid gas is higher, gas concentration lwevel is not bery high, the absorbed probability of hydrogen sulfide increases, and there is Sodium sulfhydrate probability in absorption liquid increases.In order to ensure the quality of decarburization end article, need hydrogen sulfide decomposition and separation from absorption liquid to go out.Be hydrolyzed during the heating of the Sodium sulfhydrate aqueous solution, separate out hydrogen sulfide, and generate sodium hydroxide.
NaHS+H
2O＝NaOH+H
2S↑
This hydrolysis reaction is reversible in theory, but separates out hydrogen sulfide after sucked back acid gas system, broken above-mentioned molecular balance, above-mentioned reaction is in fact irreversible.In order to ensure the irreversible of above reaction, the present invention adopts heating hydrolysis and negative pressure-pumping.Heating hydrolysis temperature controls between 70 ~ 100 DEG C, and negative pressure is in-0.01 ~-0.09Mpa scope.Under vacuum heating conditions, separate out hydrogen sulfide, the sodium hydroxide of generation and reaction of sodium bicarbonate generate sodium carbonate, by carbon dioxide fixation in sodium carbonate salt.
NaHCO
3+NaOH＝Na
2CO
3+H
2O
The present invention solve from acid gas with in soda absorbing carbon dioxide process to the decrease uptake of hydrogen sulfide and absorb after decomposition and separation technology, in addition this invention exploits the process unit of this decarburization technique, see accompanying drawing 1, device mainly arranges the reactive tank adopting tubular-mix reactor, decarbonizing liquid thermal decomposer, sodium carbonate moisture eliminator etc.
3, the acid gas after decarburization is absorbed to generate Sodium sulfhydrate.Two to three reactors are adopted to absorb.In acid gas, concentration of hydrogen sulfide reduces successively, and new alkali lye injects from last reactor.And the supplementary alkali lye of second reactor is supplemented by the residue alkali lye of the 3rd reactor, the alkali lye of first reactor is supplemented by the residue alkali lye of second reactor.Therefore, concentration of lye successively decreases from back to front successively.Reaction product becomes Sodium sulfhydrate gradually by generating sodium sulphite.
3rd or the second reactor absorption reaction:
2NaOH+H
2S==Na
2S+2H
2O
First reactor absorption reaction:
Na
2S+H
2S==2NaHS
NaOH+H
2S==NaHS+H
2O。
4, evaporation concentration is containing Sodium sulfhydrate rich solution, can obtain the Sodium sulfhydrate product that mass concentration is 40% to 70% different grade.
Present invention process flow process effectively controls the generation of sodium sulphite in product, and effectively control the residual quantity of Hydrogen Sulfide Tail Gas after absorbing, make exhaust quality reach environmental protection standard, after seeing Fig. 2 decarburization, acid gas prepares Sodium sulfhydrate technical process principle schematic simultaneously.
The inventive method can carbon dioxide removal from hydrogen sulfide acid gas effectively, and can change into useful products sodium carbonate salt, and carbon-drop rate can reach 60 ~ 90%.The mass ratio of hydrogen sulfide and carbonic acid gas in carbon dioxide content and acid gas in acid gas is depended in the determination of carbon-drop rate height.Decarbonization process unit operation does not produce secondary pollution source, and obtains product.Amount of carbon dioxide residual after decarburization does not form the Mass Interference to Sodium sulfhydrate product.Hydrogen sulfide absorption prepares the controllable joint of Sodium sulfhydrate quality of item.Because the grade arranging evaporation concentration device product can be increased to 70% from 40%.
Accompanying drawing illustrates:
Fig. 1 buffered soln carbon rejection processes technical process principle schematic;
After Fig. 2 decarburization, acid gas prepares Sodium sulfhydrate technical process principle schematic.
In figure: A-non-decarburization acid gas; Acid gas after B-decarburization; The new alkali lye of C-decarburization; D-water coolant; E-pyrolysis periodic off-gases; F-heating steam; G-sodium carbonate; V-dry off-gas; Q-decarburization rich solution; L-decarburization circulation alkali liquor; S-hot blast; R-water of condensation; H-desulphurization circulating alkali lye; The new alkali lye of K-desulfurization; J-containing Sodium sulfhydrate rich solution; M-Sodium sulfhydrate product; W-phlegma; 1: decarburizing reaction groove, 2: tubular-mix reactor, 3: partial condenser, 4: circulation alkali pump, 5: thermal decomposer, 6: moisture eliminator; 7: desulphurization reactor, 8: tubular-mix reactor, 9: NaOH solution circulating pump, 10: evaporation concentrator, 11: finished pot, 12: partial condenser, 13: gas-liquid separator.
Embodiment:
The inventive method concrete operations are shown in shown in decarbonization process Fig. 1 and Sodium sulfhydrate preparation technology Fig. 2.
Decarbonization process Fig. 1: non-decarburization acid gas A is sprayed suction by decarburization circulation alkali liquor L at tubular-mix reactor 2, absorbs carbonic acid gas in acid gas and partial vulcanization hydrogen with alkali lye hybrid reaction.Alkali lye after reactive absorption acid gas enters decarburizing reaction groove 1 and sufficient dwell time, bicarbonate ion in alkali lye and Sodium sulfhydrate react, sulphur hydrogen radical ion is cemented out from Sodium sulfhydrate molecules of salt, produce displacement to hydrogen sulfide, partial vulcanization hydrogen molecule again leaves alkali lye and returns acid gas B after decarburization.Decarburization circulation alkali liquor main component is sodium bicarbonate, and according to pH value or the free alkali concentration of acid gas amount of carbon dioxide determination circulation alkali liquor, the new alkali lye C of decarburization adds before circulation alkali pump 4.Decarburization rich solution Q after the absorbing carbon dioxide of decarburizing reaction groove 1 and partial vulcanization hydrogen delivers to thermal decomposer 5, heat treated is carried out with heating steam F, to be absorbed in decarburization rich solution Q and the Sodium sulfhydrate generated issues raw hydrolysis reaction in heat effect generates hydrogen sulfide and sodium hydroxide, the hydrogen sulfide of separating out discharges thermal decomposer 5 with pyrolysis periodic off-gases E, is sucked be mixed into row decarburization absorption with non-decarburization acid gas and react after partial condenser 3 cools by tubular-mix reactor 2.Sodium hydroxide after hydrogen sulfide separated out by thermal decomposer 5 and reaction of sodium bicarbonate generate sodium carbonate and are concentrated.Sodium carbonate solution concentrated in thermal decomposer 5 is sent to moisture eliminator 6 hot blast S heating, concentrated, dry, and dried solid sodium carbonate G is by wrapping machine packaging final prod.Dry off-gas V enters environment through cleaning, and the condensed liquid of partial condenser 3 joins alkali lye recycling as decarburization.
Sodium sulfhydrate preparation technology flow process principle schematic as shown in Figure 2.After decarburization, acid gas B enters the tubular-mix reactor 8 at three grades of desulphurization reactor 7 tops successively, desulphurization circulating alkali lye H introduces NaOH solution circulating pump 9 bottom desulphurization reactor 7, tubular-mix reactor 8 is pressed into by NaOH solution circulating pump 9, and by acid gas B after jet power suction decarburization during press-in.Desulfurization new alkali lye K introduces before the 3rd NaOH solution circulating pump 9 from high-order alkali groove (not marking figure), before third stage circulation alkali liquor excess electron excess fraction shunts press-in second NaOH solution circulating pump 9 after NaOH solution circulating pump, the excess electron excess fraction of second stage circulation alkali liquor is before the second NaOH solution circulating pump 9 rear shunting press-in first NaOH solution circulating pump 9.Alkali lye and the acid gas of system form countercurrent flow and contact, finally, first step reactor cycles alkali lye excess electron excess fraction enrichment Sodium sulfhydrate, separate after first step recycle pump containing Sodium sulfhydrate rich solution J, and enter evaporation concentrator 10, with the rich solution J containing Sodium sulfhydrate in heating steam F chuck heating evaporation thickener 10.Water of condensation R enters condensate system, what evaporation concentrator 10 steamed cools fractional condensation containing sour water vapour at partial condenser 12 water coolant D, be separated at gas-liquid separator 13, the phlegma W separated enters Technics in Condensate System, and the pyrolysis periodic off-gases E separated is sucked back desulphurization reactor 7 by tubular-mix reactor 8 and together absorbed by alkali lye with acid gas again.Sodium sulfhydrate product enters finished pot 11 by the bottom of evaporation concentrator 10.The output of product can adopt tank car also can transport outward sale by modes such as barreleds.
Claims (1)
1. utilize carbonated hydrogen sulfide acid gas to prepare a method for Sodium sulfhydrate, it is characterized in that the method concrete steps are as follows:
(1) buffered soln and the hydrogen sulfide acid gas of non-decarburization are carried out the carbonic acid gas in the hydrogen sulfide acid gas of non-decarburization described in hybrid reaction absorption and partial vulcanization hydrogen, obtain the decarburization rich solution containing sodium bicarbonate and Sodium sulfhydrate;
Described buffered soln is the alkali lye containing sodium hydroxide and sodium bicarbonate; In described alkali lye, sodium bicarbonate comes from the absorption reaction of sodium hydroxide to the carbonic acid gas in the hydrogen sulfide acid gas of described non-decarburization, in described alkali lye, the mass concentration of sodium hydroxide is 10% ~ 40%, the pH value of described alkali lye is 8 ~ 12, the time of described hybrid reaction is 10 ~ 40 seconds, described hybrid reaction temperature is 50 ~ 100 DEG C, the internal circulating load of described alkali lye for described in non-decarburization hydrogen sulfide acid gas in 30 ~ 100 times of carbonic acid gas quality;
(2) heat the decarburization rich solution that described step (1) obtains, make the Sodium sulfhydrate generation hydrolysis reaction in decarburization rich solution, change into sodium hydroxide, and analyse release hydrogen sulfide return acid gas system; Free alkali in the sodium hydroxide that described hydrolysis reaction generates and described decarburization rich solution and reaction of sodium bicarbonate generate sodium carbonate; The final Formed acid sodium-salt of carbonic acid gas in the hydrogen sulfide acid gas of described non-decarburization is fixed, and obtains the hydrogen sulfide acid gas after carbon dioxide removal; And in the final sucked back acid gas of hydrogen sulfide that described hydrolysis reaction generates, enter and remove hydrogen sulfide and the unit operation preparing Sodium sulfhydrate; Described hydrolysising reacting temperature: 70 ~ 100 DEG C, described hydrolysis reaction pressure :-0.01 ~-0.09MPa;
(3) the hydrogen sulfide acid gas after the carbon dioxide removal described step (2) obtained enters tubular-mix reactor, obtains the rich solution containing Sodium sulfhydrate with the reverse absorption of circulation alkali liquor; This tubular-mix reactor relies on the injection of circulation alkali liquor to produce suction and is sucked by the hydrogen sulfide acid gas after carbon dioxide removal, adopt gas-liquid conversed flowing contact reacts mode, add alkali continuous production Sodium sulfhydrate continuously, described circulation alkali liquor is the solution containing sodium hydroxide, the mass concentration of described circulation alkali liquor is 30% ~ 35%, the described gas-liquid conversed flowing catalytic time is 2 ~ 3 seconds, and described gas-liquid conversed flowing contact reacts temperature controls in 65 ~ 85 DEG C;
(4) the rich solution evaporation concentration containing Sodium sulfhydrate described step (3) obtained, the Sodium sulfhydrate product of obtained different grade, described evaporation concentration temperature is 35 ~ 60 DEG C, and the pressure of described evaporation concentration is normal pressure.
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| CN104071758A (en) * | 2014-07-15 | 2014-10-01 | 袁磊 | Device and method for preparing sodium hydrosulfide |
| CN105731388B (en) * | 2014-12-06 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method and device for preparing NaHS |
| CN105731387B (en) * | 2014-12-06 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of method and device that sodium acid carbonate is prepared by sour gas |
| KR101795466B1 (en) * | 2016-10-31 | 2017-11-10 | 주식회사 포스코 | Gas treating method and apparatus therefor |
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| CN114854457B (en) * | 2022-01-20 | 2023-04-18 | 中国中煤能源集团有限公司 | Decarbonization and desulfurization method for mixed gas containing combustible gas |
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