CN116445198B - 一种高效脱硫剂及其制备方法 - Google Patents
一种高效脱硫剂及其制备方法 Download PDFInfo
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- CN116445198B CN116445198B CN202310463810.XA CN202310463810A CN116445198B CN 116445198 B CN116445198 B CN 116445198B CN 202310463810 A CN202310463810 A CN 202310463810A CN 116445198 B CN116445198 B CN 116445198B
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- sulfur
- sodium
- desulfurizing agent
- chelating agent
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 39
- 239000011593 sulfur Substances 0.000 claims abstract description 39
- 239000002738 chelating agent Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 16
- 230000002745 absorbent Effects 0.000 claims abstract description 16
- 239000006172 buffering agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 15
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 15
- 239000011775 sodium fluoride Substances 0.000 claims description 10
- 235000013024 sodium fluoride Nutrition 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical group [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 abstract description 28
- 230000023556 desulfurization Effects 0.000 abstract description 28
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 239000007789 gas Substances 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 18
- -1 nitrate ions Chemical class 0.000 description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 5
- NNXNKLLWTKSODZ-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate;iron;sodium Chemical compound [Na].[Fe].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O NNXNKLLWTKSODZ-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940080260 iminodisuccinate Drugs 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WKVMOQXBMPYPGK-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CC(O)=O WKVMOQXBMPYPGK-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- QPWHIXUCVYSLML-UHFFFAOYSA-K C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].[Fe+2].C(CN)N.[Na+] Chemical group C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].[Fe+2].C(CN)N.[Na+] QPWHIXUCVYSLML-UHFFFAOYSA-K 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/90—Chelants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0204—Metals or alloys
- C10L2200/024—Group VIII metals: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/02—Absorbents, e.g. in the absence of an actual absorbent column or scavenger
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
- C10L2300/40—Mixture of four or more components
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- Analytical Chemistry (AREA)
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- Gas Separation By Absorption (AREA)
Abstract
本发明涉及脱硫剂技术领域,尤其涉及IPC B01D53领域,进一步的,涉及一种高效脱硫剂及其制备方法。按质量百分比计,原料包括:可溶性铁盐2~6%、吸收剂2~6%、硫磺颗粒调节剂2~4%、缓冲剂1~4%、螯合剂0.5~2%、去离子水补充余量。本发明制备得到的高效脱硫剂硫容高,化学性质稳定;实现硫单质的迅速分离,缓解对反应釜的腐蚀率,脱硫效率高。
Description
技术领域
本发明涉及脱硫剂技术领域,尤其涉及IPC B01D53领域,进一步的,涉及一种高效脱硫剂及其制备方法。
背景技术
通常油气田,沼气,天然气,焦炉煤气开发过程中都含有一定量的H2S组分,为了保证清洁、安全生产,满足后续产品加工要求,需要将H2S脱出。目前焦炉煤气净化基本上采用传统PDS(双核磺化酞菁钴)脱硫技术,但是传统的PDS脱硫技术由于在脱出H2S的同时也能脱除HCN,煤气中含有CO2、O2、HCN等气体,脱硫过程中会产生大量复盐,不仅会造成PDS失去催化性能,还会造成系统管路堵塞,减少循环量,影响脱硫液喷淋密度,因此需要定期排放进行处理,造成后续处理费用和环保压力比较大。
中国专利CN110559831 A公开了一种络合铁脱硫剂,包括:水;可溶性铁盐;铁盐络合剂;稳定剂;硫磺改性剂;碱性物质。制备得到的脱硫剂脱硫速度快且效率高;吸收速率快、低毒性、副盐产率低;添加了特定的硫磺改性剂,硫磺易回收,在5分钟内硫颗粒粒度增大至30微米而沉降分离;添加了独特的稳定剂,能使络合铁脱硫剂在3个月的连续运转中降解量小于5%。但是该技术方案引入了氯离子,会对设备造成一定的腐蚀。
中国专利CN 112973404 A公开了一种络合铁脱硫剂及其制备方法和应用。所述络合铁脱硫剂包括:可溶性铁盐、亚氨基二琥珀酸盐、聚天冬氨酸盐、硫化氢吸收剂、缓蚀剂和水。该技术方案提供的络合铁脱硫剂的硫容高,副盐产生量少且不受温度影响,生成的硫磺颗粒纯度高、粒径大、易于分离的优势,具有较高的应用价值。但是该技术方案引入了硝酸根离子,废水难处理。
发明内容
为解决上述技术问题,本发明第一方面提供了一种高效脱硫剂,按质量百分比计,原料包括:可溶性铁盐2~6%、吸收剂2~6%、硫磺颗粒调节剂2~4%、缓冲剂1~4%、螯合剂0.5~2%、去离子水补充余量。
在一些优选的实施方式中,所述可溶性铁盐选自铁钠盐、铁铵盐、硝酸铁、氯化铁、硫酸铁中的一种或多种组合。
优选的,所述可溶性铁盐为铁钠盐。
进一步优选的,所述铁钠盐为乙二胺四乙酸铁钠。
在一些优选的实施方式中,所述吸收剂选自N-甲基二乙醇胺、乙二胺、N-羟乙基哌嗪、二氮杂二环、环丁砜中的一种或多种组合。
优选的,所述吸收剂为N-甲基二乙醇胺。
优选的,所述乙二胺四乙酸铁钠和N-甲基二乙醇胺的质量比为(3~5):(3~4)。
进一步优选的,所述乙二胺四乙酸铁钠和N-甲基二乙醇胺的质量比为4.2:3.9。
申请人在实验过程中发现,采用乙二胺四乙酸铁钠和N-甲基二乙醇胺作为脱硫组合物,可以提高复合脱硫剂的吸收和再生速度,提高脱硫效率,猜测可能的原因是:乙二胺四乙酸铁钠与硫化氢接触反应,高价铁离子的氧化性将硫化氢氧化成单质硫,铁离子被还原为低价亚铁离子,生产氢离子,形成的氢离子与碱性的N-甲基二乙醇胺相互作用,氢离子被消耗,促使硫化氢的吸收反应正向进行,提高了脱硫剂的吸收效率。形成的低价的亚铁离子与氧气和水反应被重新氧化为三甲铁离子,实现脱硫剂的循环再生,高价态的铁离子可以重新参与脱硫反应,吸收和再生过程都主要是化学反应,且再生过程中不会汽提出硫化物,消除了二次污染,减小了二氧化碳对脱硫剂的吸收反应影响。
并且在乙二胺四乙酸铁钠和N-甲基二乙醇胺的共同作用下,含有N-甲基二乙醇胺的水溶液呈碱性可以进一步提高水溶液对硫化氢的吸收率,进一步提高脱硫效率。
在一些优选的实施方式中,所述硫磺颗粒调节剂为氟化钠、氢氧化钠、氢氧化钾中的一种或多种组合。
优选的,所述硫磺颗粒调节剂为氟化钠。
在一些优选的实施方式中,所述缓冲剂选自碳酸盐、碳酸氢盐、磷酸盐、磷酸氢盐中的一种或多种组合。
优选的,所述缓冲剂为碳酸盐。
进一步优选的,所述碳酸盐选自碳酸钠、碳酸钾中的一种或两种组合。
进一步优选的,所述碳酸盐为碳酸钾。
申请人在实验过程中发现,采用合适水解电离常数的碳酸钾作为缓冲剂可以稳定脱硫体系稳定的酸碱环境,使脱硫反应稳定持续进行,猜测可能的原因是:硫化氢为二级水解电离物质,在被吸收分离的过程中,会影响脱硫体系的酸碱稳定性,脱硫剂的脱硫效率与脱硫体系的酸碱性息息相关,脱硫体系的酸碱值剧烈变化会影响脱硫剂的吸收硫化氢和脱硫剂再生的效率。当脱硫体系呈现酸性时,会引起脱硫反应逆向进行,导致硫化氢的吸收量减少,影响脱硫进度。水解电离常数不在优选范围内的缓冲剂,不能实现硫化氢逐渐被吸收后,维持脱硫体系pH稳定的效果。
在一些优选的实施方式中,所述螯合剂选自氨基羧酸盐、羟基羧酸盐中的至少一种。
优选的,所述螯合剂为氨基羧酸盐。
优选的,所述氨基羧酸盐选自次氮基三乙酸盐、乙二胺四乙酸盐、亚氨基二琥珀酸盐中的一种或多种组合。
进一步优选的,所述氨基羧酸盐为次氮基三乙酸盐。
进一步优选的,所述氨基羧酸盐为次氮基三乙酸钠。
申请人在实验过程中发现,采用次氮基三乙酸钠作为螯合剂,提高了复合脱硫剂的稳定性,在10~60℃条件下,复合脱硫剂的吸收与再生反应的效率变化不大,避免了高浓度硫化氢条件下的硫容下降,猜测可能的原因是:当原料气中的硫化氢气体含量较高时会产生大量的硫化铁或硫化亚铁沉淀,溶液组成不稳定,一旦Fe3+减少,硫容便会大幅度降低,影响脱硫效率,采用次氮基三乙酸钠,其为配位数高的螯合剂,在10~60℃条件下,次氮基三乙酸钠可以与铁离子发生共同螯合作用,稳定脱硫剂中的铁离子组合,避免硫化铁和硫化亚铁沉淀的生成,造成溶液的不稳定。并且次氮基三乙酸钠可以与铁离子的络合稳定常数高于硫化铁和硫化亚铁,可以维持铁离子含量稳定,稳定脱硫反应。
优选的,所述次氮基三乙酸钠和氟化钠的质量比为(0.9~1.3):(2.8~3.4)。
进一步优选的,所述次氮基三乙酸钠和氟化钠的质量比为1.1:3.1。
申请人在实验过程中发现脱硫体系的溶液中存在钙、镁等离子,钙镁离子与螯合剂具有一定的反应性,会与铁离子竞争螯合,降低螯合剂对铁离子的螯合效果,申请人通过引入一定的氟化钠可以与钙镁等离子形成氟化钙和氟化镁颗粒,减少了干扰离子对螯合剂的影响。申请人进一步发现,脱硫反应过程中生成的硫磺颗粒较小,会附着于溶液中的小气泡并上浮到液面形成硫泡沫层,细小的硫化颗粒与氟化钙和氟化镁颗粒之间具有一定的吸附作用,可以聚集增加颗粒的粒径,使硫磺颗粒的粒径增大,降低了分离压力,简化了分离工艺。
本发明第二方面提供了一种高效脱硫剂的制备方法,其特征在于,包括以下步骤:
(1)将螯合剂完全溶于去离子水后加入可溶性铁盐使之完全溶解;
(2)将缓冲剂、硫磺颗粒调节剂、吸收剂依次加入步骤(1)中,搅拌均匀即得。
本发明的原理利用水溶液中正价铁离子的氧化还原性,使含硫化氢气体与含络合铁催化剂的水溶液进行气液相接触反应。该气液相接触反应首先通过水溶液的偏碱性,在气液接触时通过酸碱化学吸收将原料气中的硫化氢吸收进入水溶液;在水溶液中,利用高价铁离子的氧化性将硫化氢氧化成单质硫,铁离子被还原为低价亚铁离子。其主要反应如下:
1)碱性水溶液吸收H2S、CO2
Na2CO3+H2S→NaHCO3+NaHS
Na2CO3+CO2+H2O→2NaHCO3
2)析硫过程
2Fe3+(络合态)+HS-→2Fe2+(络合态)+S↓+H
nS↓+Fe2+→H2S→Fe(S)n(溶解态)
3)再生反应
Fe(S)n(溶解态)+O2→Fe3+(络合态)+S↓
2Fe2+(络合态)+1/2O2+H+→2Fe3+(络合态)+OH-2NaHCO3→Na2CO3+CO2+H2O
有益效果:
1、本申请采用乙二胺四乙酸铁钠和N-甲基二乙醇胺作为脱硫组合物,可以提高复合脱硫剂的吸收和再生速度,提高脱硫效率。
2、本申请采用合适水解电离常数的碳酸钾作为缓冲剂可以稳定脱硫体系的脱硫反应,提高脱硫剂的吸收硫化氢和脱硫剂再生的效率。
3、本申请采用次氮基三乙酸钠作为螯合剂,可以提高复合脱硫剂的使用稳定性,维持脱硫剂的高硫容量。
4、本申请引入一定的氟化钠可以与钙镁等离子形成氟化钙和氟化镁颗粒,减少了干扰离子对螯合剂的影响。
5、本申请通过先将螯合剂、可溶性铁盐以及水混合均匀,随后再依次加入缓冲剂、硫磺颗粒调节剂和吸收剂,使得各组分之间可以充分混匀并且保证组分的优异效果,制备方法简单、方便。
6、本申请实施例1制备得到的脱硫剂为红色透明流动性液体,pH值为9.7,密度为1.154g/cm3,保质期为2年,可以用于油气田、天然气、闪蒸气、伴生气、废气以及焦炉煤气开发过程的脱硫处理,原料气压力范围为0.1~0.6MPa,应用场景包括单井、场站、净化厂、集输站等。
具体实施方式
实施例1
实施例1提供了一种高效脱硫剂,按质量百分数计,原料包括:可溶性铁盐4.2%、吸收剂3.9%、硫磺颗粒调节剂3.1%、缓冲剂2.5%、螯合剂1.1%、去离子水补充余量。
所述可溶性铁盐为乙二胺四乙酸铁钠(CAS号:15708-41-5)。
所述吸收剂为N-甲基二乙醇胺(CAS号:105-59-9)。
所述硫磺颗粒调节剂为氟化钠。
所述缓冲剂为碳酸钾。
所述螯合剂为次氮基三乙酸钠(CAS号:5064-31-3)。
一种高效脱硫剂的制备方法,其特征在于,包括以下步骤:
(1)将螯合剂完全溶于去离子水后加入可溶性铁盐使之完全溶解;
(2)将缓冲剂、硫磺颗粒调节剂、吸收剂依次加入步骤(1)中,搅拌均匀即得。
实施例2
实施例2提供了一种高效脱硫剂,按质量百分数计,原料包括:可溶性铁盐4.0%、吸收剂4.0%、硫磺颗粒调节剂3.5%、缓冲剂3%、螯合剂1.5%、去离子水补充余量。
所述可溶性铁盐为乙二胺四乙酸铁钠(CAS号:15708-41-5)。
所述吸收剂为N-甲基二乙醇胺(CAS号:105-59-9)。
所述硫磺颗粒调节剂为氟化钠。
所述缓冲剂为碳酸钾。
所述螯合剂为次氮基三乙酸钠(CAS号:5064-31-3)。
一种高效脱硫剂的制备方法,其特征在于,包括以下步骤:
(1)将螯合剂完全溶于去离子水后加入可溶性铁盐使之完全溶解;
(2)将缓冲剂、硫磺颗粒调节剂、吸收剂依次加入步骤(1)中,搅拌均匀即得。
对比例1
对比例1提供了一种高效脱硫剂,其具体实施方式同实施例1,不同点在于,将次氮基三乙酸钠替换为柠檬酸钠。
对比例2
对比例2提供了一种高效脱硫剂,其具体实施方式同实施例1,不同点在于,所述螯合剂的质量百分数为2.5%。
对比例3
对比例3提供了一种高效脱硫剂,其具体实施方式同实施例1,不同点在于,将碳酸钾替换为磷酸钾。
对比例4
对比例4提供了一种高效脱硫剂,其具体实施方式同实施例1,不同点在于,不添加N-甲基二乙醇胺。
性能测试:
1、硫容量:将实施例1~2和对比例1~4制备得到的高效脱硫剂处理焦炉煤气,通过GC-2014C气相色谱仪进行尾气在线分析,检测硫化氢尾气含量,计算硫容量。
处理条件为:含硫气(体积分数)组成:H2S 20%,N2 80%;酸气流量:0.4L/min;空气流量:10L/min;压力:常压;吸收温度:45℃;再生温度:50℃
2、将实施例1制备得到高效脱硫剂用于焦化厂焦炉气的脱硫,参数及结果见表2~3。
测试结果:
表1
硫容量(g/L) | |
实施例1 | 3.0 |
实施例2 | 2.9 |
对比例1 | 2.2 |
对比例2 | 2.3 |
对比例3 | 2.4 |
对比例4 | 2.0 |
表2:山西某焦化厂
表3:山东某焦化厂
Claims (2)
1.一种高效脱硫剂,其特征在于,按质量百分比计,原料包括:可溶性铁盐2~6%、吸收剂2~6%、硫磺颗粒调节剂2~4%、缓冲剂1~4%、螯合剂0.5~2%、去离子水补充余量;
所述缓冲剂为碳酸钾;
所述吸收剂为N-甲基二乙醇胺;
所述可溶性铁盐为乙二胺四乙酸铁钠;
所述螯合剂为次氮基三乙酸钠;所述硫磺颗粒调节剂为氟化钠;所述次氮基三乙酸钠和氟化钠的质量比为(0.9~1.3):(2.8~3.4)。
2.一种根据权利要求1所述的高效脱硫剂的制备方法,其特征在于,包括以下步骤:
(1)将螯合剂完全溶于去离子水后加入可溶性铁盐使之完全溶解;
(2)将缓冲剂、硫磺颗粒调节剂、吸收剂依次加入步骤(1)中,搅拌均匀即得。
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CN115738631A (zh) * | 2022-11-24 | 2023-03-07 | 中国科学院大连化学物理研究所 | 一种离场电化学中的硫磺沉降剂及其应用 |
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