CN109432990A - A kind of desulfurization and decarburization absorbent - Google Patents
A kind of desulfurization and decarburization absorbent Download PDFInfo
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- CN109432990A CN109432990A CN201811392639.3A CN201811392639A CN109432990A CN 109432990 A CN109432990 A CN 109432990A CN 201811392639 A CN201811392639 A CN 201811392639A CN 109432990 A CN109432990 A CN 109432990A
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- China
- Prior art keywords
- iron
- absorbent
- complexing
- desulfurization
- organic solvent
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- 239000002250 absorbent Substances 0.000 title claims abstract description 62
- 230000002745 absorbent Effects 0.000 title claims abstract description 56
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 22
- 230000023556 desulfurization Effects 0.000 title claims abstract description 22
- 238000005261 decarburization Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 150000007530 organic bases Chemical class 0.000 claims abstract description 13
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000000536 complexating effect Effects 0.000 claims description 29
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 4
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical compound C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 claims description 3
- CEXIRVJKCXNSCM-UHFFFAOYSA-J C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Fe+4].C(CCC)N1CN(C=C1)C Chemical compound C(CN(CC(=O)[O-])CC(=O)[O-])N(CC(=O)[O-])CC(=O)[O-].[Fe+4].C(CCC)N1CN(C=C1)C CEXIRVJKCXNSCM-UHFFFAOYSA-J 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000008139 complexing agent Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- -1 1-butyl-3-methylimidazolium ethylenediaminetetraacetic acid iron Chemical compound 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 abstract description 3
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 abstract 2
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 abstract 1
- 229940078031 sodium ironedetate Drugs 0.000 abstract 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 17
- 239000011734 sodium Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- BXOAIZOIDUQOFA-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydroxide Chemical compound [OH-].CCCC[N+]=1C=CN(C)C=1 BXOAIZOIDUQOFA-UHFFFAOYSA-M 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 2
- XJECNSWAHCMYNZ-UHFFFAOYSA-N C=C.[Fe].[Na] Chemical group C=C.[Fe].[Na] XJECNSWAHCMYNZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- 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
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- 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
-
- 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
- C10L3/104—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/202—Alcohols or their derivatives
- B01D2252/2023—Glycols, diols or their derivatives
- B01D2252/2026—Polyethylene glycol, ethers or esters thereof, e.g. Selexol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2053—Other nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
- B01D2252/2056—Sulfur compounds, e.g. Sulfolane, thiols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
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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
- 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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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
Abstract
本发明公开了一种脱硫脱碳吸收剂，所述吸收剂包括络合铁、有机溶剂和有机碱，其中：铁的质量含量为0.3‑10g/L，有机碱的质量含量为0‑100g/L；所述络合铁包括1‑丁基‑3‑甲基咪唑乙二胺四乙酸铁、乙二胺四乙酸铁铵和乙二胺四乙酸铁钠；所述有机溶剂包括二甲基亚砜或聚乙二醇二甲醚或两者的混合物；所述有机碱能溶于所述有机溶剂，具体包括氢氧化1‑丁基‑3‑甲基咪唑。该吸收剂采用络合铁的非水溶液来避免络合剂的降解，降低液相催化氧化的成本。且该吸收液在氧化吸收硫化氢的同时物理吸收二氧化碳，降低了吸收的设备费用。The invention discloses a desulfurization and decarburization absorbent, the absorbent comprises complex iron, an organic solvent and an organic base, wherein: the iron content is 0.3-10 g/L, and the mass content of the organic base is 0-100 g/ L; the complexed iron includes 1-butyl-3-methylimidazolium ethylenediaminetetraacetic acid iron, iron ammonium diamine tetraacetate and sodium iron edetate; the organic solvent includes dimethyl Sulfone or polyethylene glycol dimethyl ether or a mixture of the two; the organic base is soluble in the organic solvent, specifically 1-t-butyl-3-methylimidazolium hydroxide. The absorbent uses a non-aqueous solution of complex iron to avoid degradation of the complexing agent and reduce the cost of liquid phase catalytic oxidation. Moreover, the absorbing liquid physically absorbs carbon dioxide while oxidizing and absorbing hydrogen sulfide, thereby reducing the equipment cost of absorption.
Description
Technical field
The present invention relates to gas purification processing technology field more particularly to a kind of desulfurization and decarburization absorbents.
Background technique
Hydrogen sulfide (H2S) this toxic acid contaminant, after not only corroding metallic conduit in transmission process but also burning
Acid Rain Pollution environment is formed, concentration is (20-30) × 10 in air-6When there is overpowering odor, increase to (100-150) ×
10-6When, smell paralysis is made one, reaches 1000 × 10-6When, causing death in a few seconds, therefore no matter from safety, environment or
From the aspect of health, the H of the industries such as petroleum refining, natural gas, coal chemical industry discharge2S has to pass through purified treatment.In addition, gas
Carbon dioxide in fluid fuel can also corrode equipment, influence combustibility, must also locate before being transported to end user
Reason.
Carbon dioxide (CO in the prior art2) the main direct emission after using hydramine absorption, parsing of purification, H2S purification master
The technique to be catalytically conveted to sulphur using Crouse (Claus) device is entered after hydramine absorption, parsing concentration, but Crouse
Treated that sulfurous gas is difficult to meet existing discharge standard for method.In this context, Complexing Iron liquid phase catalytic oxidation hydrogen sulfide skill
Art causes wide hair concern, and typical Complexing Iron aqueous solution catalytic system (LO-CAT technique) has the following characteristics that (1) directly will
Oxidation of Hydrogen Sulfide is sulphur, it is not necessary that hydrogen sulfide is first carried out concentration；(2) hydrogen sulfide treatment of various concentration, desulfurization are adapted to
Efficiency reaches 99.99% or more, is fully able to meet existing most stringent of hydrogen sulfide emission standard.Although LO-CAT patent work
Skill has been set up more set hydrogen sulphide disposal units in worldwide, but the operating cost of LO-CAT technique is quite high,
Need regular addition iron-retention agent, complexing iron stabilizers, bacterial inhibitor, surfactant etc. more to guarantee that it is operated normally
Kind reagent.The degradation of this high operating cost of LO-CAT technique complexing agent in complexing water solution, iron-retention agent
Degradation occur mainly in the ferrous regenerative process of complexing, when the oxygen being complexed in ferrous aqueous solution and air contacts, produce
H is given birth to2O2, H2O2Modified Fenton reaction is constituted with ferrous complex, modified Fenton reaction generates energy of oxidation in aqueous solution
The very strong hydroxyl free radical of power, hydroxyl free radical are then used as main oxidant by organic complexing agent oxidative degradation, this is because
Activity of the modified Fenton reaction in most organic solvent is lower, it is difficult to generate the hydroxyl free radical of oxidation complexation agent.
Summary of the invention
The object of the present invention is to provide a kind of desulfurization and decarburization absorbent, which is kept away using the non-aqueous solution of Complexing Iron
The degradation for exempting from complexing agent reduces the cost of liquid phase catalytic oxidation.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of desulfurization and decarburization absorbent, the absorbent include Complexing Iron, organic solvent and organic base, in which:
The mass content of iron is 0.3-10g/L, and the mass content of organic base is 0-100g/L；
The Complexing Iron includes 1- butyl -3- methylimidazole iron ethylenediaminetetraacetate ([Bmim] [Fe (EDTA)]), second two
Amine tetraacethyl iron ammonium (NH4[Fe (EDTA)]) and sodium iron ethylene diamine tetra acetate (Na [Fe (EDTA)])；
The organic solvent includes the mixture of dimethyl sulfoxide or polyethylene glycol dimethyl ether or both；
The organic base can be dissolved in the organic solvent, specifically include hydroxide 1- butyl -3- methylimidazole ([Bmim]
OH)。
The absorbent can absorb CO simultaneously2And H2S, in which:
CO2Purification realized by Physical Absorption, H2The purification of S is realized by liquid phase catalytic oxidation.
The H2The process that the purification of S is realized by liquid phase catalytic oxidation specifically:
H2S generates sulphur by the Complexing Iron oxidative absorption in the absorbent, while Complexing Iron is reduced to complexing ferrous iron；
It then passes to excessive air and the complexing ferrous iron is regenerated as Complexing Iron, and by the CO in the absorbent2It blows
It takes off, realizes the regeneration of absorbent.
As seen from the above technical solution provided by the invention, above-mentioned absorbent is kept away using the non-aqueous solution of Complexing Iron
The degradation for exempting from complexing agent reduces the cost of liquid phase catalytic oxidation, while during catalysis oxidation hydrogen sulfide, realizes to titanium dioxide
The synchronous removal of carbon further decreases installation cost, power cost and the medicament of desulfurization and decarburization without in addition increasing equipment and reagent
Expense.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the composed structure schematic diagram of desulfurization and decarburization absorbent provided in an embodiment of the present invention.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
Novel natural gas, coal superior the embodiment of the invention provides a kind of absorbent properties and that parsing energy consumption can be effectively reduced
Change the desulfurization and decarburization absorbent of gas, refinery gas, biogas.Work of the embodiment of the present invention is further retouched in detail below in conjunction with attached drawing
It states, is as shown in Figure 1 the composed structure schematic diagram of desulfurization and decarburization absorbent provided in an embodiment of the present invention, which mainly wraps
Include Complexing Iron, organic solvent and organic base, in which:
The mass content of iron is 0.3-10g/L, and the mass content of organic base is 0-100g/L；
The Complexing Iron includes 1- butyl -3- methylimidazole iron ethylenediaminetetraacetate ([Bmim] [Fe (EDTA)]), second two
Amine tetraacethyl iron ammonium (NH4[Fe (EDTA)]) and sodium iron ethylene diamine tetra acetate (Na [Fe (EDTA)])；
The organic solvent includes the mixture of dimethyl sulfoxide or polyethylene glycol dimethyl ether or both；
The organic base can be dissolved in the organic solvent, specifically include hydroxide 1- butyl -3- methylimidazole ([Bmim]
OH).In the specific implementation, being also possible to other organic bases that can be dissolved in the organic solvent.
During carrying out desulfurization and decarburization processing using the absorbent, which can absorb CO simultaneously2And H2S,
In:
CO2Purification realized by Physical Absorption, H2The purification of S is realized by liquid phase catalytic oxidation.
In the specific implementation, H2The process that the purification of S is realized by liquid phase catalytic oxidation specifically:
H2S generates sulphur by the Complexing Iron oxidative absorption in the absorbent, while Complexing Iron is reduced to complexing ferrous iron；
It then passes to excessive air and the complexing ferrous iron is regenerated as Complexing Iron, and by the CO in the absorbent2It blows
It takes off, realizes the regeneration of absorbent.
It is described in detail below with desulfurization and decarburization treatment process of the specific example to above-mentioned absorbent:
The dimethyl sulfoxide absorbent of embodiment 1, Na [Fe (EDTA)]
1.6230g Na [Fe (EDTA)] is dissolved in 80mL dimethyl sulphoxide solution, is configured to absorbent, the absorbent
Concentration of iron be 2.5607g/L, acidity 0.0350mmoL/mL.
At room temperature, flow is 99.9% (v/v) O of 25mL/min2, flow is 99.9% (v/v) H of 10mL/min2S, together
When be passed through in the absorbing liquid of above-mentioned 40mL, catalysis-oxidation 4h is obtained by filtration sulphur solid, and dry weighing obtains unit time sulphur
Sulphur yield is 13.8705 (mg/ (mLh).
99.9% (v/v) CO that the 4g absorbent absorption pressure is 156.00Kpa, flow is 25mL/min2Reach balance
It afterwards, is the regeneration of 95mL/min air stripping, five cyclic absorption CO of every gram of absorbent with flow2Amount be followed successively by 0.0106g,
0.010g,0.0101g,0.0101g,0.0101g。
The polyethylene glycol dimethyl ether absorbent of embodiment 2, Na [Fe (EDTA)]
0.15g Na [Fe (EDTA)] is dissolved in 100mL polyethylene glycol dimethyl ether solution, crosses filter solid, supernatant is taken to make
For absorbent, the concentration of iron of the absorbent is 0.3795g/L.
At room temperature, flow is 99.9% (v/v) O of 25mL/min2, flow is 99.9% (v/v) H of 10mL/min2S, together
When be passed through in the absorbing liquid of above-mentioned 40mL, catalysis-oxidation 8h is obtained by filtration sulphur solid, and dry weighing obtains unit time sulphur
Sulphur yield is 0.7058 (mg/ (mLh).
99.9% (v/v) CO that the 4g absorbing liquid absorption pressure is 156.00Kpa, flow is 25mL/min2Reach balance
It afterwards, is the regeneration of 95mL/min air stripping with flow.Reach absorption equilibrium in 2.5 minutes, parsing balance reached in 2.5 minutes,
Five cyclic absorption CO of every gram of absorbent2Amount be 0.0092g.
The polyethylene glycol dimethyl ether absorbent of embodiment 3, [Bmim] [Fe (EDTA)]
0.32g [Bmim] [Fe (EDTA)] is dissolved in 100mL polyethylene glycol dimethyl ether solution, is crossed filter solid, is taken supernatant
Liquid is 1.0074g/L, acidity 0.0120mmoL/mL as absorbent, the concentration of iron of the absorbent.
At room temperature, flow is 99.9% (v/v) O of 25mL/min2, flow is 99.9% (v/v) H of 10mL/min2S, together
When be passed through in the absorbing liquid of above-mentioned 40mL, catalysis-oxidation 7h is obtained by filtration sulphur solid, and dry weighing obtains unit time sulphur
Sulphur yield is 4.2980 (mg/ (mLh).
99.9% (v/v) CO that the 4g absorbing liquid absorption pressure is 156.00Kpa, flow is 25mL/min2Reach balance
It afterwards, is the regeneration of 95mL/min air stripping with flow.Reach absorption equilibrium in 18min minutes, reaches parsing in 12 minute minute
Balance, five cyclic absorption CO of every gram of absorbent2Amount be followed successively by 0.0134g, 0.0137g, 0.0136g, 0.0136g,
0.0136g。
Embodiment 4, [Bmim] [Fe (EDTA)], [Bmim] OH polyethylene glycol dimethyl ether absorbent
0.32g [Bmim] [Fe (EDTA)] is dissolved in 100mL polyethylene glycol dimethyl ether solution, is added a certain amount of
[Bmim] OH adjusts acid-base property, crosses filter solid, takes supernatant as absorbent, and the concentration of iron of the absorbent is 1.0074g/L, acid
Degree is 0.0105mmoL/mL.
At room temperature, flow is 99.9% (v/v) O of 25mL/min2, flow is 99.9% (v/v) H of 10mL/min2S, together
When be passed through in the absorbing liquid of above-mentioned 40mL, catalysis-oxidation 8h is obtained by filtration sulphur solid, and dry weighing obtains unit time sulphur
Sulphur yield is 6.2714 (mg/ (mLh).
99.9% (v/v) CO that the 4g absorbing liquid absorption pressure is 156.00Kpa, flow is 25mL/min2Reach balance
It afterwards, is the regeneration of 95mL/min air stripping with flow.Reach absorption equilibrium in 6min minutes, it is flat that parsing is reached in 6 minute minute
Weighing apparatus, five cyclic absorption CO of every gram of absorbent2Amount be followed successively by 0.0104g, 0.0104g, 0.0103g, 0.0102g,
0.0101g。
The polyethylene glycol dimethyl ether and dimethyl sulfoxide absorbent of embodiment 5, Na [Fe (EDTA)]
0.6230g Na [Fe (EDTA)] is dissolved in 40mL polyethylene glycol dimethyl ether and the mixing of 20mL dimethyl sulfoxide is molten
In liquid, filter solid is crossed, takes supernatant as absorbent, the concentration of iron of the absorbent is 1.9226g/L, and acidity is
0.0175mmoL/mL。
At room temperature, flow is 99.9% (v/v) O of 25mL/min2, flow is 99.9% (v/v) H of 10mL/min2S, together
When be passed through in the absorbing liquid of above-mentioned 40mL, catalysis-oxidation 4h is obtained by filtration sulphur solid, and dry weighing obtains unit time sulphur
Sulphur yield is 13.4675 (mg/ (mLh).
It is worth noting that, the content being not described in detail in the embodiment of the present invention belongs to professional and technical personnel in the field's public affairs
The prior art known.
The difference that absorbent described in the embodiment of the present invention is absorbed with hydramine is: CO2And H2S is absorbed there is no competitive,
H2That the absorption of S relies on is the oxidation of iron complex, CO2It is simple physical dissolution, therefore air stripping can be fast
Speed realizes the complete regeneration of organic solvent, and air stripping also achieves the ferrous rapid regeneration of complexing.Therefore the absorbent has
By reusable after air regenesis, and the characteristics of low energy consumption in regenerative process.
Meanwhile the viscosity of the absorbent viscosity and water is in an order of magnitude, operation temperature can reach 100 DEG C, acidity value compared with
Low, there is no degradation and etching problems for nonaqueous phase, have huge energy-saving potential, are suitable for natural gas, coalification gas, refining
Factory's gas, the desulfurization of biogas, decarburization.
In conclusion absorbent described in the embodiment of the present invention has the advantages that
1) organic solvent is high boiling substance in the absorbent, has not volatile, stablizes that not oxidizable, corrosivity is low etc.
Advantage, and cheap, especially dimethyl sulfoxide, price is very low, and Na used [Fe (EDTA)] also has multiple commercial vendors confession
It answers, price is more reasonable, so the price of the absorbent is lower compared with other desulfurization and decarburization absorbents.
2) compared with single desulfurization or decarburization system, the absorbent system can simultaneously desulfurization and decarburization, reduce equipment
Expense, and the regeneration air of desulfurization, also stripping carbon dioxide simultaneously, reduces the energy consumption of whole system；
3) absorbent in use, without adding other reagents such as complexing agent, complexing agent stabilizer, is saved
Operating cost.
4) absorbent of the replaceable existing liquid phase catalytic oxidation hydrogen sulfide of the absorbent is directly used in existing apparatus,
After existing decarbonization device can also being transformed, become while the device of desulfurization and decarburization.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (3)
1. a kind of desulfurization and decarburization absorbent, which is characterized in that the absorbent includes Complexing Iron, organic solvent and organic base,
In:
The mass content of iron is 0.3-10g/L, and the mass content of organic base is 0-100g/L；
The Complexing Iron includes 1- butyl -3- methylimidazole iron ethylenediaminetetraacetate, ferric ammonium ethylene diamine tetraacetate and ethylenediamine tetraacetic
Acetic acid ferrisodium；
The organic solvent includes the mixture of dimethyl sulfoxide or polyethylene glycol dimethyl ether or both；
The organic base can be dissolved in the organic solvent, specifically include hydroxide 1- butyl -3- methylimidazole.
2. desulfurization and decarburization absorbent according to claim 1, which is characterized in that the absorbent can absorb CO simultaneously2And H2S,
Wherein:
CO2Purification realized by Physical Absorption, H2The purification of S is realized by liquid phase catalytic oxidation.
3. desulfurization and decarburization absorbent according to claim 2, which is characterized in that the H2The purification of S passes through liquid phase catalytic oxidation
Come the process realized specifically:
H2S generates sulphur by the Complexing Iron oxidative absorption in the absorbent, while Complexing Iron is reduced to complexing ferrous iron；
It then passes to excessive air and the complexing ferrous iron is regenerated as Complexing Iron, and by the CO in the absorbent2Stripping goes out
Come, realizes the regeneration of absorbent.
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