CN108840311A - It is a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium - Google Patents
It is a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium Download PDFInfo
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- CN108840311A CN108840311A CN201810659695.2A CN201810659695A CN108840311A CN 108840311 A CN108840311 A CN 108840311A CN 201810659695 A CN201810659695 A CN 201810659695A CN 108840311 A CN108840311 A CN 108840311A
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- eutectic solvent
- gas
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- phase oxidation
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- 239000002904 solvent Substances 0.000 title claims abstract description 63
- 230000005496 eutectics Effects 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 50
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- 239000007791 liquid phase Substances 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 59
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005864 Sulphur Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960001231 choline Drugs 0.000 claims abstract description 5
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims description 48
- 238000005660 chlorination reaction Methods 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 10
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 3
- 235000019743 Choline chloride Nutrition 0.000 claims description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 3
- 229960003178 choline chloride Drugs 0.000 claims description 3
- 238000011026 diafiltration Methods 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- 229940057054 1,3-dimethylurea Drugs 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical group CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- ICXXXLGATNSZAV-UHFFFAOYSA-N butylazanium;chloride Chemical compound [Cl-].CCCC[NH3+] ICXXXLGATNSZAV-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical group [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- -1 alcohol amine Chemical class 0.000 description 8
- 238000013478 data encryption standard Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- QQYKZHJPCRZEGB-UHFFFAOYSA-N CCCCCCN1C=CN(C1CC(=O)N)C Chemical compound CCCCCCN1C=CN(C1CC(=O)N)C QQYKZHJPCRZEGB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000031872 Body Remains Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 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 1
- 239000000975 dye Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/05—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by wet processes
-
- 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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing 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
- B01D53/14—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 by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a kind of methods removed using eutectic solvent as the hydrogen sulfide liquid phase oxidation of medium, belong to chemical separating field.The present invention using in amide derivatives, diol, derivatives one or more of mixtures as hydrogen bond donor, imidazole salts, quaternary ammonium salt or choline are as hydrogen bond receptor, it is mixed by certain mol proportion, thus the eutectic solvent of multiple functions is obtained, these eutectic solvents have stable physicochemical properties, cheap easily preparation, to H2S gas has excellent solubility, the easily characteristics such as recycling.Eutectic solvent designed by the present invention can be towards the H in various types of sulphur-containing gas sources2S gas is efficiently realized to H2The selectivity of S gas traps, and through room temperature liquid phase oxidation by the H of enrichment2S is rapidly converted into the sulphur of high-purity, and eutectic solvent renewable re-using after drying, whole process have many advantages, such as that desulfuration efficiency is high, operating condition is mild, energy consumption is small, VOC free s discharge, are a kind of efficient H of novel green2S oxidation removal method.
Description
Technical field
The invention belongs to chemical separating field, it is related to a kind of method of the removing and its resource utilization of hydrogen sulfide, specifically
It is to aoxidize the method for being converted into sulphur through room temperature efficient liquid phase after being enriched with hydrogen sulfide in eutectic solvent.
Background technique
Hydrogen sulfide (H2S it is) that one kind has strong corrosive, flammable hypertoxic gas, is widely present in natural gas, refining
In the gaseous fuels such as factory's gas, synthesis gas, also appear in the industrial or agricultural gas such as coal bed gas, biogas.H2The presence of S not only serious prestige
Environment and personal safety is coerced, and can also cause equipment and corrosion of piping, catalyst poisoning during gas conveys and utilizes
Deng.How by the H of hypertoxicity and highly corrosive2Resource utilization is S gas with carrying out safely and reliably storage and green high-efficient
One of project most challenged, and developing efficient hydrogen sulfide isolation technics is to reduce H in atmosphere2S concentration is the most effective
Strategy.Currently, industrial existing trapping and removing H2The method of S mainly includes dry and wet two major classes.Common dry method
Desulfurization such as membrane separation process, solid absorption-catalytic oxidation, gas phase Claus method etc..Compared with dry method, wet process removes H2S is always
The technology mainstream of industrial process, most typical hydramine method, there is also many bottleneck problems in application process：(1) it traps simultaneously
Remove H2The energy consumption of S process is high；(2) most alcohol amine absorbents have volatility, can generate volatile materials in use
(VOCs) it is discharged into atmosphere, forms secondary pollution；(3) organic amine is degradable or oxidation causes desulfuration efficiency to reduce.Therefore,
Develop the H of green high-efficient2S capture method has particularly important science and realistic meaning.
Eutectic solvent (DESs) is as a kind of novel green solvent, usually by the hydrogen bond receptor of certain stoichiometric ratio
It is composed with hydrogen-bond donor, property is very much like with ionic liquid, especially in gas separation field, either in H2S
Or SO2Removing aspect, DESs show brilliant absorption and regenerability, and about H2Converted in-situ after S trapping is ground
It is relatively slow to study carefully progress, if H can will be trapped2S and SO2Technique combine, through Claus process, (Claus method is a kind of to use SO2
By H2S is oxidized to the classical processes of sulphur simple substance) can be achieved element sulphur maximization recycling, and produce sulphur can be widely used for making
Make dyestuff, pesticide, match, gunpowder, rubber etc..The gas phase Claus technique of early stage is using metal oxide as catalyst (reaction temperature
>180 DEG C), but the sulphur generated easily condenses in solid catalyst surface, makes catalyst inactivation, and be often accompanied by 3~5% H2S gas
Body remains in the tail gas of Claus technique, needs additional purification process to handle Claus tail gas, and United States Patent (USP)
The liquid phase Claus technique of the reports such as US5733516A, US592860A and US7381393B2 then can effectively overcome gas phase Claus
The problems in technique can be realized in relatively relatively mild condition to H2The complete conversion of S.These novel liquid-phases Claus technique
Usually using polyglycol ether as reaction medium, but the volatilization problems of organic solvent still are difficult to overcome, and generate environmentally harmful
VOCs also brings many problems to actual mechanical process.Therefore, existing Claus technique needs further greenization improvement.It examines
H with higher in system need to be ensured by considering traditional Claus technique2S concentration, and it is being in excess in SO2In the case where react ability
It sufficiently carries out, so that Claus technique is in low H2The application of the field of gas treatment of S content is centainly limited to.Therefore, how will
Low concentration H2S enrichment is the key that liquid phase Claus process efficient carries out.Applicant is in Chinese patent
Use is provided in CN105521696A6 dissolved with SO2Ionic liquid (ILs) absorb H2The method of S, corresponding H2S can be with
96% conversion ratio and SO2Reaction generates sulphur, but the process is still limited by H2Low solubility of the S in ILs.In contrast,
DESs is to H2S, which has, more preferably absorbs accumulation ability, this is that low H is handled by Claus technique2S content gas provides elder generation
Machine.Currently, numerous publication (CN101961598A, CN101993378A, CN103159632A,
US2009291872A1 and WO2009142663A1) it is only report H2Reversible trapping new process of the S in absorbent, and there has been no
DESs traps H2S and its correlation technique of converted in-situ report, especially replace traditional effumability organic solvent with DESs, will
It is obviously more attractive that it is applied to liquid-phase oxidation process.
Summary of the invention
Goal of the invention：In view of the deficiencies of the prior art, it is an object of the present invention to provide one kind using eutectic solvent as medium
Hydrogen sulfide liquid phase oxidation removal method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
It is a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium, it is characterised in that with amide derivatives,
One or both of diol, derivatives be used as hydrogen bond donor, using one of imidazole salts, quaternary ammonium salt, choline as hydrogen bond by
Body is combined into eutectic solvent in proportion, realizes to H2The trapping of S, and the H that will be captured2S is converted through room temperature liquid phase oxidation
For sulphur, specific step is as follows：
(1) hydrogen bond donor and hydrogen bond receptor are mixed first by certain mol proportion, is stirred under proper temperature to keeping it total
Molten, gained liquid is eutectic solvent after being cooled to room temperature, and the mass percentage of water is less than in eutectic solvent obtained
0.5%；
(2) by above-mentioned eutectic solvent from H2Enter at the top of the absorption tower S, counter-current absorption contains certain volume through what tower bottom entered
The H of score2S gas to be processed, makes H2S is enriched in eutectic solvent, the H of formation2S rich solution is used for subsequent oxidation；
(3) by above-mentioned eutectic solvent from SO2Enter at the top of absorption tower, counter-current absorption contains certain volume through what tower bottom entered
The SO of score2Gas to be processed, makes SO2It is enriched in eutectic solvent, the SO of formation2Rich solution is used for subsequent oxidation；
(4) by H obtained in above-mentioned steps2S and SO2Rich solution be pumped to liquid phase oxidation reaction tower respectively, in tower top static state
Enter liquid phase oxidation reaction tower after vortex mixer mixing, reaction obtains the eutectic solvent emulsion containing sulphur；
(5) after by the eutectic solvent emulsion containing sulphur by the discharge of liquid phase oxidation reaction tower tower bottom, it was sent into diafiltration
It washs dry integrated machine and filters out eutectic solvent, separate, be dried to obtain sulphur finished product, and the eutectic solvent filtered out is through drying unit
Make water quality percentage composition therein less than 0.5% after dry regeneration, is re-fed into H2The absorption tower S and SO2Absorption tower, Oxygen in Liquid
Change excessive H in reaction tower tail-gas2S then reenters H2The absorption tower S.
Preferably, the hydrogen bond donor and hydrogen bond receptor are (1~5) in molar ratio:(1~5), whipping temp are room temperature
~150 DEG C.
Preferably, the hydrogen bond donor amide and its derivative are acetamide, urea, 1,3- dimethyl urea, 2- imidazolidine
One of ketone, 2-Pyrrolidone；The hydrogen bond donor diol, derivatives are ethylene glycol, diethylene glycol, triethylene glycol, tetrem two
One of alcohol, polyethylene glycol, 1,3 butylene glycol, 1,4- butanediol, glycerine；The hydrogen bond receptor choline is glycine betaine
(Beta), one of choline chloride (ChCl)；The hydrogen bond receptor quaternary ammonium salt is etamon chloride (N2222Cl), triethyl group
Butyl ammonium chloride (N2224Cl), tetrabutylammonium chloride (N4444One of Cl)；The hydrogen bond receptor imidazole salts are chlorination 1- second
Base -3- methylimidazole (EmimCl), chlorination 1- butyl -3- methylimidazole (BmimCl), chlorination 1- hexyl -3- methylimidazole
(HmimCl), 1- ethyl-3-methylimidazole rhodanate (EmimSCN), 1- butyl -3- methylimidazole rhodanate
(BmimSCN), one of 1- hexyl -3- methylimidazole rhodanate (HmimSCN).
Preferably, the H2The operation temperature on the absorption tower S is room temperature, and operating pressure 1.0Mpa, operation liquid-gas ratio is 8
~10Kg/Nm3, it is passed through containing H2S gas to be processed is H2Natural gas, oven gas plus the hydrogen that S volume fraction is 0.8%~1.8%
It is a kind of in sweet gas.
Preferably, the SO2The operation temperature on absorption tower is room temperature, and operating pressure 0.1Mpa, operating liquid-gas ratio is
40~50Kg/Nm3, it is passed through containing SO2Gas to be processed is H2The coal-fired flue-gas that S volume fraction is 0.2%.
Preferably, the tower top operation temperature of the liquid phase oxidation reaction tower is room temperature, and tower bottom operation temperature is 60~80
DEG C, operating pressure 1.0Mpa, H2S is relative to SO2With excessive (0~15) % of stoichiometric ratio.
Preferably, the H2The absorption tower S and SO2Absorption tower is mellapak250Y packed tower.
Beneficial effect：
Compared with the prior art, beneficial effects of the present invention are：
(1) DESs that the present invention is screened has stable physicochemical properties, and circulation benefit can be recycled in cheap easily preparation
With, while to H2S and SO2With excellent solubility property, and the H developed2S room temperature liquid phase oxidation has low operation temperature, energy
Consume it is small, discharge and can obtain the sulphur of high-purity without subsequent vent gas treatment, VOC free s.
(2) of the present invention using DESs as medium H2S liquid phase oxidation is suitable for a variety of sulphur-containing gas sources (natural gas, coke
Furnace gas, hydrodesulfurization gas, industrial waste gas, raw material of industry gas etc.), it can effectively realize to H2The removing of S, while obtaining high-purity
Sulphur.
Detailed description of the invention
Fig. 1 is method schematic diagram of the invention；
1 is SO2Absorption tower, 2 be H2The absorption tower S, 3 be liquid phase oxidation reaction tower, and 4 is are separated by filtration dry integrated machine, and 5 are
Drying unit.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1：With eutectic solvent chlorination 1- ethyl-3-methylimidazole -2- imidazolidinone (molar ratio 1:2) it is prepared as
Example, it is 1 that preparation is by hydrogen bond donor 2- imidazolidinone and hydrogen bond receptor chlorination 1- ethyl-3-methylimidazole in molar ratio:2 is mixed
It closes, is stirred at 80 DEG C to its congruent melting is made, gained liquid is eutectic solvent after being cooled to room temperature.It is used in following example
The preparation method of eutectic solvent is similar.
Embodiment 2：Using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium, its method schematic diagram is shown in attached drawing 1,
By H2The natural gas that S volume fraction is 0.8% is from H21 bottom input of the absorption tower S, eutectic solvent chlorination 1- ethyl -3- methyl miaow
Azoles -2- imidazolidinone (molar ratio 1:2) it is inputted at the top of absorption tower 1.H2Behaviour's temperature on the absorption tower S 1 is room temperature, operating pressure is
1.0MPa, operation liquid-gas ratio are 10Kg/Nm3.By SO2The coal-fired flue-gas that volume fraction is 0.2% is from SO22 bottom of absorption tower is defeated
Enter, eutectic solvent chlorination 1- ethyl-3-methylimidazole -2- imidazolidinone (molar ratio 1:2) it is inputted at the top of absorption tower 2.SO2
The operation temperature on absorption tower 2 is room temperature, and operating pressure 0.1MPa, operation liquid-gas ratio is 50Kg/Nm3.Used in absorption tower 1 and 2
Filler be mellapak250Y.H will be contained respectively2S and SO2Rich solution in static vortex mixer mixing after enter liquid phase oxidation reaction
Tower 3, tower top operation temperature are room temperature, and tower bottom operation temperature is 60 DEG C, operating pressure 1.0MPa, wherein H2S is relative to SO2With
Stoichiometric ratio excessive 12%.Containing sulphur eutectic solvent chlorination 1- ethyl-3-methylimidazole -2- imidazolidinone (mole
Than 1:2) emulsion enters filtration washing dry integrated machine 4 by 3 bottom of reaction tower and is filtered to remove eutectic solvent, separation, dry
Obtain sulphur finished product, and eutectic solvent chlorination 1- ethyl-3-methylimidazole -2- imidazolidinone (molar ratio 1:2) through dry single
Make water quality percentage composition therein less than 0.5% after the dry regeneration of member 5, is re-fed into the recycling of absorption tower 1 and 2.Eutectic
Solvent chlorination 1- ethyl-3-methylimidazole -2- imidazolidinone (molar ratio 1:2) H in the natural gas after washing2S and coal-fired flue-gas
In SO2Content measured by dynamic flue gas analyzer.Analysis is the result shows that H2S removal efficiency >=99.2%, after natural gas purification
H2S content is down to 30mg/m3, the proportion of goods damageds of natural gas are less than 1.0%, SO in cleaning of off-gas2Content be lower than 10mg/m3, it is based on
SO2Sulfur recovery rate >=98.0%.
Embodiment 3：Its technique and embodiment 2 are similar, see attached drawing 1, by H2The oven gas that S volume fraction is 3% is from H2S inhales
Receive 1 bottom input of tower, eutectic solvent chlorination 1- butyl -3- methylimidazole -2-Pyrrolidone (molar ratio 1:2) from absorption tower 1
Top input.H2Behaviour's temperature on the absorption tower S 1 is room temperature, operating pressure 1.0MPa, and operation liquid-gas ratio is 8Kg/Nm3.By SO2Body
The coal-fired flue-gas that fraction is 0.2% is from SO22 bottom input of absorption tower, low cosolvent chlorination 1- butyl -3- methylimidazole -2-
Pyrrolidones (molar ratio 1:2) it is inputted at the top of absorption tower 1.SO2The operation temperature on absorption tower 2 is room temperature, and operating pressure is
0.1MPa, operation liquid-gas ratio are 40Kg/Nm3.Filler used in absorption tower 1 and 2 is mellapak250Y.H will be contained respectively2S and
SO2Rich solution in static vortex mixer mixing after enter liquid phase oxidation reaction tower 3, tower top operation temperature be room temperature, tower bottom operation temperature
Degree is 80 DEG C, operating pressure 1.0MPa, wherein H2S is relative to SO2With stoichiometric ratio excessive 8%.Eutectic containing sulphur
Solvent chlorination 1- butyl -3- methylimidazole -2-Pyrrolidone (molar ratio 1:2) emulsion entered diafiltration by 3 bottom of reaction tower
It washs dry integrated machine 4 and is filtered to remove eutectic solvent, separate, be dried to obtain sulphur finished product, and eutectic solvent chlorination 1- butyl-
3- methylimidazole -2-Pyrrolidone (molar ratio 1:2) keep water quality percentage composition therein small after the dry regeneration of drying unit 5
In 0.5%, it is re-fed into the reuse of absorption tower 1 and 2.Low cosolvent chlorination 1- butyl -3- methylimidazole -2-Pyrrolidone (rubs
That ratio 1:2) H in the natural gas after washing2SO in S and coal-fired flue-gas2Content is measured by dynamic flue gas analyzer.Analyze result
Show H2S removal efficiency >=99.0%, oven gas purification after cure hydrogen content are down to 45mg/m3, the proportion of goods damageds of oven gas are less than
1.3%, SO in cleaning of off-gas2Content be lower than 10mg/m3, it is based on SO2Sulfur recovery rate >=98.0%.
Embodiment 4：Its technique and embodiment 2 are similar, see attached drawing 1, by H2The hydrodesulfurization gas that S volume fraction is 1.8%
From H21 bottom input of the absorption tower S, eutectic solvent chlorination 1- hexyl -3- methylimidazole-acetamide (molar ratio 1:1) from absorption
It is inputted at the top of tower 1.H2Behaviour's temperature on the absorption tower S 1 is room temperature, operating pressure 1.0MPa, and operation liquid-gas ratio is 10Kg/Nm3.It will
SO2The coal-fired flue-gas that volume fraction is 0.2% is from SO22 bottom input of absorption tower, eutectic solvent chlorination 1- hexyl -3- methyl miaow
Azoles-acetamide (molar ratio 1:1) it is inputted at the top of absorption tower 1.SO2The operation temperature on absorption tower 2 is room temperature, and operating pressure is
0.1MPa, operation liquid-gas ratio are 50Kg/Nm3.Filler used in absorption tower 1 and 2 is mellapak250Y.H will be contained respectively2S and
SO2Rich solution in static vortex mixer mixing after enter liquid phase oxidation reaction tower 3, tower top operation temperature be room temperature, tower bottom operation temperature
Degree is 60 DEG C, operating pressure 1.0MPa, wherein H2S is relative to SO2With stoichiometric ratio excessive 5%.Eutectic containing sulphur
Solvent chlorination 1- hexyl -3- methylimidazole-acetamide (molar ratio 1:1) emulsion enters filtration washing by 3 bottom of reaction tower and does
Dry all-in-one machine 4 is filtered to remove eutectic solvent, separates, is dried to obtain sulphur finished product, and eutectic solvent triethyl group butyl chlorination
Ammonium (N2224Cl)-malonic acid (molar ratio 2:1) it is less than water quality percentage composition therein after the dry regeneration of drying unit 5
0.5%, it is re-fed into the reuse of absorption tower 1 and 2.Eutectic solvent chlorination 1- hexyl -3- methylimidazole-acetamide (molar ratio
1:1) H in the natural gas after washing2SO in S and coal-fired flue-gas2Content is measured by dynamic flue gas analyzer.Analysis the result shows that
H2S removal efficiency >=99.0%, H after oven gas purification2S content is down to 40mg/m3, the proportion of goods damageds of oven gas are less than 1.0%, purification
SO in tail gas2Content be lower than 15mg/m3, it is based on SO2Sulfur recovery rate >=98.0%.
Above-mentioned eutectic solvent and other representative eutectic solvents, specific proportion, H2S removal efficiency and sulphur recovery
Rate is as shown in the table：
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention.The present invention
Claimed range is delineated by the appended claims, the specification and equivalents thereof from the appended claims.
Claims (7)
1. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium, it is characterised in that with amide derivatives, two
One or both of 01 derivatives are used as hydrogen bond donor, using one of imidazole salts, quaternary ammonium salt, choline as hydrogen bond receptor,
It is combined into eutectic solvent in proportion, realizes to H2The trapping of S, and the H that will be captured2S is converted into sulphur through room temperature liquid phase oxidation
Sulphur, specific step is as follows：
(1) hydrogen bond donor and hydrogen bond receptor are mixed first by certain mol proportion, are stirred under proper temperature to making its congruent melting,
Gained liquid is eutectic solvent after being cooled to room temperature, and the mass percentage of water is less than in eutectic solvent obtained
0.5%；
(2) by above-mentioned eutectic solvent from H2The absorption tower S（1）Top enters, and counter-current absorption is divided through what tower bottom entered containing certain volume
Number H2The gas to be processed of S, makes H2S is enriched in eutectic solvent, the H of formation2S rich solution is used for subsequent oxidation；
(3) by above-mentioned eutectic solvent from SO2Absorption tower（2）Top enters, and counter-current absorption is divided through what tower bottom entered containing certain volume
Number SO2Gas to be processed, make SO2It is enriched in eutectic solvent, the SO of formation2Rich solution is used for subsequent oxidation；
(4) by H obtained in above-mentioned steps2S and SO2Rich solution be pumped to liquid phase oxidation reaction tower respectively（3）, in tower top static state
Enter liquid phase oxidation reaction tower after vortex mixer mixing（3）, react and obtain the eutectic solvent emulsion containing sulphur；
(5) by the eutectic solvent emulsion containing sulphur by liquid phase oxidation reaction tower（3）After tower bottom discharge, it was sent into diafiltration
Wash dry integrated machine（4）Eutectic solvent is filtered out, separates, be dried to obtain sulphur finished product, and the eutectic solvent filtered out is through drying
Unit（5）Make water quality percentage composition therein after dry regeneration<0.5%, it is re-fed into H2The absorption tower S（1）And SO2Absorption tower
（2）, liquid phase oxidation reaction tower（3）Excessive H in tail gas2S then reenters H2The absorption tower S（1）.
2. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The molar ratio of the hydrogen bond donor and hydrogen bond receptor is (1 ~ 5):(1 ~ 5), whipping temp are room temperature ~ 150oC。
3. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The amide derivatives are one kind of acetamide, urea, 1,3- dimethyl urea, 2- imidazolidinone, 2-Pyrrolidone；The glycol
Derivative is ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3 butylene glycol, 1,4- butanediol, the third three
One of alcohol；The choline is one of glycine betaine, choline chloride；The quaternary ammonium salt is etamon chloride, triethyl group
One of butyl ammonium chloride, tetrabutylammonium chloride；The imidazole salts are chlorination 1- ethyl-3-methylimidazole, chlorination 1- butyl-
3- methylimidazole, chlorination 1- hexyl -3- methylimidazole, 1- ethyl-3-methylimidazole rhodanate, 1- butyl -3- methylimidazole
One of rhodanate, 1- hexyl -3- methylimidazole rhodanate.
4. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The H2The absorption tower S（1）Operation temperature be room temperature, operating pressure be 1.0 Mpa, operation liquid-gas ratio be 8 ~ 10 Kg/Nm3,
It is passed through containing H2S gas to be processed is H2It is a kind of in the natural gas, oven gas, hydrodesulfurization gas that S volume fraction is 0.8% ~ 1.8%.
5. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The SO2Absorption tower（2）Operation temperature be room temperature, operating pressure be 0.1 Mpa, operation liquid-gas ratio be 40 ~ 50 Kg/Nm3,
It is passed through containing SO2Gas to be processed is H2The coal-fired flue-gas that S volume fraction is 0.2%.
6. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The liquid phase oxidation reaction tower（3）Tower top operation temperature be room temperature, tower bottom operation temperature is 60 ~ 80 DEG C, and operating pressure is
1.0 Mpa, H2S is relative to SO2With excessive (0 ~ 15) % of stoichiometric ratio.
7. a kind of using eutectic solvent as the hydrogen sulfide liquid phase oxidation removal method of medium according to right 1, it is characterised in that
The H2The absorption tower S（1）And SO2Absorption tower（2）The packed tower for being mellapak250Y for filler.
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