CN116920570A - Selective separation of CO 2 Is desulphurized liquid and high concentration H 2 S desulfurization method and device - Google Patents
Selective separation of CO 2 Is desulphurized liquid and high concentration H 2 S desulfurization method and device Download PDFInfo
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- CN116920570A CN116920570A CN202210319275.6A CN202210319275A CN116920570A CN 116920570 A CN116920570 A CN 116920570A CN 202210319275 A CN202210319275 A CN 202210319275A CN 116920570 A CN116920570 A CN 116920570A
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 367
- 230000023556 desulfurization Effects 0.000 title claims abstract description 367
- 239000007788 liquid Substances 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 108
- 239000011593 sulfur Substances 0.000 claims abstract description 104
- 239000007789 gas Substances 0.000 claims abstract description 103
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 101
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 51
- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 18
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 18
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 230000005587 bubbling Effects 0.000 claims description 63
- 239000007921 spray Substances 0.000 claims description 57
- 238000011069 regeneration method Methods 0.000 claims description 54
- 230000008929 regeneration Effects 0.000 claims description 52
- 238000005507 spraying Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 11
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- -1 1-butyl-3-methyl chloroimidazole iron Chemical compound 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 27
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
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- 230000036961 partial effect Effects 0.000 description 4
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- 238000005261 decarburization Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 1
- PLWSZOQYWKLNIL-UHFFFAOYSA-N 1-butyl-2-chloro-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Cl PLWSZOQYWKLNIL-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 230000002745 absorbent Effects 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
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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
- B01D53/14—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
- B01D53/1406—Multiple stage absorption
-
- 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
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
Abstract
Selective separation of CO 2 Is desulphurized liquid and high concentration H 2 The S desulfurization method and the S desulfurization device have the advantages that the concentration of Fe (III) in the desulfurization solution exceeds 10%, the strong oxidizing property is realized, no extra pH control is needed, the S desulfurization method and the S desulfurization device can adapt to various adverse conditions, and the desulfurization solution can not be subjected to CO under the assistance of auxiliary agents of 1, 3-dimethyl imidazolinone, tributyl phosphate, sodium dodecyl sulfate and Tween-80 2 The influence is avoided, no secondary pollution is generated, and the treatment cost is low; the desulfurizing liquid has large sulfur capacity, and the active ingredients are not easy to lose efficacy; desulfurizing liquid against CO even under high pressure conditions 2 Has very low absorption capacity and very high H 2 S/CO 2 The separation selectivity. High-concentration desulfurization method and device for H in feed gas containing high-concentration hydrogen sulfide 2 Four-stage mixing is carried out on the desulfurization solution of the S and iron-based ionic liquid compound system to obtain purified gas and multistage desulfurization rich solution, thereby realizing H 2 Almost 100% removal of S. Simultaneously mixing all levels of desulfurization rich liquid and desulfurization liquid to obtain molecular H 2 S is completely converted into sulfur, and the desulfurization lean solution is regenerated into desulfurization solution for recycling, so that the method is environment-friendly.
Description
Technical Field
The invention relates to the technical field of petroleum drilling equipment, in particular to a method for selectively separating CO 2 Is desulphurized liquid and high concentration H 2 S desulfurization method and device.
Background
Containing H 2 The raw gas of S comprises natural gas, biomass fuel gas, sour water stripping tail gas, claus hydrogenation tail gas and the like. Natural gas includes conventional natural gas, dense gas, coalbed gas, shale gas, and natural gas hydrates. They are not only H 2 High S content and will often contain a relatively high concentration of dioxygenationCarbon, and the like. The acidic gas can severely corrode transportation equipment, such as tankers, pipelines, gas tankers, etc., and the malodorous gas emitted by the acidic gas can severely pollute the environment surrounding the pipelines and other transportation equipment. So contain H 2 In situ desulfurization of the S feed gas prior to transportation is very important.
The block of China Chuan northeast da county-Xuan Han is a natural gas producing area with high sulfur content, H 2 The S content is 13-18%, and the carbon dioxide content is 8-10%. The Chongyu regional Pu' er gas field is a typical high sulfur-containing gas field in China, H 2 The S content can reach 15 percent, and the carbon dioxide content is about 8 percent. In general, natural gas, oilfield associated gas, etc. are all high-pressure system systems. The volume of the raw material gas is reduced by times under the high pressure condition, which is very beneficial to the simplification of the desulfurization device, but H in the raw material gas under the pressure condition 2 The higher concentration of S is very challenging to the desulfurization fluids and desulfurization processes used in the selected desulfurization technique.
For H 2 Different requirements of S separation technical parameters and processes and H 2 Weak acidity and reducibility of S itself, absorb H 2 The method of S can be broadly classified into two main types, dry and wet. The dry desulfurization has the advantages of simple flow, convenient operation, high acid gas purification degree and the like, but is only suitable for treating gases with lower sulfur content, and common desulfurizing agents include active carbon, metal oxides and the like. The liquid absorption method uses lye as an absorbent, such as ADA method, PDS method, TV method, alkanolamine method, thermal potassium carbonate method, etc. These processes treat high concentrations of H 2 S, the active components of the desulfurizing liquid are easy to lose efficacy; the sulfur capacity of the desulfurizing liquid is low, the purifying requirement can be met only by accelerating the circulating mode of the desulfurizing liquid, and a great deal of loss of power and chemicals is caused, so that the cost is extremely high. In addition, the quality of the sulfur simple substance generated after desulfurization is very poor, and the sulfur simple substance cannot be used and can only be used as solid waste treatment. Importantly, contains H 2 High concentration of CO is associated with the raw material gas of S 2 The alkaline solution can not selectively absorb H 2 S, at the same time, can absorb high-concentration CO 2 So that the alkali liquor is deteriorated and the desulfurization process is hindered.
Disclosure of Invention
The invention provides a selective separation method of CO 2 Is desulphurized liquid and high concentration H 2 S desulfurization method and device can adapt to various adverse conditions, and desulfurization liquid cannot be subjected to CO 2 The influence is avoided, no secondary pollution is generated, and the treatment cost is low; the desulfurizing liquid has large sulfur capacity, and the active ingredients are not easy to lose efficacy; desulfurizing liquid against CO even under high pressure conditions 2 Has very low absorption capacity and very high H 2 S/CO 2 Separation selectivity to realize high concentration H 2 H in S feed gas 2 Almost 100% removal of S.
The technical scheme of the invention is as follows:
selective separation of CO 2 The desulfurizing liquid comprises the following components in parts by weight:
200 parts of iron-based ionic liquid;
1-100 parts of cosolvent;
the iron-based ionic liquid is 1-butyl-3-methyl chloroimidazole iron-based ionic liquid BmimFeCl 4 Synthesizing by ferric trichloride, chloro-N-butane and N-methylimidazole; wherein, the mass ratio of the ferric trichloride to the chloro-N-butane to the N-methylimidazole is (0.5-2) 1 (0.5-2);
the cosolvent comprises 1, 3-dimethyl-2-imidazolidinone (DMI), tributyl phosphate (TBP), sodium Dodecyl Sulfate (SDS) and Tween 80 (Tween-80).
Preferably, the mass ratio of 1, 3-dimethyl-2-imidazolidinone (DMI), tributyl phosphate (TBP), sodium Dodecyl Sulfate (SDS) and Tween 80 (Tween-80) is (200-400): (2-8): (0.1-1): (0.1-1).
High-concentration H 2 S desulfurization method using the above selective separation of CO 2 The multi-stage desulfurization is carried out on the feed gas by the desulfurization liquid, which comprises the following steps:
s1, H-containing 2 S, introducing the raw material gas into a first-stage bubbling desulfurization tower containing desulfurization liquid to obtain first purified gas and first desulfurization rich liquid;
s2, introducing the first purified gas into a second-stage bubbling desulfurization tower containing desulfurization liquid to obtain second purified gas and second desulfurization rich liquid;
s3, introducing the second purified gas into a third-stage spray desulfurization tower, and dispersing the desulfurization liquid in a gas phase in a droplet shape in a spray manner in the third-stage spray desulfurization tower to obtain a third purified gas and a third desulfurization rich liquid;
s4, introducing the third purified gas into a fourth-stage spray desulfurization tower, and dispersing the desulfurization liquid in a gas phase in a droplet shape in a spraying manner in the fourth-stage spray desulfurization tower to obtain fourth purified gas and fourth desulfurization rich liquid; the fourth purified gas is free of H 2 A cleaning gas of S;
s5, collecting the first desulfurization rich solution and the second desulfurization rich solution, adding a proper amount of desulfurization solution, and ensuring the dissolved molecular state H in the desulfurization rich solution 2 S is completely converted into sulfur to obtain the product without H 2 S, desulfurizing rich liquid;
s6, mixing the third desulfurization rich solution, the fourth desulfurization rich solution and the rich solution without H 2 S, collecting the desulfurization rich liquid, sending the desulfurization rich liquid to a regeneration tower, and simultaneously introducing oxygen-containing gas into the regeneration tower to oxidize and regenerate the desulfurization rich liquid into desulfurization lean liquid;
s7, delivering the desulfurization lean solution into a sulfur separation device, and separating a solid-liquid mixture rich in sulfur and regenerated desulfurization solution by adopting filtering, sedimentation or centrifugal operation; the regenerated desulfurization liquid is returned to the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower for recycling; the solid-liquid mixture rich in sulfur is sent into a sulfur melting kettle to be heated, so that high-purity sulfur and separated desulfurization liquid are obtained, and the separated desulfurization liquid is recycled to the regeneration tower to perform regeneration operation;
wherein the order of S5, S4 and S3 is adjustable.
Preferably, the feed gas comprises an alcohol amine refined sulfur-containing tail gas, an oilfield associated gas and/or a crude natural gas.
Preferably, in S1 and S2, the desulfurization temperatures in the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spray desulfurization tower, and the fourth-stage spray desulfurization tower are in the range of 10 to 80 ℃.
Preferably, the desulfurization temperatures in the first-stage bubbling desulfurization tower and the second-stage bubbling desulfurization tower are in the range of 40-60 ℃; and/or the desulfurization temperature in the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower is in the range of 40-50 ℃.
Preferably, in S6, the third desulfurization rich solution and the fourth desulfurization rich solution are mixed with the H-free solution 2 Before S desulfurization rich solution is collected, adding proper amount of desulfurization solution into the third desulfurization rich solution and the fourth desulfurization rich solution to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur; or S5 and S6, directly collecting the third desulfurization rich solution and the fourth desulfurization rich solution with the first desulfurization rich solution and the second desulfurization rich solution, and then adding a proper amount of desulfurization solution to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur.
Preferably, in S6, the oxygen-containing gas is air, the regeneration pressure in the regeneration tower is not more than 0.1MPa, and the regeneration temperature is 20 to 100 ℃.
High-concentration H 2 S' S desulfurization device, including first level bubble desulfurization tower, second level bubble desulfurization tower, third level spray desulfurization tower, fourth level spray desulfurization tower, regeneration tower, sulphur separator and slurry pump; the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are sequentially connected through gas pipelines; the regeneration tower, the sulfur separator and the liquid pipeline of the slurry pump are sequentially connected; the liquid output pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel and then connected to the liquid input pipeline of the regeneration tower; the liquid input pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel to the liquid output pipeline of the slurry pump to form a liquid circulation loop;
the liquid output pipelines of the first-stage bubbling desulfurization tower and the second-stage bubbling desulfurization tower are connected in parallel and then are connected with the liquid input pipeline of the slurry pump so as to ensure that the dissolved molecular H therein 2 S is completely converted into sulfur and then sent into a regeneration tower; or saidThe liquid output pipelines of the third-stage spray desulfurizing tower and the fourth-stage spray desulfurizing tower are connected in parallel and then connected with the liquid input pipeline of the slurry pump so as to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur and then sent into a regeneration tower; or the liquid input pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel and then connected with the liquid input pipeline of the slurry pump so as to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur and then sent into a regeneration tower;
the upper parts of the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower are provided with ejectors and/or sprayers which are communicated with the liquid input pipelines of the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower, and the ejectors and/or sprayers are used for ejecting desulfurization liquid into the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower;
the sulfur separator comprises a filtering device or a centrifugal device or a sedimentation device;
the proportion of the desulfurizing liquid supplied to the first-stage bubbling desulfurizing tower and the second-stage bubbling desulfurizing tower by the slurry pump through the liquid input pipeline is 50% -100%, and the proportion of the desulfurizing liquid supplied to the third-stage spraying desulfurizing tower and the fourth-stage spraying desulfurizing tower is 0% -50%.
Preferably, the high-concentration desulfurization device further comprises a sulfur melting kettle, wherein the sulfur melting kettle is used for heating the sulfur-rich solid-liquid mixture separated by the sulfur separator to 105-150 ℃ under normal pressure, so that the solid-liquid mixture is separated into liquid sulfur and desulfurization lean, the separated desulfurization lean solution is recycled, and the separated liquid sulfur is naturally cooled and crystallized to obtain high-purity solid sulfur.
Compared with the prior art, the invention has the advantages that:
1. the selective separation of CO according to the invention 2 The iron-based ionic liquid is imidazole-based ionic liquid, such as 1-butyl-3-methyl chloroimidazole (BmimCl) iron-based ionic liquid BmimFeCl 4 . Wherein the iron-based ionic liquid is synthesized by ferric trichloride, N-butyl chloride and N-methylimidazole, the mass ratio of the three is (0.5-2) 1 (0.5-2), so that the iron-based ionic liquid has good oxidizing property and hydrophobicity,the problem of byproducts caused by absorption of the alkaline aqueous phase can be avoided. In particular to the mass fraction of Fe (III) in the Fe-based ionic liquid, which exceeds 10 percent and is 0.2 percent in the far ultra Lo-Cat process. This is because the concentration of iron ions in the Lo-Cat process is maintained by means of complex iron, and the acid-base properties of the solution have a great influence on the catalytic oxidation activity. The iron-based ionic liquid has strong oxidizing property, and does not need extra pH control; the large amount of Fe (III) can also physically absorb H 2 S is oxidized internally to generate a sulfur element separation system, and is reduced to Fe (II) which is easily oxidized by oxygen. Namely, the content of active ingredients is reduced, so that the input cost and the construction cost of raw materials are further increased. Because the viscosity of the iron-based ionic liquid is higher, the overall mass transfer efficiency is poor, which hinders H 2 Dissolution of S and H 2 S, subsequent dissociation and oxidation processes. When the iron-based ionic liquid exists alone, the desulfurization effect of the iron-based ionic liquid is difficult to meet the requirement of desulfurization operation. Therefore, the following auxiliary agents are added into the iron-based ionic liquid: 1, 3-dimethylimidazolidinone, tributyl phosphate, sodium dodecyl sulfate and tween-80. The viscosity of the desulfurizing liquid is reduced, the gas-liquid mass transfer is promoted, and the absorption performance is improved; neutralizing the acidity of the iron-based ionic liquid and reducing the corrosiveness of the iron-based ionic liquid to metal materials; can also be used for H 2 S and CO 2 Has selective absorption and little absorption to methane; inhibiting the foaming performance of the desulfurizing liquid; meanwhile, the surface of the sulfur particles can be modified, the aggregation and growth of the particles are promoted, and the sedimentation of the sulfur is facilitated.
2. The invention relates to high-concentration H 2 S desulfurization method and device, H in high-sulfur feed gas 2 Four-stage mixing is carried out on the desulfurization solution of the S and iron-based ionic liquid compound system to obtain purified gas and multistage desulfurization rich solution, and the iron-based ionic liquid compound system is used for H 2 S has high solubility and high oxidizing power, so that H in the first purified gas and the second purified gas 2 The S concentration is greatly reduced, and the first and the second desulfurization rich liquids contain sulfur generated by oxidation and H dissolved in molecular state in the desulfurization liquid 2 S, reprocessing the second-level purified gas, and spraying or jetting the second-level purified gas on a third stageSupplying desulfurizing liquid to the stage spray desulfurizing tower and the fourth stage spray desulfurizing tower to purify H in the second gas 2 S is completely purified to realize H 2 Almost 100% removal of S. At the same time, the desulfurization rich liquid at each level is fully mixed with the desulfurization liquid in the bottom of the tower or a conveying pipeline to thoroughly oxidize molecular H in the desulfurization rich liquid at each level 2 S, completely converting the sulfur into sulfur suspended in the desulfurization lean solution, regenerating the desulfurization lean solution suspended with the sulfur into the desulfurization solution in a regeneration tower, separating the sulfur in the desulfurization solution by sedimentation, filtration, centrifugation and other modes, and obtaining high-purity liquid sulfur and regenerated desulfurization solution. Wherein, the regenerated desulfurization liquid can be directly circulated into desulfurization towers at all levels for recycling.
3. The invention relates to high-concentration H 2 S desulfurization method and device using selective separation of CO 2 Multistage desulfurization is carried out on high-sulfur raw material gas by the desulfurization liquid, and CO is selectively separated by compounding iron-based ionic liquid and DMI 2 The desulfurization solution has high sulfur capacity, and Fe (III) in the desulfurization solution oxidizes H 2 S is converted into Fe (II), H 2 S conversion to Sulfur and H + Sulfur may be removed. In the regeneration stage of the desulfurizing liquid, fe (II) and H in the liquid + React with oxygen to produce Fe (III) and H 2 O, the oxidation capacity of the system is restored. And (3) discharging a small amount of generated water along with air, separating generated sulfur, and recycling the desulfurizing liquid. But the desulfurizing liquid absorbs high-concentration H 2 S, part H 2 S is dissolved in molecular state in the desulfurization rich solution, and H is 2 S is not converted into sulfur, and then in the regeneration process of the regeneration tower and the air, the desulfurization rich solution has molecular H 2 S, it will be blown off to cause secondary pollution to gas phase, so this part of molecular H 2 S must be removed. The invention can make the molecular state H dissolved in the desulfurization rich solution by only mixing the desulfurization rich solution with the desulfurization solution before the desulfurization rich solution is regenerated 2 S is completely converted into sulfur, so that a desulfurization lean solution is obtained.
4. The invention relates to high-concentration H 2 S desulfurization method and device for selectively separating CO 2 CO in the desulfurizing liquid of (2) 2 Only trace amount is physically absorbed, will not be toThe active components of the desulfurizing liquid have no influence on the desulfurizing process and the regenerating process, and the gas-liquid contact time is not required to be shortened or the raw material gas decarburization treatment is not required to be carried out, so that the process flow is shortened and the desulfurizing effect is improved.
5. The invention relates to high-concentration H 2 S desulfurization method and device, sulfur purity is high, quality is good and separation is easy: and (3) separating and purifying the sulfur product by adopting a hot melting mode, heating a sulfur filter cake obtained by solid-liquid separation in a sulfur melting kettle, and directly separating liquid sulfur, wherein the purity is more than 99.0 weight percent.
6. The invention relates to high-concentration H 2 The desulfurization method and the device for S have the advantages that the reversibility of the regeneration of the desulfurization solution is good, the regeneration of the desulfurization solution can be completed through oxygen or air, the performance after the regeneration is good, the efficient recycling is realized, and the environment is protected.
Drawings
FIG. 1 shows a high concentration of H 2 S, a technological process schematic diagram of a desulfurization method and a desulfurization device;
FIG. 2 shows the high concentration H according to the present invention 2 S desulfurization method and device are used for XRD spectrum of yellow precipitate filtered out from desulfurization liquid after high-sulfur feed gas is desulfurized.
The reference numerals in the figures are:
1-first-stage bubbling desulfurization tower, 2-second-stage bubbling desulfurization tower, 3-third-stage spraying desulfurization tower, 4-fourth-stage spraying desulfurization tower, 5-regeneration tower, 6-slurry pump, 7-sulphur separator, 8-sulfur melting kettle, 9-regeneration desulfurization lean liquid pump, 10-raw gas, 11-first purified gas, 12-second purified gas, 13-third purified gas, 14-fourth purified gas, 15-first desulfurization rich liquid, 16-second desulfurization rich liquid, 17-third desulfurization rich liquid, 18-fourth desulfurization rich liquid and 19-air.
Detailed Description
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to specific embodiments that are illustrated in the appended drawings.
Example 1
Selective separation of CO 2 The desulfurizing liquid comprises the following components in parts by weight:
200 parts of iron-based ionic liquid;
1-100 parts of cosolvent;
wherein the iron-based ionic liquid is 1-butyl-3-methyl chloroimidazole iron-based ionic liquid BmimFeCl 4 Synthesizing by ferric trichloride, chloro-N-butane and N-methylimidazole; wherein, the mass ratio of the ferric trichloride to the chloro-N-butane to the N-methylimidazole is (0.5-2) 1 (0.5-2);
the cosolvent comprises 1, 3-dimethyl-2-imidazolidinone (DMI), tributyl phosphate (TBP), sodium Dodecyl Sulfate (SDS) and Tween 80 (Tween-80). The mass ratio of the 1, 3-dimethyl-2-imidazolidinone (DMI), tributyl phosphate (TBP), sodium Dodecyl Sulfate (SDS) and Tween 80 (Tween-80) is preferably (200-400): (2-8): (0.1-1): (0.1-1)
Selective separation of CO 2 The preparation method of the desulfurizing liquid comprises the following steps:
s1, preparing raw materials according to the proportion;
s2, preparing an iron-based ionic liquid: taking raw materials according to the mass ratio (0.5-2) of ferric trichloride, N-butyl chloride and N-methylimidazole, adding the N-butyl chloride into a high-pressure reaction kettle, adding the N-methylimidazole, heating to 70 ℃ by utilizing steam or water bath, starting a stirrer to perform constant-temperature reaction for 72 hours, closing a heating device, and slowly adding the ferric trichloride into the reaction kettle; after all the materials are put into the reactor, the reactor is cooled to room temperature, and the iron-based ionic liquid is obtained;
s3, adding 1, 3-dimethyl-2-imidazolone, tributyl phosphate, sodium Dodecyl Sulfate (SDS) and Tween 80 (Tween-80) into a high-pressure reaction kettle, and stirring for 2h to obtain the selective separation CO compounded by the iron-based ionic liquid-DMI-TBP and the surfactant 2 Is a desulfurization solution.
In particular, selective separation of CO is prepared 2 The step of the desulfurization solution A is as follows:
s1, taking ferric trichloride 1T, n-butyl chloride 759kg, N-methylimidazole 641kg,1, 3-dimethyl-2-imidazolidinone 300kg, tributyl phosphate 4kg, sodium Dodecyl Sulfate (SDS) 1kg and Tween 80 (Tween-80) 1kg;
s2, preparing an iron-based ionic liquid a; 759kg of N-butyl chloride and 641kg of N-methylimidazole are added into the high-pressure reaction kettle, and the mixture is heated to 70 ℃ by steam or water bath and kept at a constant temperature as far as possible, and a stirrer is started for constant-temperature reaction for 72 hours. After 72 hours, the heating device is closed, ferric chloride is slowly added into the high-pressure reaction kettle, and the ferric chloride can be added for 20 times within 12 hours for safety because the ferric chloride is dissolved in the substances to react and generate heat, so that 1T ferric chloride is added altogether. And after all the materials are put into the reactor, the reactor is cooled to room temperature, and the iron-based ionic liquid a is manufactured.
S3, adding 300kg of tributyl phosphate 4kg, sodium Dodecyl Sulfate (SDS) 1kg, tween 80 (Tween-80) 1kg into a reaction kettle, and stirring for 2h to obtain the selective separation CO of the iron-based ionic liquid-DMI-TBP and surfactant compound 2 Is a desulfurization solution A.
Selective CO separation of 30mL 2 Is put into a reactor with the volume of 200mL, the reactor is put into a constant temperature water bath kettle with the temperature of 40 ℃, and pure H is introduced after the system is kept constant 2 S, the result shows that the maximum absorption of hydrogen sulfide by the desulfurizing liquid exceeds 3.0mol/L at 2.7Mpa, wherein the physical absorption reaches 1.2mol/L, namely 40 percent of absorbed hydrogen sulfide is not converted into sulfur, but exists in the desulfurizing liquid in a molecular state. If the pressure of the feed gas is reduced, for example, at 0.2MPa, the amount of hydrogen sulfide absorbed by the desulfurizing liquid is as high as 0.42mol/L, and about 26% of the absorbed hydrogen sulfide is not converted. It can be seen that the desulfurization liquid has high absorption capacity and stable structure when treating high-concentration acid gas containing hydrogen sulfide, but can not realize 100% absorption of hydrogen sulfide to be converted into sulfur products.
CO is separated in the range of 1-5MPa in a direction selectivity under the condition of 298K at room temperature 2 10% H was introduced into the desulfurization solution 2 S、10％CO 2 80% nitrogen gas M, and a separate absorption experiment and a competitive absorption experiment were performed. Wherein, 1-5Mpa refers to the total pressure of the mixed gas M, which is the sum of the partial pressures of each component in the mixed gas. At 10% H 2 S、10％CO 2 For example, 80% nitrogen gas mixture M, when the total pressure of the mixture is 1Mpa, H 2 The partial pressure of S is 0.1MPa, CO 2 Also 0.1MPa. At the same time, CO is separated selectively under the same conditions 2 Is led to in desulfurization liquidInto 10% CO 2 The gas N was mixed with 90% nitrogen and a separate absorption experiment and a competitive absorption experiment were performed.
As a result, it was found that, when CO was absorbed alone 2 The absorption capacity increases markedly with increasing pressure, exhibiting the absorption characteristics of physical absorption. Selective separation of CO during competitive absorption 2 CO is the desulfurization solution of (2) 2 Is significantly reduced with increasing pressure, and selectively separates CO under competitive absorption conditions 2 CO is the desulfurization solution of (2) 2 The absorption capacity of the catalyst is greatly reduced. When H is 2 The S partial pressure reached 0.35MPa. When the desulfurization solution is used for CO 2 Almost no absorption.
Selective CO separation with 30mL 2 Is subjected to desulfurization at 25℃and 0.1MPa (lower absorption of pure CO 2 After the balance is reached, the mixture is heated for 1 hour under the conditions of normal pressure and 80 ℃ to finish the primary decarburization regeneration process. After the decarburization and regeneration process is repeated four times, the absorption capacity of the 4 times regenerated liquid is reduced by only 0.02 percent compared with that of the stock solution, because the regenerated desulfurization liquid also contains partial CO which is not released 2 And the infrared characteristic is that the structure of the desulfurizing liquid is not changed. CO absorption by desulfurization solution 2 The process is physical absorption only, and CO absorption of the desulfurizing liquid can be recovered by heating 2 Is provided).
Selective CO separation 2 Under the conditions of normal temperature of 25 ℃ and 0.4MPa, 10 percent hydrogen sulfide and 90 percent nitrogen mixed gas are introduced to carry out desulfurization operation for 20 minutes. After desulfurization is completed, oxygen is continuously introduced into an oxygen cylinder for 3 hours, and the oxygen flow is 60 mL.min -1 And (5) finishing the regeneration process of the desulfurizing liquid. The process is repeated for 3 times, fresh desulfurization liquid, regeneration desulfurization liquid 1 st time, regeneration desulfurization liquid 2 nd time and regeneration desulfurization liquid 3 rd time are taken, the desulfurization rate is calculated, and the result shows that the desulfurization rate is still maintained at 100% after the desulfurization liquid is regenerated for many times by using oxygen.
Example 2
High-concentration H 2 S desulfurization method using the above selective separation of CO 2 The process flow diagram of the multi-stage desulfurization of the feed gas by the desulfurization liquid is shown in figure 1, and the multi-stage desulfurization process comprises the following steps:
s1, oilfield associated gas (containing H) 2 S at about 10%) was fed with a catalyst containing selectively separated CO 2 In the first-stage bubbling desulfurization tower 1 of the desulfurization liquid, a first purified gas 11 and a first desulfurization rich liquid 15 are obtained; wherein the desulfurization temperature in the first-stage bubbling desulfurization tower 1 is 50 ℃, the desulfurization pressure is 0.4MPa, and the introducing rate of oilfield associated gas is 50m 3 /h; detection of H content in first purge gas 11 2 S ratio 4.5％；
S2, introducing the first purified gas 11 into a second-stage bubbling desulfurization tower 2 containing a desulfurization solution to obtain a second purified gas 12 and a second desulfurization rich solution 16; wherein the desulfurization temperature in the second-stage bubbling desulfurization tower 2 is 50 ℃, the desulfurization pressure is 0.4MPa, and the gas inlet rate is 50m 3 /h; detection of H content in the second purge gas 12 2 S ratio of 1.6；
S3, introducing the second purified gas 12 into a third-stage spray desulfurization tower 3, and dispersing the desulfurization liquid in a gas phase in a droplet-shaped manner in a spraying manner in the third-stage spray desulfurization tower 3 to obtain a third purified gas 13 and a third desulfurization rich liquid 17; wherein the desulfurization temperature in the third-stage spray desulfurization tower 3 is 50 ℃, the desulfurization pressure is 0.15MPa, and the gas inlet rate is 50m 3 /h; detection of H in third purge gas 13 2 S ratio of 0.35The%; no detection in the third desulfurization rich solution 17Dissolved molecular state H 2 S；
S4, introducing the third purified gas 13 into a fourth-stage spray desulfurization tower 4, and dispersing the desulfurization liquid in a gas phase in a liquid drop manner in a spray manner in the fourth-stage spray desulfurization tower 4 to obtain fourth purified gas 14 and fourth desulfurization rich liquid 18; wherein the desulfurization temperature in the fourth-stage spray desulfurization tower 4 is 50 ℃, the desulfurization pressure is 0.1MPa, and the gas inlet rate is 50m 3 /h; detecting the fourth purified 14 gas as being free of H 2 A cleaning gas of S;
s5, collecting the first desulfurization rich solution 15 and the second desulfurization rich solution 16, adding a proper amount of desulfurization solution (the original desulfurization solution or the regenerated desulfurization solution can be used) to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur to obtain the product without H 2 S, desulfurizing rich liquid;
s6, mixing the third desulfurization rich solution 17 and the fourth desulfurization rich solution 18 with the H-free solution 2 S, collecting the desulfurization rich liquid, delivering the desulfurization rich liquid to a regeneration tower 5, and simultaneously introducing enough air 19 into the regeneration tower 5 to oxidize and regenerate the desulfurization rich liquid into desulfurization lean liquid; the regeneration pressure in the regeneration tower 5 is 0.1MPa, and the regeneration temperature is 40 ℃;
s7, delivering the desulfurization lean solution into a sulfur separation device 7, and separating a solid-liquid mixture rich in sulfur and regenerated desulfurization solution by adopting filtering, sedimentation and/or centrifugal operation; the regenerated desulfurization liquid is returned to the first-stage bubbling desulfurization tower 1, the second-stage bubbling desulfurization tower 2, the third-stage spray desulfurization tower 3 and the fourth-stage spray desulfurization tower 4 through a lean liquid pump 9 for recycling; and the solid-liquid mixture rich in sulfur is sent into a sulfur melting kettle 8 for heating to obtain high-purity sulfur and separated desulfurization liquid, and the separated desulfurization liquid is recycled to the regeneration tower for regeneration operation. Through detection, the active components and the structure of the regenerated separation liquid are the same as those of the original desulfurization liquid.
And standing the desulfurization lean solution for 2 hours to generate a large amount of yellow precipitate, and separating the yellow precipitate by a centrifugal machine to obtain the yellow precipitate. The yellow precipitate is divided into two parts, one part is washed by a large amount of deionized water, and is put into a vacuum drying oven after being washed, dried for 6 hours at the temperature of 60 ℃, and then is put into a dryer after being dried, and the sample is analyzed by XRD. The other part is placed in an oven, heated to 130 ℃ and kept for 20min, then the liquid sulfur of the lower layer is decanted, cooled and analyzed by sample XRD. The results obtained by the two treatment methods are the same, and the XRD spectra of the two treatment methods are shown in figure 2. Compared with a sulfur XRD standard sketch library, the product sulfur presents the characteristics of monoclinic phase sulfur particles and is monoclinic phase sulfur. Therefore, the direct sulfur melting can well separate the desulfurizing liquid carried in the sulfur precipitate, and a high-quality sulfur product is obtained.
Example 3
High-concentration H 2 The desulfurization device of S, as shown in figure 1, comprises a first-stage bubbling desulfurization tower 1, a second-stage bubbling desulfurization tower 2, a third-stage spraying desulfurization tower 3, a fourth-stage spraying desulfurization tower 4, a regeneration tower 5, a slurry pump 6 and a sulfur separator 7; wherein, the first-stage bubbling desulfurization tower 1 and the second-stage drumThe bubble desulfurization tower 2, the third-stage spray desulfurization tower 3 and the fourth-stage spray desulfurization tower 4 are sequentially connected through gas pipelines; the liquid pipelines of the regeneration tower 5, the slurry pump 6 and the sulfur separator 7 are connected in sequence; the liquid output pipelines of the first-stage bubbling desulfurization tower 1, the second-stage bubbling desulfurization tower 2, the third-stage spraying desulfurization tower 3 and the fourth-stage spraying desulfurization tower 4 are connected in parallel and then connected to the liquid input pipeline of the regeneration tower 5; the liquid input pipelines of the first-stage bubbling desulfurization tower 1, the second-stage bubbling desulfurization tower 2, the third-stage spraying desulfurization tower 3 and the fourth-stage spraying desulfurization tower 4 are connected in parallel to the liquid output pipeline of the slurry pump 6 to form a liquid circulation loop;
the liquid output pipelines of the first-stage bubbling desulfurization tower 1 and the second-stage bubbling desulfurization tower 2 are connected in parallel and then are connected with the liquid input pipeline of the slurry pump 6 so as to ensure that the dissolved molecular H2S in the slurry pump is completely converted into sulfur and then sent into the regeneration tower 5; or the liquid output pipelines of the third-stage spray desulfurization tower 3 and the fourth-stage spray desulfurization tower 4 are connected in parallel and then connected with the liquid input pipeline of the slurry pump 6 so as to ensure that the dissolved molecular H2S in the slurry pump is completely converted into sulfur and then sent into the regeneration tower 5; or the liquid input pipelines of the first-stage bubbling desulfurization tower 1, the second-stage bubbling desulfurization tower 2, the third-stage spraying desulfurization tower 3 and the fourth-stage spraying desulfurization tower 4 are connected in parallel and then are connected with the liquid input pipeline of the slurry pump 6 so as to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur and then sent into a regeneration tower 5;
the upper parts of the third-stage spray desulfurization tower 4 and the fourth-stage spray desulfurization tower 5 are provided with ejectors and/or sprayers which are communicated with liquid input pipelines of the ejectors and/or sprayers, and the ejectors and/or sprayers are used for ejecting desulfurization liquid into the third-stage spray desulfurization tower 4 and the fourth-stage spray desulfurization tower 5;
the sulfur separator 6 comprises a filtering device or a centrifugal device or a sedimentation device;
the lean liquid pump 9 supplies 50% -100% of the desulfurization liquid to the first-stage bubbling desulfurization tower 1 and the second-stage bubbling desulfurization tower 2 through liquid input pipelines, and 0% -50% of the desulfurization liquid to the third-stage spraying desulfurization tower 3 and the fourth-stage spraying desulfurization tower 4.
The sulfur melting kettle 8 is used for heating the sulfur-rich solid-liquid mixture (sulfopaste) separated by the sulfur separator 7 to 105-150 ℃ under normal pressure to enable the solid sulfur to be in a molten state, and standing, separating and cooling and crystallizing the solid sulfur to obtain the high-purity solid sulfur.
It should be noted that the above-described embodiments provide a more complete understanding of the present invention to those skilled in the art, but do not limit the present invention in any way. Therefore, although the present invention has been described in detail with reference to the drawings and examples, it will be understood by those skilled in the art that the present invention may be modified or equivalent, and in all cases, all modifications and changes may be made without departing from the spirit and scope of the present invention, which is intended to be covered by the scope of the present invention.
Claims (10)
1. Selective separation of CO 2 The desulfurizing liquid is characterized by comprising the following components in parts by weight:
200 parts of iron-based ionic liquid;
1-100 parts of cosolvent;
the iron-based ionic liquid is 1-butyl-3-methyl chloroimidazole iron-based ionic liquid BmimFeCl 4 Synthesizing by ferric trichloride, chloro-N-butane and N-methylimidazole; wherein, the mass ratio of the ferric trichloride to the chloro-N-butane to the N-methylimidazole is (0.5-2) 1 (0.5-2);
the cosolvent comprises 1, 3-dimethyl-2-imidazolidinone, tributyl phosphate, sodium dodecyl sulfate and Tween 80.
2. The selective separation of CO according to claim 1 2 The desulfurization solution is characterized in that the mass ratio of the 1, 3-dimethyl-2-imidazolidinone, tributyl phosphate, sodium dodecyl sulfate and tween 80 is (200-400): (2-8): (0.1-1): (0.1-1).
3. High-concentration H 2 A process for desulfurizing S, characterized by using the selective separation of CO according to claim 1 or 2 2 Is to the original desulfurization solutionThe feed gas is subjected to multistage desulfurization, which comprises the following steps:
s1, H-containing 2 S, introducing the raw material gas into a first-stage bubbling desulfurization tower containing desulfurization liquid to obtain first purified gas and first desulfurization rich liquid;
s2, introducing the first purified gas into a second-stage bubbling desulfurization tower containing desulfurization liquid to obtain second purified gas and second desulfurization rich liquid;
s3, introducing the second purified gas into a third-stage spray desulfurization tower, and dispersing the desulfurization liquid in a gas phase in a droplet shape in a spray manner in the third-stage spray desulfurization tower to obtain a third purified gas and a third desulfurization rich liquid;
s4, introducing the third purified gas into a fourth-stage spray desulfurization tower, and dispersing the desulfurization liquid in a gas phase in a droplet shape in a spraying manner in the fourth-stage spray desulfurization tower to obtain fourth purified gas and fourth desulfurization rich liquid; the fourth purified gas is free of H 2 A cleaning gas of S;
s5, collecting the first desulfurization rich solution and the second desulfurization rich solution, adding a proper amount of desulfurization solution, and ensuring the dissolved molecular state H in the desulfurization rich solution 2 S is completely converted into sulfur to obtain the product without H 2 S, desulfurizing rich liquid;
s6, mixing the third desulfurization rich solution, the fourth desulfurization rich solution and the rich solution without H 2 S, collecting the desulfurization rich liquid, sending the desulfurization rich liquid to a regeneration tower, and simultaneously introducing oxygen-containing gas into the regeneration tower to oxidize and regenerate the desulfurization rich liquid into desulfurization lean liquid;
s7, delivering the desulfurization lean solution into a sulfur separation device, and separating a solid-liquid mixture rich in sulfur and regenerated desulfurization solution by adopting filtering, sedimentation or centrifugal operation; the regenerated desulfurization liquid is returned to the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower for recycling; the solid-liquid mixture rich in sulfur is sent into a sulfur melting kettle to be heated, so that high-purity sulfur and separated desulfurization liquid are obtained, and the separated desulfurization liquid is recycled to the regeneration tower to perform regeneration operation;
wherein the order of S5, S4 and S3 is adjustable.
4. A high concentration H as claimed in claim 3 2 S is characterized in that the raw gas comprises alcohol amine refined sulfur-containing tail gas, oilfield associated gas and/or crude natural gas.
5. A high concentration H as claimed in claim 3 2 The desulfurization method of S is characterized in that in S1 and S2, the desulfurization temperature ranges of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are 10-80 ℃.
6. A high concentration H as claimed in claim 3 2 S, wherein the desulfurization temperature in the first-stage bubbling desulfurization tower and the second-stage bubbling desulfurization tower is 40-60 ℃; and/or the desulfurization temperature in the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower is in the range of 40-50 ℃.
7. A high concentration H as claimed in claim 3 2 S, wherein in S6, the third desulfurization rich solution, the fourth desulfurization rich solution and the non-H-containing desulfurization rich solution are mixed 2 Before S desulfurization rich solution is collected, adding proper amount of desulfurization solution into the third desulfurization rich solution and the fourth desulfurization rich solution to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur; or S5 and S6, directly collecting the third desulfurization rich solution and the fourth desulfurization rich solution with the first desulfurization rich solution and the second desulfurization rich solution, and then adding a proper amount of desulfurization solution to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur.
8. A high concentration H as claimed in claim 3 2 S6, wherein the oxygen-containing gas is air, the regeneration pressure in the regeneration tower is not more than 0.1MPa, and the regeneration temperature is 20-100 ℃.
9. High-concentration H 2 S desulfurization device, characterized by comprising a firstThe device comprises a stage bubbling desulfurization tower, a second stage bubbling desulfurization tower, a third stage spraying desulfurization tower, a fourth stage spraying desulfurization tower, a regeneration tower, a sulfur separator and a slurry pump; the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are sequentially connected through gas pipelines; the regeneration tower, the sulfur separator and the liquid pipeline of the slurry pump are sequentially connected; the liquid output pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel and then connected to the liquid input pipeline of the regeneration tower; the liquid input pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel to the liquid output pipeline of the slurry pump to form a liquid circulation loop;
the liquid output pipelines of the first-stage bubbling desulfurization tower and the second-stage bubbling desulfurization tower are connected in parallel and then are connected with the liquid input pipeline of the slurry pump so as to ensure that the dissolved molecular H therein 2 S is completely converted into sulfur and then sent into a regeneration tower; or the liquid output pipelines of the third-stage spray desulfurizing tower and the fourth-stage spray desulfurizing tower are connected in parallel and then connected with the liquid input pipeline of the slurry pump so as to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur and then sent into a regeneration tower; or the liquid input pipelines of the first-stage bubbling desulfurization tower, the second-stage bubbling desulfurization tower, the third-stage spraying desulfurization tower and the fourth-stage spraying desulfurization tower are connected in parallel and then connected with the liquid input pipeline of the slurry pump so as to ensure the dissolved molecular state H therein 2 S is completely converted into sulfur and then sent into a regeneration tower;
the upper parts of the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower are provided with ejectors and/or sprayers which are communicated with the liquid input pipelines of the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower, and the ejectors and/or sprayers are used for ejecting desulfurization liquid into the third-stage spray desulfurization tower and the fourth-stage spray desulfurization tower;
the sulfur separator comprises a filtering device or a centrifugal device or a sedimentation device;
the proportion of the desulfurizing liquid supplied to the first-stage bubbling desulfurizing tower and the second-stage bubbling desulfurizing tower by the slurry pump through the liquid input pipeline is 50% -100%, and the proportion of the desulfurizing liquid supplied to the third-stage spraying desulfurizing tower and the fourth-stage spraying desulfurizing tower is 0% -50%.
10. High concentration H according to claim 9 2 S, the desulfurization device is characterized by further comprising a sulfur melting kettle, wherein the sulfur melting kettle is used for heating the sulfur-rich solid-liquid mixture separated by the sulfur separator to 105-150 ℃ under normal pressure, so that the solid-liquid mixture is separated into liquid sulfur and desulfurization lean solution, the separated desulfurization lean solution is recycled, and the separated liquid sulfur is naturally cooled and crystallized to obtain high-purity solid sulfur.
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