CN110013751B - Device and method for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method - Google Patents
Device and method for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method Download PDFInfo
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- CN110013751B CN110013751B CN201910115733.2A CN201910115733A CN110013751B CN 110013751 B CN110013751 B CN 110013751B CN 201910115733 A CN201910115733 A CN 201910115733A CN 110013751 B CN110013751 B CN 110013751B
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 244
- 230000023556 desulfurization Effects 0.000 claims abstract description 244
- 239000007788 liquid Substances 0.000 claims abstract description 180
- -1 compound amine Chemical class 0.000 claims abstract description 163
- 239000000835 fiber Substances 0.000 claims abstract description 158
- 239000012528 membrane Substances 0.000 claims abstract description 153
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 60
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims description 105
- 230000003009 desulfurizing effect Effects 0.000 claims description 86
- 150000001412 amines Chemical class 0.000 claims description 33
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000011162 core material Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 232
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 68
- 238000005406 washing Methods 0.000 description 26
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 24
- 238000005259 measurement Methods 0.000 description 20
- 125000001741 organic sulfur group Chemical group 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 239000003513 alkali Substances 0.000 description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- 230000001172 regenerating effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Gas Separation By Absorption (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Industrial Gases (AREA)
Abstract
An apparatus for wet stripping non-mercaptan sulfur and mercaptans from liquefied gas, comprising: the fiber membrane contact reactor is provided with an air inlet for liquefied gas to enter, and is connected with the compound amine liquid tank and used for enabling the compound amine liquid and the liquefied gas to contact in the fiber membrane contact reactor for desulfurization; the desulfurization separating tank is arranged at the bottom of the fiber membrane contact reactor, is connected with the fiber membrane contact reactor and is used for separating the desulfurized liquefied gas and the compound amine liquid containing sulfide. The invention also discloses a method for wet-process removal of non-mercaptan sulfur and mercaptan from liquefied gas. Compared with the prior art, the device has the advantages of simple structure, simple operation, no solid waste, and capability of effectively removing non-mercaptan sulfur and mercaptan from the liquefied gas.
Description
Technical Field
The invention belongs to the technical field of liquefied gas desulfurization, and particularly relates to a device and a method for removing non-mercaptan sulfur and mercaptan sulfur in liquefied gas by liquid-liquid extraction.
Background
The liquefied gas processed by catalytic cracking, delayed coking, hydrocracking, atmospheric and vacuum pressure, catalytic reforming and other devices has the main components of C3, C4, small amount of C2, C5 and the like, and contains a large amount of sulfides. Wherein, the sulfide content is higher and higher along with the inferior and high-sulfidation of crude oil, and the morphology is also more and more complex.
By tracking investigation of the liquefied gas production device, the sulfide in the liquefied gas mainly contains hundreds to tens of thousands of mg/m 3 Hydrogen sulfide of several hundred to several thousand mg/m 3 And (2) thiol, but dimethyl sulfide, dimethyl disulfide, carbonyl sulfide (COS), carbon disulfide (CS) 2 ) The difference is large and several to tens of mg/m depending on the source 3 Even hundreds of mg/m 3 Even more, it reaches several thousand mg/m 3 。
With the improvement of the requirements of chemical products taking liquefied gas as raw materials, the quality of the liquefied gas products is correspondingly improved, and the requirements on the total sulfur content in the liquefied gas are more and more strict, and never exceed 343mg/m 3 Gradually to not more than 100mg/m 3 To not more than 50mg/m 3 To the present 20mg/m 3 Even more demanding 10mg/m 3 . As Methyl Tertiary Butyl Ether (MTBE) yields decrease, the total sulfur requirements of liquefied gas used in alkylation and gasometric feeds also increase.
In order to meet the requirements of more and more strict total sulfur content of liquefied gas products, the liquefied gas needs to be refined and desulfurized, and the existing liquefied gas refining and desulfurizing technology mainly adds corresponding COS, thioether and CS removal on the basis of amine eluting hydrogen sulfide and alkali eluting mercaptan in a matched manner 2 And the like. However, from the current follow-up investigation, it was found that thioether, COS, CS 2 The presence of such non-mercaptan sulfur has been a bottleneck as to whether the total sulfur of the liquefied gas product is acceptable.
The prior removal of non-mercaptan sulfur in liquefied gas is mainly aimed at removing a certain type of sulfide.
Aiming at hydrogen sulfide, an N-Methyldiethanolamine (MDEA) extraction process is mainly adopted at present, and the process is very mature. The utility model patent of patent application No. CN201410077771.0 (the patent application No. CN 103805274B), the utility model patent of application No. CN201210269574.X (the patent application No. CN 102757832B) and the utility model patent of application No. CN201520069733.0 (the patent application No. CN 204455017U) are all made of a fiber membrane contactor or an amine washing tower and a fiber membrane contactor which are combined as mass transfer equipment, and MDEA solution is adopted to remove hydrogen sulfide in liquefied gas.
Aiming at COS, at present, COS is basically hydrolyzed into hydrogen sulfide and carbon dioxide by a solid hydrolysis catalyst, and then the hydrogen sulfide is removed by adsorption desulfurizing agents such as zinc oxide, ferric oxide and the like; there are, of course, liquid phase hydrolysis catalysts for the hydrolytic removal of carbonyl sulfide. The method for hydrolyzing and removing the solid hydrolysis catalyst of carbonyl sulfide and the preparation method of the solid hydrolysis catalyst are described in the utility model patent application No. CN201410218662.6, CN103992831B, CN200410074539.8, CN1308073C, CN200510012331.8 and CN 1331596C. The utility model patent No. CN201610256214.4 discloses a device and a method for removing carbonyl sulfide in liquid hydrocarbon (the application publication No. CN 105778991B), the utility model patent No. CN201620347339.3 discloses a device for removing carbonyl sulfide in liquid hydrocarbon by an alkali liquor extraction method (the application publication No. CN 205528612U), the utility model patent No. CN201610449572.7 discloses a method for removing carbonyl sulfide by refined desulfurization of liquid hydrocarbon (the application publication No. CN 105885937B), wherein a liquid organic solution is used as a carbonyl sulfide hydrolytic agent, carbonyl sulfide is hydrolyzed into hydrogen sulfide and carbon dioxide, alkali liquor or MDEA is used as an adsorbent after carbonyl sulfide hydrolysis, and a fiber membrane contactor is used as an equipment carrier to realize removal of carbonyl sulfide.
For thioether, CS 2 The invention patent No. CN201610449572.7, a liquid hydrocarbon fine desulfurization method, relates to a part of the method, which mainly comprises the steps of arranging an extractive distillation tower, adding a desulfurizing agent and arranging an adsorption desulfurizing tower with a built-in modified molecular sieve to remove thioether and CS 2 Etc. But has the problems of overlarge energy consumption, solid waste discharge, complex operation and the like and is not enough.
In 2015, 46 (6), 68-72 of petroleum refining and chemical industry, the experimental conditions of using a fiber membrane contactor as mass transfer equipment and adopting compound amine liquid for removing organic sulfur from coking liquefied gas are described. But does not relate to process index control and corresponding specification equipment for process and production level equipment.
In summary, the methods for removing various non-mercaptan sulfur in liquefied gas are different, if several forms of non-mercaptan sulfur are removed at the same time, the corresponding methods for removing non-mercaptan sulfur need to be overlapped, so that several sets of desulfurization facilities need to be correspondingly added when several forms of sulfur exist, and thus, the desulfurization device is huge, the flow is complex and the operation is complicated; in addition, the existing non-mercaptan sulfur removal process needs different desulfurization facilities and desulfurization chemical agents to correspond to different forms of sulfur, so that high desulfurization cost and new or reconstruction cost of the device are caused; meanwhile, the solid catalyst and the adsorption desulfurizing agent for decarbonylation sulfur have the limit of sulfur capacity, so that solid waste landfill treatment is needed after failure, a large amount of solid waste is generated, and secondary pollution is easy to cause; and part of corresponding form sulfur is lost and wasted along with the landfill of solid waste, so that sulfur resource waste is caused.
To overcome the defects, the invention patent No. CN200910233505.1 of the invention (high-efficiency purifying desulfurizing agent for high-acidity petroleum and natural gas) (publication No. CN 102051244B) discloses a compound amine liquid, namely, the high-efficiency purifying desulfurizing agent (Unitedly developed d)The high-efficiency purifying desulfurizing agent is used for removing mercaptan, carbonyl sulfide and CS 2 Is a desulfurizing agent of (a). However, the composition of the UDS desulfurizing agent is disclosed only in the patent, and the method and apparatus for specific application are not described. In practical application, the device can meet the requirements of production devices by combining proper equipment, process and process parameters so as to reach the standard of total sulfur content in liquefied gas.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a device which has a simple structure and can remove non-mercaptan sulfur and mercaptan in liquefied gas by a wet method.
The second technical problem to be solved by the invention is to provide a method which is simple to operate, has no solid waste and can effectively remove non-mercaptan sulfur and mercaptan in liquefied gas by a wet method aiming at the current state of the art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: an apparatus for wet stripping non-mercaptan sulfur and mercaptans from liquefied gas, comprising:
Compounding an amine liquid tank;
the fiber membrane contact reactor is provided with an air inlet for liquefied gas to enter, and is connected with the compound amine liquid tank and used for enabling the compound amine liquid and the liquefied gas to contact in the fiber membrane contact reactor for desulfurization; the desulfurization separating tank is arranged at the bottom of the fiber membrane contact reactor, is connected with the fiber membrane contact reactor and is used for separating the desulfurized liquefied gas and the compound amine liquid containing sulfide.
In order to further improve the desulfurization efficiency, the desulfurization tower is connected with the air inlet of the first-stage fiber membrane contactor, is connected with the compound amine liquid tank and is used for primarily removing non-mercaptan sulfur and mercaptan in the liquefied gas to obtain compound amine liquid containing sulfide and primarily desulfurized liquefied gas.
The desulfurizing tower is preferably a packed amine sulfur-eluting tower or a sieve plate amine sulfur-eluting tower.
The device is connected with the desulfurizing tower and the desulfurizing separation tank and is used for separating the compound amine liquid containing sulfide so as to recover sulfide and the compound amine liquid. Thus, the compound amine liquid can be reused, and sulfide can be sent to a sulfur device for recycling.
The composition of the compound amine liquid in the compound amine liquid tank is preferably as follows:
1-50% (wt) of UDS desulfurizing agent, 0-50% (wt) of N-methyl diethanol amine, and water is used for supplementing the desulfurizing agent when the total amount is less than 100% (wt).
The composition of the compound amine liquid in the compound amine liquid tank is further preferably:
3-20% (wt) of UDS desulfurizing agent, 10-35% (wt) of N-methyl diethanol amine and the balance of water.
The UDS desulfurizing agent is UDS-01 or UDS-02 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co.
In order to fully contact the liquefied gas with the compound amine liquid, the inner core material in the fiber membrane contact reactor is stainless steel wires, and the length-diameter ratio of the fiber membrane contact reactor is 3-24.
The fiber membrane contactor is suitable for liquefied gas with higher sulfur content, improves desulfurization efficiency, reduces the content of non-mercaptan sulfur and mercaptan in the liquefied gas, and is improved in two or more stages, and the two or more stages of fiber membrane contactors are connected in series.
The invention solves the second technical problem by adopting the technical proposal that: a method for desulfurizing by using the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method, which is characterized in that:
when the fiber membrane contactor is at one stage, the desulfurization step is as follows:
The compound amine liquid and the liquefied gas enter a fiber membrane contact reactor according to the mass ratio of 0.06-3 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the fiber membrane contact reactor is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure is 0.8-3.5MPaG, and the temperature is 10-60 ℃;
then enters a desulfurization separation tank to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank, and the liquefied gas after desulfurization is discharged from the top of the desulfurization separation tank;
when the fiber membrane contactor is more than one stage, the fiber membrane contactors of all stages are connected in series, and the desulfurization step is as follows:
1. the compound amine liquid and the liquefied gas enter a first-stage fiber membrane contact reactor according to the mass ratio of 0.06-3 to complete desulfurization by forward contact, the apparent linear velocity of the liquefied gas in the first-stage fiber membrane contact reactor is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure is 0.8-3.5MPaG, and the temperature is 10-60 ℃;
2. then enters a desulfurization separation tank of the first stage to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank of the first stage, and the liquefied gas after desulfurization flows out from the top of the desulfurization separation tank of the first stage;
3. The liquefied gas coming out from the top of the first-stage desulfurization separating tank enters the fiber membrane contactor of the second stage adjacent to the first-stage desulfurization separating tank, desulfurization is carried out according to the first step and the second step, and the cycle is carried out until the desulfurization in the fiber membrane contactor of each stage is completed, and the liquefied gas after desulfurization is discharged from the top of the last-stage desulfurization separating tank.
The technical scheme adopted by the invention for solving the second technical problem can be as follows: a method for desulfurizing by using the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method, which is characterized in that:
when the fiber membrane contactor is at one stage, the desulfurization step is as follows:
1. the compound amine liquid and the liquefied gas enter a desulfurizing tower such as a packing tower, a sieve plate tower and the like according to the mass ratio of 0.2-0.5, are reversely contacted to complete preliminary desulfurization, are separated, the pressure in the desulfurizing tower is 0.8-3.5MPaG, the temperature is 10-60 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower and enters a fiber membrane contactor to further desulfurize;
2. the compound amine liquid and the liquefied gas from the desulfurizing tower enter a fiber membrane contact reactor according to the mass ratio of 0.06-3 to complete desulfurization by forward contact, the apparent linear velocity of the liquefied gas is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure in the fiber membrane contact reactor is 0.8-3.5MPaG, and the temperature is 10-60 ℃; then enters a desulfurization separation tank to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank, and the liquefied gas after desulfurization is discharged from the top of the desulfurization separation tank;
When the fiber membrane contactor is more than one stage, the fiber membrane contactors of all stages are connected in series, and the desulfurization step is as follows:
(1) the compound amine liquid and the liquefied gas enter a desulfurizing tower according to the mass ratio of 0.2-0.5 to reversely contact to complete preliminary desulfurization, the primary desulfurization is carried out, the pressure in the desulfurizing tower is 0.8-3.5MPaG, the temperature is 10-60 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower, and the liquefied gas after preliminary desulfurization flows out from the top of the desulfurizing tower and enters a first-stage fiber membrane contactor to further desulfurize;
(2) the compound amine liquid and the liquefied gas from the desulfurization tower enter a first-stage fiber membrane contact reactor according to the mass ratio of 0.06-3 to complete further desulfurization, the apparent linear velocity of the liquefied gas is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure in the first-stage fiber membrane contact reactor is 0.8-3.5MPaG, and the temperature is 10-60 ℃; then enters a desulfurization separation tank of the first stage to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank of the first stage, and the liquefied gas after desulfurization flows out from the top of the desulfurization separation tank of the first stage;
(3) and (3) feeding the liquefied gas coming out of the top of the first-stage desulfurization separation tank into a second-stage fiber membrane contactor adjacent to the liquefied gas, and carrying out desulfurization according to the step (2), and circulating in such a way until desulfurization in each-stage fiber membrane contactor is completed, and discharging the desulfurized liquefied gas from the top of the last-stage desulfurization separation tank.
Finally, the mass ratio of the compound amine liquid to the liquefied gas in the first step and/or the step (1) is preferably 0.25-0.35; the mass ratio of the compound amine liquid to the liquefied gas in the second step and/or the step (2) is preferably 0.15-0.25, the apparent linear velocity of the liquefied gas is preferably 0.5-0.9m/s, the apparent linear velocity of the compound amine liquid is preferably 0.06-0.10m/s, and the residence time in the desulfurization separation tank is preferably 10-30 minutes.
Compared with the prior art, the invention has the advantages that: the compound amine liquid and at least one stage of fiber membrane contactor are combined for use, so that the structure is simple, the fiber membrane contactor with one stage or more stages can be flexibly designed according to the content of non-mercaptan sulfur and mercaptan in raw materials, and the compound amine liquid and the liquefied gas are contacted and desulfurized in the fiber membrane contactor, so that the liquefied gas comprising hydrogen sulfide, thioether, COS and CS can be effectively removed 2 Non-mercaptan sulfur content in the treated liquefied gas is not more than 10mg/m 3 Thereby reducing the load of the subsequent alkaline washing and mercaptan removal device and ensuring that the total sulfur index of the liquefied gas reaches the standard of 5-10mg/m 3 。
The device and the method are suitable for non-mercaptan sulfur with different forms, and can meet the removal of the form sulfur without setting specific desulfurization facilities and corresponding desulfurization programs for the sulfur with a certain form, thereby simplifying the flow, reducing the operation difficulty and reducing the investment and the operation cost. The method has the advantages that no solid desulfurizing agent and no extractive distillation desulfurizing facility are provided, the solid waste emission is avoided, meanwhile, excessive energy consumption is avoided, the compound amine liquid rich in sulfide after desulfurization can be heated and regenerated for recycling, and the removed non-mercaptan sulfur and mercaptan can be sent to a sulfur device for recycling.
Drawings
FIG. 1 is a flow chart of the wet process for removing non-mercaptan sulfur and mercaptans in liquefied gas according to example 1 of the present invention;
FIG. 2 is a flow chart of the wet process for removing non-mercaptan sulfur and mercaptans from liquefied gas in accordance with example 7 of the present invention;
FIG. 3 is a flow chart of the wet process for removing non-mercaptan sulfur and mercaptans in liquefied gas according to example 9 of the present invention;
FIG. 4 is a flow chart of the wet stripping of non-mercaptan sulfur and mercaptans in liquefied gas in accordance with example 10 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1:
as shown in fig. 1, the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method comprises a compound amine liquid tank 3, a constant temperature water bath 200, a compound amine liquid feed pump 300, a liquid distributor 23, a fiber membrane contactor 2 (comprising a fiber membrane contact reactor 21 and a desulfurization separation tank 22, wherein the inner core material in the fiber membrane contact reactor 21 is stainless steel wire, the length-diameter ratio of the fiber membrane contact reactor 21 is 18), a liquefied gas storage tank 900, a liquefied gas feed pump 910, a flowmeter 920, a rich liquid collection tank 8, a purified liquefied gas sampling port 710, a tail gas absorber 720 and a nitrogen steel bottle 730. The built-up amine liquid introduced into the system enters the fiber membrane contact reactor 21 through a liquid distributor 23 at the top of the fiber membrane contactor 2 and flows down the fiber surface (i.e., the aqueous phase). The liquefied gas (i.e. oil phase) introduced into the fiber membrane contactor and the water phase flow downwards along the fiber filaments in parallel, and the two phases are fully contacted and subjected to mass transfer in the flowing process. When the mass transfer process is completed, the two phases enter the desulfurization and separation tank 22 together; under the action of the larger density difference, the two are rapidly and thoroughly layered, wherein the water phase with higher density is discharged from the lower outlet of the sedimentation tank and is collected in the rich liquid collection tank 8, and the oil phase with lower density is discharged from the upper outlet.
The properties of the liquefied gas in this example are shown in table 1 below:
TABLE 1 Main Property parameter table of liquefied gas
The compound amine liquid in the embodiment comprises the following components in percentage by weight: 3.50% (wt) of a commercialized efficient organic sulfur removal formula component UDS-F (namely UDS desulfurizing agent, in the embodiment, UDS-01 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd. Is selected, of course, compound amine liquid produced by other units or prepared by self-regulating according to the formula disclosed in the invention patent No. CN200910233505.1 of highly acidic efficient desulfurizing agent for petroleum and natural gas), 31.5% (wt) of N-methyldiethanolamine and the balance of water.
The compound amine liquid and the liquefied gas enter a fiber membrane contactor according to the mass ratio of 3 to contact and complete desulfurization, and the specific steps are as follows:
the compound amine liquid and the liquefied gas enter a fiber membrane contact reactor 21 according to the mass ratio of 3 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the fiber membrane contact reactor 21 is 0.04m/s, the apparent linear velocity of the compound amine liquid is 0.11m/s, the pressure is 0.9MPaG, and the temperature is 40 ℃;
then enters the desulfurization and separation tank 22 to stay for 8 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22 and is collected in the rich liquid collection tank 8, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22. As a result, it was found that the removal rate of COS in the liquefied gas from the top of the desulfurization separator tank 22 was 97.1%, the removal rate of methyl mercaptan was 74.1%, and the removal rate of total organic sulfur was 77.8%.
Example 2:
substantially the same as in example 1, except that: the compound amine liquid in the embodiment comprises the following components in percentage by weight: 7% (wt) of the commercial high-efficiency organic sulfur removal formula component UDS-F, 28% (wt) of N-methyldiethanolamine and the balance of water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 97.7%, the removal rate of methyl mercaptan was 80.1%, and the removal rate of total organic sulfur was 82.8%.
Example 3:
substantially the same as in example 1, except that: the compound amine liquid in the embodiment comprises the following components in percentage by weight: 10.5% (wt) of the commercial high-efficiency organic sulfur removal formulation component UDS-F, 24.5% (wt) of N-methyldiethanolamine, and the balance water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 97.9%, the removal rate of methyl mercaptan was 90%, and the removal rate of total organic sulfur was 90.7%.
Example 4:
substantially the same as in example 1, except that: the compound amine liquid in the embodiment comprises the following components in percentage by weight: 14% (wt) of the commercial high-efficiency organic sulfur removal formulation component UDS-F, 21% (wt) of N-methyldiethanolamine and the balance water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 99.3%, the removal rate of methyl mercaptan was 93.4%, and the removal rate of total organic sulfur was 93.6%.
Example 5:
substantially the same as in example 1, except that: the compound amine liquid in the embodiment comprises the following components in percentage by weight: 12% (wt) of the commercial high-efficiency organic sulfur removal formulation component UDS-F, 18% (wt) of N-methyldiethanolamine, and the balance water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 96.3%, the removal rate of methyl mercaptan was 92%, and the removal rate of total organic sulfur was 92.1%.
Example 6:
substantially the same as in example 1, except that: the compound amine liquid in the embodiment comprises the following components in percentage by weight: 20% (wt) of the commercial high-efficiency organic sulfur removal formula component UDS-F, 30% (wt) of N-methyldiethanolamine and the balance of water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 99.6%, the removal rate of methyl mercaptan was 95.4%, and the removal rate of total organic sulfur was 95.6%.
Comparative example 1:
substantially the same as in example 1, except that: the amine liquid in the comparative example comprises the following components in percentage by weight: 35% (wt) of N-methyldiethanolamine, the balance being water.
As a result, it was found that the removal rate of COS in the liquefied gas from the top of the liquefied gas separation tank was 82.2%, the removal rate of methyl mercaptan was 43.7%, and the removal rate of total organic sulfur was 47.9%.
Example 7:
as shown in fig. 2, the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method comprises a desulfurizing tower 1 (filler amine eluting sulfur tower is selected), a fiber membrane contactor 2 (comprising a fiber membrane contact reactor 21 and a desulfurizing separation tank 22, wherein the inner core material in the fiber membrane contact reactor 21 is stainless steel wire, the length-diameter ratio of the fiber membrane contact reactor 21 is 4.2), a compound amine liquid tank 3, a liquefied gas filter 4, a compound amine liquid filter 5 and a regenerating device 6. The liquefied gas to be desulfurized is connected to the desulfurizing tower 1 through a first liquefied gas line 91, the top outlet of the desulfurizing tower 1 is connected to the fiber membrane contact reactor 21 through a second liquefied gas line 92, and the liquefied gas filter 4 is provided on the second liquefied gas line 92 to filter the liquefied gas coming out of the desulfurizing tower 1. The desulfurization and separation tank 22 is arranged at the bottom of the fiber membrane contact reactor 21 and is connected with the fiber membrane contact reactor 21, and the outlet at the top of the desulfurization and separation tank 22 is used for leading the desulfurized liquefied gas out of the device through a third liquefied gas pipeline 93.
The complex amine liquid tank 3 is connected with the desulfurizing tower 1 and the fiber membrane contact reactor 21 through a first complex amine liquid pipeline 31, and the complex amine liquid filter 5 is arranged on the first complex amine liquid pipeline 31 to filter the complex amine liquid from the complex amine liquid tank 3.
The above-mentioned regenerating unit 6 is connected to the bottom outlets of the desulfurization tower 1 and the desulfurization separation tank 22 through a line 61 to regenerate the sulfide-rich compound amine liquid flowing out from the bottom outlets of the desulfurization tower 1 and the desulfurization separation tank 22.
In this embodiment, the composition of the compound amine liquid in the compound amine liquid tank is as follows: 25% (wt) of a commercial efficient organic sulfur removal formula component UDS-F (UDS-02 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd.), 40% (wt) of N-methyldiethanolamine and the balance of water;
the properties of the liquefied gas in this example are shown in table 2 below:
TABLE 2 Main Property parameter values of liquefied gas
The desulfurization method comprises the following steps:
1. the compound amine liquid and the liquefied gas enter a packing type desulfurizing tower 1 according to the mass ratio of 0.35 to reversely contact to complete preliminary desulfurization, the separation is carried out, the pressure in the desulfurizing tower 1 is 1.6MPaG, the temperature is 40 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower 1 and enters a regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower 1 and enters a fiber membrane contact reactor 21 through a second liquefied gas pipeline 92 and a liquefied gas filter 4 to further desulfurize;
2. the compound amine liquid and the liquefied gas from the desulfurizing tower 1 enter a fiber membrane contact reactor 21 according to the mass ratio of 0.2 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas is 0.9m/s, the apparent linear velocity of the compound amine liquid is 0.09m/s, the pressure in the fiber membrane contact reactor 21 is 1.48MPaG, and the temperature is 40 ℃; then enters the desulfurization and separation tank 22 for 25 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
In this example, in order to intuitively observe the desulfurization effect, the amounts of sulfide in the liquefied gas from the top of the desulfurization tower 1 and the liquefied gas from the top of the desulfurization separator 22 were measured, respectively, and the measurement results are shown in table 3.
Example 8:
substantially the same as in example 7, except that: in this embodiment, the desulfurizing tower 1 is a sieve plate amine-washing desulfurizing tower, and the aspect ratio of the fibrous membrane contact reactor 21 is 4.2.
The desulfurization method of the embodiment comprises the following steps:
1. the compound amine liquid and the liquefied gas enter a desulfurizing tower 1 according to the mass ratio of 0.35 to reversely contact to complete preliminary desulfurization, the separation is carried out, the pressure in the desulfurizing tower 1 is 1.6MPaG, the temperature is 40 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower 1 and enters a regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower 1 and enters a fiber membrane contact reactor 21 through a second liquefied gas pipeline 92 and a liquefied gas filter 4 to further desulfurize;
2. the compound amine liquid and the liquefied gas from the desulfurizing tower 1 enter a fiber membrane contact reactor 21 according to the mass ratio of 0.18 to be in forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas is 0.79m/s, the apparent linear velocity of the compound amine liquid is 0.07m/s, the pressure in the fiber membrane contact reactor 21 is 1.53MPaG, and the temperature is 40 ℃; then enters the desulfurization and separation tank 22 for 20 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the desulfurizing tower and the liquefied gas from the top of the desulfurizing separator, respectively, and the measurement results are shown in table 3.
Example 9:
as shown in fig. 3, the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method comprises a fiber membrane contactor 2 (comprising a fiber membrane contact reactor 21 and a desulfurization separation tank 22, wherein the inner core material of the fiber membrane contact reactor 21 is stainless steel wire, and the length-diameter ratio of the fiber membrane contact reactor 21 is 5.5), a compound amine liquid tank 3, a liquefied gas filter 4, a compound amine liquid filter 5 and a regeneration device 6. The liquefied gas to be desulfurized is connected to the fiber membrane contact reactor 21 through a first liquefied gas line 91, and the above liquefied gas filter 4 is provided on the first liquefied gas line 91 to filter the liquefied gas. The desulfurization and separation tank 44 is disposed at the bottom of the fiber membrane contact reactor 21 and connected to the fiber membrane contact reactor 21, and the outlet at the top of the desulfurization and separation tank 22 is configured to discharge the desulfurized liquefied gas from the device through a third liquefied gas line 93.
The compound amine liquid tank 3 is connected with the fiber membrane contact reactor 21 through a first compound amine liquid pipeline 31, and the compound amine liquid filter 5 is arranged on the first compound amine liquid pipeline 31 to filter the compound amine liquid from the compound amine liquid tank 3.
The regeneration device 6 is connected to the bottom outlet of the desulfurization separator tank 22 through a line 61 to regenerate the sulfide-enriched compound amine solution flowing out of the bottom outlet of the desulfurization separator tank 22.
The composition of the compound amine liquid in the compound amine liquid tank in this embodiment is: 25% (wt) of a commercial efficient organic sulfur removal formula component UDS-F (UDS-01 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd.), 35% (wt) of N-methyldiethanolamine and the balance of water;
the properties of the liquefied gas in this example are the same as those of the liquefied gas in example 7 described above.
The desulfurization method comprises the following steps:
the compound amine liquid and the liquefied gas enter a fiber membrane contact reactor 21 according to the mass ratio of 0.25 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the fiber membrane contact reactor 21 is 0.99m/s, the apparent linear velocity of the compound amine liquid is 0.11m/s, the pressure is 1.58MPaG, and the temperature is 40 ℃;
then enters the desulfurization and separation tank 22 for 20 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content of the liquefied gas discharged from the top of the desulfurization separator was performed, and the measurement results are shown in table 3.
Example 10:
as shown in fig. 4, the device for removing non-mercaptan sulfur and mercaptan in liquefied gas by wet method comprises two stages of fiber membrane contactors (a first stage fiber membrane contactor 2a positioned on the left and a second stage fiber membrane contactor 2b positioned on the right), a compound amine liquid tank 3, a liquefied gas filter 4, a compound amine liquid filter 5 and a regeneration device 6. The first-stage fiber membrane contactor 2a comprises a first-stage fiber membrane contact reactor 21a and a first-stage desulfurization separation tank 22a, wherein the inner core of the first-stage fiber membrane contact reactor 21a is made of stainless steel wires, and the length-diameter ratio of the first-stage fiber membrane contact reactor 21a is 3.6; the second-stage fiber membrane contactor 2b comprises a second-stage fiber membrane contact reactor 21b and a second-stage desulfurization separation tank 22b, wherein the inner core material in the second-stage fiber membrane contact reactor 21b is stainless steel wires, and the length-diameter ratio of the second-stage fiber membrane contact reactor 21b is 3.6. The liquefied gas to be desulfurized is connected to the first-stage fiber membrane contact reactor 21a through a first liquefied gas line 91, and the above liquefied gas filter 4 is provided on the first liquefied gas line 91 to filter the liquefied gas. The first stage desulfurization separating tank 22a is arranged at the bottom of the first stage fiber membrane contact reactor 21a and is connected with the first stage fiber membrane contact reactor 21a, and the outlet at the top of the first stage desulfurization separating tank 22a is connected with the second stage fiber membrane contact reactor 21b through a second liquefied gas pipeline 92, so that the liquefied gas after preliminary desulfurization enters the second stage fiber membrane contact reactor 21b for further desulfurization. The second-stage desulfurization separating tank 22b is arranged at the bottom of the second-stage fiber membrane contact reactor 21b and is connected with the second-stage fiber membrane contact reactor 21b, and the outlet at the top of the second-stage desulfurization separating tank 22b is used for leading the desulfurized liquefied gas out of the device through a third liquefied gas pipeline 93.
The compound amine liquid tank 3 is connected with the first stage fiber membrane contact reactor 21a and the second stage fiber membrane contact reactor 21b through a first compound amine liquid pipeline 31, and the compound amine liquid filter 5 is arranged on the first compound amine liquid pipeline 31 to filter the compound amine liquid from the compound amine liquid tank 3.
The regeneration device 6 is connected to the bottom outlets of the first stage desulfurization separating tank 22a and the second stage desulfurization separating tank 22b through a line 61 to regenerate the sulfide-enriched compound amine solution flowing out from the bottom outlets of the first stage desulfurization separating tank 22a and the second stage desulfurization separating tank 22 b.
The composition of the compound amine liquid in this example is: 25% (wt) of a commercial efficient organic sulfur removal formula component UDS-F (UDS-01 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd.), 30% (wt) of N-methyldiethanolamine and the balance of water;
the properties of the liquefied gas in this example are the same as those of the liquefied gas in example 7 described above.
The desulfurization method comprises the following steps:
the compound amine liquid and the liquefied gas enter a first-stage fiber membrane contact reactor 21a according to the mass ratio of 0.2 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the first-stage fiber membrane contact reactor 21a is 0.79m/s, the apparent linear velocity of the compound amine liquid is 0.07m/s, the pressure is 1.58MPaG, and the temperature is 40 ℃; then enters the first-stage desulfurization separating tank 22a for 15 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the first-stage desulfurization separating tank 22a, enters the regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the first-stage desulfurization separating tank 22a and enters the second-stage fiber membrane contact reactor 21b through a second liquefied gas pipeline 92 for further desulfurization.
The compound amine liquid and the liquefied gas from the first-stage desulfurization separation tank 22a enter a second-stage fiber membrane contact reactor 21b according to the mass ratio of 0.2 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the second-stage fiber membrane contact reactor 21b is 0.79m/s, the apparent linear velocity of the compound amine liquid is 0.07m/s, the pressure is 1.53MPaG, and the temperature is 40 ℃; then enters the second-stage desulfurization separating tank 22b for 15 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the second-stage desulfurization separating tank 22b, enters the regeneration device 6 through a pipeline 61, and the liquefied gas subjected to further desulfurization comes out from the top of the second-stage desulfurization separating tank 22b and comes out of the device through a third liquefied gas pipeline 93.
In the same manner, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the first-stage desulfurization separator and the liquefied gas from the top of the second-stage desulfurization separator, and the measurement results are shown in table 3.
Example 11:
substantially the same as in example 7, except that: the aspect ratio of the fiber membrane contact reactor 21 in this example was 24; in this embodiment, the composition of the compound amine liquid in the compound amine liquid tank is as follows: 1% (wt) of a commercial efficient organic sulfur removal formula component UDS-F (UDS-02 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd.), 50% (wt) of N-methyldiethanolamine and the balance of water;
The desulfurization method of the embodiment comprises the following steps:
1. the compound amine liquid and the liquefied gas enter a desulfurizing tower 1 according to the mass ratio of 0.5 to reversely contact to complete preliminary desulfurization, the separation is carried out, the pressure in the desulfurizing tower 1 is 3.5MPaG, the temperature is 10 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower 1 and enters a regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower 1 and enters a fiber membrane contact reactor 21 through a second liquefied gas pipeline 92 and a liquefied gas filter 4 to further desulfurize;
2. the compound amine liquid and the liquefied gas from the desulfurizing tower 1 enter a fiber membrane contact reactor 21 according to the mass ratio of 0.06 to be in forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas is 1m/s, the apparent linear velocity of the compound amine liquid is 0.15m/s, the pressure in the fiber membrane contact reactor 21 is 3.5MPaG, and the temperature is 60 ℃; then enters the desulfurization and separation tank 22 for 45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the desulfurizing tower and the liquefied gas from the top of the desulfurizing separator, respectively, and the measurement results are shown in table 3.
Example 12:
substantially the same as in example 7, except that: the aspect ratio of the fiber membrane contact reactor 21 in this example was 3; in this embodiment, the composition of the compound amine liquid in the compound amine liquid tank is as follows: 50% (wt) of a commercial efficient organic sulfur removal formula component UDS-F (UDS-02 compound amine liquid produced by Jiangsu Jinlu environmental protection technology Co., ltd.) and the balance of water;
the desulfurization method of the embodiment comprises the following steps:
1. the compound amine liquid and the liquefied gas enter a desulfurizing tower 1 according to the mass ratio of 0.2 to reversely contact to complete preliminary desulfurization, the separation is carried out, the pressure in the desulfurizing tower 1 is 0.8MPaG, the temperature is 60 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower 1 and enters a regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower 1 and enters a fiber membrane contact reactor 21 through a second liquefied gas pipeline 92 and a liquefied gas filter 4 to further desulfurize;
2. the compound amine liquid and the liquefied gas from the desulfurizing tower 1 enter a fiber membrane contact reactor 21 according to the mass ratio of 3 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas is 0.3m/s, the apparent linear velocity of the compound amine liquid is 0.02m/s, the pressure in the fiber membrane contact reactor 21 is 0.8MPaG, and the temperature is 10 ℃; then enters the desulfurization and separation tank 22 for 5 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the desulfurizing tower and the liquefied gas from the top of the desulfurizing separator, respectively, and the measurement results are shown in table 3.
Example 13:
substantially the same as in example 9, except that the steps of the desulfurization method in this example are:
the compound amine liquid and the liquefied gas enter a fiber membrane contact reactor 21 according to the mass ratio of 0.06 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the fiber membrane contact reactor 21 is 1m/s, the apparent linear velocity of the compound amine liquid is 0.02m/s, the pressure is 3.5MPaG, and the temperature is 60 ℃;
then enters the desulfurization and separation tank 22 for 5 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content of the liquefied gas discharged from the top of the desulfurization separator was performed, and the measurement results are shown in table 3.
Example 14:
substantially the same as in example 9, except that the steps of the desulfurization method in this example are:
The compound amine liquid and the liquefied gas enter a fiber membrane contact reactor 21 according to the mass ratio of 2 to be contacted in the forward direction to complete desulfurization, the apparent linear velocity of the liquefied gas in the fiber membrane contact reactor 21 is 0.3m/s, the apparent linear velocity of the compound amine liquid is 0.15m/s, the pressure is 0.8MPaG, and the temperature is 10 ℃;
then enters the desulfurization and separation tank 22 for 45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization and separation tank 22, enters the regeneration device 6 through a pipeline 61, and the liquefied gas after desulfurization comes out from the top of the desulfurization and separation tank 22 and exits the device through a third liquefied gas pipeline 93.
Also, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content of the liquefied gas discharged from the top of the desulfurization separator was performed, and the measurement results are shown in table 3.
Example 15:
substantially the same as in example 10, except that the desulfurization method in the present embodiment comprises the steps of:
the compound amine liquid and the liquefied gas enter a first-stage fiber membrane contact reactor 21a according to the mass ratio of 0.06 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the first-stage fiber membrane contact reactor 21a is 0.3m/s, the apparent linear velocity of the compound amine liquid is 0.02m/s, the pressure is 3.5MPaG, and the temperature is 10 ℃; then enters the first-stage desulfurization separating tank 22a for 5 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the first-stage desulfurization separating tank 22a, enters the regenerating device 6 through a pipeline 61, and the liquefied gas after preliminary desulfurization comes out from the top of the first-stage desulfurization separating tank 22a and enters the second-stage fiber membrane contact reactor 21b through a second liquefied gas pipeline 92 for further desulfurization.
The compound amine liquid and the liquefied gas from the first-stage desulfurization separation tank 22a enter a second-stage fiber membrane contact reactor 21b according to a mass ratio of 3 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the second-stage fiber membrane contact reactor 21b is 1m/s, the apparent linear velocity of the compound amine liquid is 0.15m/s, the pressure is 0.8MPaG, and the temperature is 60 ℃; then enters the second-stage desulfurization separating tank 22b for 45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the second-stage desulfurization separating tank 22b, enters the regeneration device 6 through a pipeline 61, and the liquefied gas subjected to further desulfurization comes out from the top of the second-stage desulfurization separating tank 22b and comes out of the device through a third liquefied gas pipeline 93.
In the same manner, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the first-stage desulfurization separator and the liquefied gas from the top of the second-stage desulfurization separator, and the measurement results are shown in table 3.
Example 16:
the difference is that the embodiment is basically the same as that of the embodiment 15, and the embodiment also comprises a packed amine washing desulfurizing tower, wherein the desulfurizing tower is connected with the first-stage fiber membrane contact reactor, and the desulfurizing tower is connected with a compound amine liquid tank and is used for preliminarily removing non-mercaptan sulfur and mercaptan in liquefied gas to obtain compound amine liquid containing sulfide and preliminarily desulfurized liquefied gas, and the preliminarily desulfurized liquefied gas enters the first-stage fiber membrane contact reactor for further desulfurization. The desulfurization method in the implementation comprises the following steps:
1. The compound amine liquid and the liquefied gas enter a desulfurizing tower according to the mass ratio of 0.2 to reversely contact and complete preliminary desulfurization, the separation is carried out, the pressure in the desulfurizing tower is 0.8MPaG, the temperature is 10 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower and enters a regenerating device through a pipeline, and the liquefied gas after preliminary desulfurization comes out from the top of the desulfurizing tower and enters a first-stage fiber membrane contact reactor to carry out further desulfurization;
the compound amine liquid and the liquefied gas enter a first-stage fiber membrane contact reactor according to the mass ratio of 3 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the first-stage fiber membrane contact reactor is 1m/s, the apparent linear velocity of the compound amine liquid is 0.02m/s, the pressure is 3.5MPaG, and the temperature is 10 ℃; then enters a first-stage desulfurization separating tank to stay for 45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the first-stage desulfurization separating tank, and enters a regenerating device through a pipeline, and the liquefied gas after preliminary desulfurization comes out from the top of the first-stage desulfurization separating tank and enters a second-stage fiber membrane contact reactor for further desulfurization.
The compound amine liquid and the liquefied gas from the first-stage desulfurization separation tank enter a second-stage fiber membrane contact reactor according to the mass ratio of 0.06 to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas in the second-stage fiber membrane contact reactor is 0.3m/s, the apparent linear velocity of the compound amine liquid is 0.15m/s, the pressure is 0.8MPaG, and the temperature is 60 ℃; then enters a second-stage desulfurization separating tank to stay for 5 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the second-stage desulfurization separating tank, and enters a regenerating device through a pipeline, and the liquefied gas after further desulfurization comes out from the top of the second-stage desulfurization separating tank and exits the device.
In the same manner, in this example, in order to intuitively observe the desulfurization effect, the measurement of the sulfide content was performed on the liquefied gas from the top of the first-stage desulfurization separator and the liquefied gas from the top of the second-stage desulfurization separator, and the measurement results are shown in table 3.
Comparative example 2:
after hydrogen sulfide is removed by amine washing (MDEA solution) of an amine washing tower, mercaptan is removed by alkaline washing of a secondary fiber membrane, and carbonyl sulfide is removed by arranging a set of carbonyl sulfide hydrolysis tower and a set of fine desulfurization tower.
The device comprises an amine washing tower (being a filler amine washing tower), two fiber film alkaline washing contactors (comprising two corresponding separating tanks, wherein the inner core of the fiber film alkaline washing contactor is made of stainless steel wires, the length-diameter ratio of the fiber film alkaline washing contactor is 6), two carbonyl sulfide hydrolysis towers (one open and one standby, solid hydrolytic agent is filled in the two carbonyl sulfide hydrolysis towers), two fine desulfurization towers (one open and one standby, solid fine desulfurization agent is filled in the two carbonyl sulfide hydrolysis towers), and liquefied gas to be desulfurized is sequentially connected with the amine washing towers, the two fiber film alkaline washing contactors, the carbonyl sulfide hydrolysis towers and the fine desulfurization towers through corresponding liquefied gas pipelines.
The required amine solution for the unit was a 30% wtmdea solution from an amine solution regeneration unit connected to the amine scrubber via a corresponding line and removed from the regeneration unit at the bottom outlet of the amine scrubber.
The required sweetening alkali liquor of the device is 10-15%wt sodium hydroxide solution, and the sodium hydroxide solution is from an alkali liquor regeneration system, is connected with a fiber membrane alkali washing contactor through a corresponding pipeline, and is removed from the bottom outlet of the separation tank to the regeneration device.
The properties of the liquefied gas in this comparative example were the same as those of the liquefied gas in example 7 described above.
The desulfurization method comprises the following steps:
1. the MDEA solution and the liquefied gas enter an amine washing tower according to the mass ratio of 35% to reversely contact and complete removal of hydrogen sulfide, the pressure in the amine washing tower is 1.6MPaG, the temperature is 40 ℃, the MDEA solution rich in sulfide flows out from the bottom of the amine washing tower and enters a regeneration device through a corresponding pipeline, and the liquefied gas after removal of hydrogen sulfide flows out from the top of the amine washing tower and enters a fiber membrane alkaline washing contactor through a corresponding pipeline to remove mercaptan;
2. the alkali liquor and the liquefied gas from the amine washing tower sequentially enter a primary fiber membrane alkali washing contactor and a secondary fiber membrane alkali washing contactor according to the mass ratio of 30% to be in forward contact for desulfurization, wherein the apparent linear velocity of the liquefied gas is 0.8m/s, the apparent linear velocity of the alkali liquor is 0.12m/s, the pressures in the primary fiber membrane alkali washing contactor and the secondary fiber membrane alkali washing contactor are respectively 1.48MpaG and 1.43MpaG, and the temperatures are 40 ℃; then the alkaline solution in the secondary separation tank flows out from the bottom of the secondary separation tank and enters the primary fiber membrane alkaline washing contactor through a corresponding pipeline, the alkaline solution in the primary separation tank flows out from the bottom of the primary separation tank and enters the regenerating device, and the liquefied gas after mercaptan removal flows out from the top of the secondary separation tank and enters the carbonyl sulfide hydrolysis tower.
3. After mercaptan removal, liquefied gas enters from the bottom of the carbonyl sulfide hydrolysis tower, after carbonyl sulfide hydrolysis is completed, the liquefied gas exits from the top of the carbonyl sulfide hydrolysis tower, enters from the bottom of the fine desulfurization tower, and exits from the top of the fine desulfurization tower after fine desulfurization is completed.
In this comparative example, in order to intuitively observe the comparison with the desulfurization effect of the example, the amounts of sulfide in the liquefied gas from the top of the amine scrubber, the liquefied gas from the top of the secondary separation tank, and the liquefied gas from the top of the fine desulfurization tower were measured, respectively, and the measurement results are shown in table 3.
TABLE 3 sulfide content table in liquefied gas after desulfurization of examples and comparative examples
As can be seen from the implementation results of the above examples, the device and the method for removing the non-mercaptan sulfur and mercaptan in the liquefied gas by the wet method provided by the invention can remove the non-mercaptan sulfur in the liquefied gas to 10mg/m 3 The method has the advantages of simple flow, no three-waste discharge, low technical upgrading difficulty, realization of recycling of sulfur resources, and finally elimination of bottleneck for continuous deep processing and utilization of liquefied gas containing non-mercaptan sulfur and mercaptan, and can be upgraded and reformed by using the existing amine-eluted hydrogen sulfide equipment and amine-washed regeneration facilities.
Therefore, the device and the method provided by the invention not only simplify the flow of removing non-mercaptan sulfur and mercaptan from the liquefied gas and greatly reduce the investment and operation cost, but also reduce the difficulty of technical upgrading and transformation and avoid the emission of three wastes. The invention overcomes and solves the defects of complex flow, high investment and operation cost, large three-waste discharge, large technical upgrading difficulty and the like in the prior art, and achieves the aim of the invention.
Claims (5)
1. An apparatus for wet stripping non-mercaptan sulfur and mercaptans from liquefied gas, comprising:
compounding an amine liquid tank;
the fiber membrane contact reactor is provided with an air inlet for liquefied gas to enter, and is connected with the compound amine liquid tank and used for enabling the compound amine liquid and the liquefied gas to contact in the fiber membrane contact reactor for desulfurization; the desulfurization separating tank is arranged at the bottom of the fiber membrane contact reactor, is connected with the fiber membrane contact reactor and is used for separating the desulfurized liquefied gas and the compound amine liquid containing sulfide;
the desulfurization tower is connected with the air inlet of the first-stage fiber membrane contactor and is used for primarily removing non-mercaptan sulfur and mercaptan sulfur in the liquefied gas to obtain compound amine liquid containing sulfide and primarily desulfurized liquefied gas;
the desulfurizing tower is a packed amine sulfur eluting tower or a sieve plate amine sulfur eluting tower;
the device also comprises a regeneration device which is connected with the desulfurization tower and the desulfurization separation tank and is used for separating the compound amine liquid containing sulfide so as to recycle the sulfide and the compound amine liquid;
The composition of the compound amine liquid in the compound amine liquid tank is as follows:
1-50% (wt) of UDS desulfurizing agent, 0-50% (wt) of N-methyl diethanol amine, and water is used for supplementing the desulfurizing agent when the total amount is less than 100% (wt).
2. The apparatus for wet stripping non-mercaptan sulfur and mercaptans in liquefied gas according to claim 1, characterized in that: the inner core material in the fiber membrane contact reactor is stainless steel wire, and the length-diameter ratio of the fiber membrane contact reactor is 3-24.
3. The apparatus for wet stripping non-mercaptan sulfur and mercaptans in liquefied gas according to claim 1, characterized in that: the fiber membrane contactor has two stages, and the two stages of fiber membrane contactors are connected in series.
4. A method for desulfurizing a wet process liquefied gas by using the apparatus for removing non-mercaptan sulfur and mercaptan according to claim 1, comprising the steps of:
when the fiber membrane contactor is at one stage, the desulfurization step is as follows:
1. the compound amine liquid and the liquefied gas enter a desulfurizing tower in a reverse contact way according to the mass ratio of 20-50% to finish preliminary desulfurization, separation is carried out, the pressure in the desulfurizing tower is 0.8-3.5MPaG, the temperature is 10-60 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower, and the liquefied gas after preliminary desulfurization flows out from the top of the desulfurizing tower and enters a fiber membrane contactor to further desulfurize;
2. The compound amine liquid and the liquefied gas from the desulfurizing tower enter a fiber membrane contact reactor according to the mass ratio of 6-30% to be subjected to forward contact to complete desulfurization, the apparent linear velocity of the liquefied gas is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure in the fiber membrane contact reactor is 0.8-3.5MPaG, and the temperature is 10-60 ℃; then enters a desulfurization separation tank to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank, and the liquefied gas after desulfurization is discharged from the top of the desulfurization separation tank;
when the fiber membrane contactor is more than one stage, the fiber membrane contactors of all stages are connected in series, and the desulfurization step is as follows:
(1) the compound amine liquid and the liquefied gas enter a desulfurizing tower in a reverse contact way according to the mass ratio of 20-50% to finish preliminary desulfurization, separation is carried out, the pressure in the desulfurizing tower is 0.8-3.5MPaG, the temperature is 10-60 ℃, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurizing tower, and the liquefied gas after preliminary desulfurization flows out from the top of the desulfurizing tower and enters a first-stage fiber membrane contactor to further desulfurize;
(2) the compound amine liquid and the liquefied gas from the desulfurization tower enter a first-stage fiber membrane contact reactor according to the mass ratio of 6-30% to be subjected to forward contact to complete further desulfurization, the apparent linear velocity of the liquefied gas is 0.3-1m/s, the apparent linear velocity of the compound amine liquid is 0.02-0.15m/s, the pressure in the first-stage fiber membrane contact reactor is 0.8-3.5MPaG, and the temperature is 10-60 ℃; then enters a desulfurization separation tank of the first stage to stay for 5-45 minutes for separation, the compound amine liquid rich in sulfide flows out from the bottom of the desulfurization separation tank of the first stage, and the liquefied gas after desulfurization flows out from the top of the desulfurization separation tank of the first stage;
(3) And (3) feeding the liquefied gas coming out of the top of the first-stage desulfurization separation tank into a second-stage fiber membrane contactor adjacent to the liquefied gas, and carrying out desulfurization according to the step (2), and circulating in such a way until desulfurization in each-stage fiber membrane contactor is completed, and discharging the desulfurized liquefied gas from the top of the last-stage desulfurization separation tank.
5. The method according to claim 4, wherein: the mass ratio of the compound amine liquid to the liquefied gas in the first step and/or the step (1) is 0.25-0.35; the mass ratio of the compound amine liquid to the liquefied gas in the second step and/or the step (2) is 0.15-0.25, the apparent linear velocity of the liquefied gas is 0.5-0.9m/s, the apparent linear velocity of the compound amine liquid is 0.06-0.10m/s, and the residence time in the desulfurization separation tank is 10-30 minutes.
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