CN115253612A - Fischer-Tropsch synthesis tail gas separation and recovery system and method - Google Patents
Fischer-Tropsch synthesis tail gas separation and recovery system and method Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 102
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 59
- 238000011084 recovery Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 234
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000001257 hydrogen Substances 0.000 claims abstract description 105
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 105
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 238000005262 decarbonization Methods 0.000 claims abstract description 14
- 238000005261 decarburization Methods 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 85
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 30
- 238000003795 desorption Methods 0.000 claims description 29
- 239000002737 fuel gas Substances 0.000 claims description 23
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 21
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003949 liquefied natural gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- -1 carbon hydrocarbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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
- B01D53/22—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
- B01D53/002—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 condensation
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01D53/26—Drying gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention provides a Fischer-Tropsch synthesis tail gas separation and recovery system and a Fischer-Tropsch synthesis tail gas separation and recovery method. The Fischer-Tropsch synthesis tail gas separation and recovery system provided by the invention comprises a membrane separation unit, a decarburization unit, a drying unit, a cryogenic separation unit and a PSA unit. The application provides a ft synthesis tail gas separation recovery system handles through with ft synthesis tail gas through membrane separation unit, decarbonization unit, drying unit, cryrogenic separation unit and PSA unit in proper order, has realized the reasonable cutting of hydrogen, carbon monoxide, methane, more than three components of carbon and carbon two components, has reduced equipment investment and energy consumption when guaranteeing the product pluralism, has improved the economic nature of ft synthesis tail gas recovery technology.
Description
Technical Field
The invention relates to the field of waste gas recycling, in particular to a Fischer-Tropsch synthesis tail gas separation and recovery system and a Fischer-Tropsch synthesis tail gas separation and recovery method.
Background
Fischer-Tropsch synthesis is a method for indirectly synthesizing oil products by using coal, natural gas and other raw materials, and utilizes a catalyst to synthesize synthesis gas (H) 2 + CO) to heavy oil, light oil, wax, lower hydrocarbons, etc. In addition to the above products, more Fischer-Tropsch synthesis tail gas is generated in the Fischer-Tropsch synthesis reaction process due to the limitation of the reaction conversion rate.
For Fischer-Tropsch synthesis tail gas, the Fischer-Tropsch synthesis tail gas mainly comprises unreacted hydrogen, carbon monoxide, nitrogen, carbon dioxide, low-carbon hydrocarbon and the like generated by side reaction, wherein the low-carbon hydrocarbon, the hydrogen and the carbon monoxide are components with higher economic values, and the economic benefit of the indirect coal liquefaction device is improved by recycling. However, at present, one mode of Fischer-Tropsch synthesis tail gas is used as fuel for heat supply or power generation, the other mode is direct relief, the two modes not only waste a large amount of precious resources, but also cause certain pollution to the environment, and if products such as hydrogen, methane, carbon monoxide, low carbon hydrocarbon and the like can be separated from the Fischer-Tropsch synthesis tail gas, the economic value of the Fischer-Tropsch synthesis tail gas can be greatly improved, and the comprehensive utilization efficiency of the energy of the whole indirect coal liquefaction is improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention mainly aims to provide a system and a method for separating and recovering Fischer-Tropsch synthesis tail gas, and aims to solve the problems of resource waste and environmental pollution caused by the fact that Fischer-Tropsch synthesis tail gas is used as fuel for heat supply and power generation or is directly exhausted in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a fischer-tropsch synthesis tail gas separation and recovery system, comprising: the membrane separation unit is used for separating Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas; the decarbonization unit is connected with the membrane separation unit and is used for removing carbon dioxide in the first tail gas to obtain a second tail gas; the drying unit is connected with the decarburization unit and is used for removing moisture in the second tail gas to obtain a third tail gas; the cryogenic separation unit is connected with the drying unit and is used for separating the third tail gas into LPG, LNG, fuel gas and light components, and the light components comprise hydrogen and carbon monoxide; and the PSA unit is respectively connected with the cryogenic separation unit and the membrane separation unit and is used for adsorbing carbon monoxide and hydrogen in light components and hydrogen in hydrogen-rich gas to obtain a desorbed gas, and the carbon monoxide and the hydrogen are recovered in a desorption manner to obtain the carbon monoxide and the hydrogen.
Further, the cryogenic separation unit comprises a deethanizer, a demethanizer, a flash tank and a methane rectification tower which are sequentially communicated, wherein the deethanizer is used for separating third tail gas into LPG and fourth tail gas, the demethanizer is used for separating fourth tail gas into fuel gas and fifth tail gas, the flash tank is used for separating fifth tail gas into a first light component and a methane crude product, the methane rectification tower is used for separating the methane crude product into LNG and a second light component, and the first light component and the second light component are mixed to obtain the light component.
Further, the PSA unit comprises a PSA-CO unit and a PSA-H unit 2 The unit, PSA-CO unit and cryrogenic separation unit link to each other for adsorb carbon monoxide in the light component, obtain crude hydrogen, PSA-H2 unit links to each other with PSA-CO unit and membrane separation unit respectively for adsorb hydrogen in hydrogen-rich gas and the crude hydrogen, obtain the desorption gas, just hydrogen is retrieved through desorption mode to PSA-H2 unit, carbon monoxide is retrieved through desorption's mode to PSA-CO unit.
Further, the stripping gas is connected to the drying unit for use as regeneration gas for the drying unit.
According to another aspect of the invention, the Fischer-Tropsch synthesis tail gas separation and recovery method is also provided, and comprises the following steps: s1, performing membrane separation treatment on Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas; s2, performing carbon dioxide removal treatment on the first tail gas to obtain a second tail gas; s3, drying the second tail gas to obtain a third tail gas; s4, performing cryogenic separation treatment on the third tail gas to obtain LPG, LNG, fuel gas and light components, wherein the light components comprise carbon monoxide and hydrogen; and S5, performing adsorption treatment on the carbon monoxide and the hydrogen in the light component, performing adsorption treatment on the hydrogen in the hydrogen-rich gas to obtain a resolved gas, and respectively recovering the hydrogen and the carbon monoxide through desorption to obtain the carbon monoxide and the hydrogen.
Further, step S4 includes: s41, separating more than three carbon components from the third tail gas to obtain LPG and a fourth tail gas; s42, separating the carbon dioxide component of the fourth tail gas to obtain fuel gas and fifth tail gas; step S43, carrying out flash evaporation treatment on the fifth tail gas to obtain a first light component and a methane crude product; s44, rectifying the crude methane product to obtain LNG and a second light component; wherein the first light component and the second light component are mixed to obtain the light component.
Further, in step S41, the separation treatment of the components with more than three carbon atoms is carried out in a deethanizer, the pressure at the top of the deethanizer is 2.2-2.4 MPa, the temperature at the top of the deethanizer is-80 to-100 ℃, and the temperature at the bottom of the deethanizer is 80-90 ℃.
Further, step S42, the separation treatment of the carbon two components is carried out in a demethanizer, the pressure at the top of the demethanizer is 1.8 to 2.0MPa, the temperature at the top of the demethanizer is-120 to-150 ℃, and the temperature at the bottom of the deethanizer is-2 to-10 ℃.
Further, step S43, the flash evaporation treatment is carried out in a flash evaporation tank, the fifth tail gas exchanges heat to-170 to-190 ℃ and then is introduced into the flash evaporation tank for the flash evaporation treatment, and the pressure in the flash evaporation tank is 0.2 to 0.5MPa.
Further, step S44, the rectification is carried out in a methane rectification tower, the pressure of the top of the methane rectification tower is 0.2-0.4 MPa, the temperature of the top of the methane rectification tower is-150 to-170 ℃, and the temperature of the bottom of the methane rectification tower is-140 to-160 ℃.
Further, step S5 includes: s51, performing carbon monoxide adsorption treatment on the light components to obtain crude hydrogen, and recovering carbon monoxide from a PSA-CO unit in a desorption manner; step S52, mixing the crude hydrogen and the hydrogen-rich gas to perform hydrogen adsorption treatment to obtain the desorbed gas, and performing desorption from PSA-H 2 The unit recovers hydrogen.
Further, in step S51, the carbon monoxide adsorption treatment is carried out in PSA-CO, the pressure of the light component is increased to 3.0-3.2 MPa, and then the light component is introduced into a PSA-CO unit to carry out the carbon monoxide adsorption treatment.
Furthermore, the drying unit is a molecular sieve drying device, and the desorption gas is used as regeneration gas of the molecular sieve drying device. Use the technical scheme of this application, the ft synthesis tail gas separation recovery system that this application provided, through with ft synthesis tail gas in proper order through membrane separation unit, decarbonization unit, drying unit, cryogenic separation unit and PSA unit treatment, realized the reasonable cutting of hydrogen, carbon monoxide, methane, more than three components of carbon and carbon two components, reduced equipment investment and energy consumption when guaranteeing the product pluralism, improved the economic nature of ft synthesis tail gas recovery technology.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a block diagram of a Fischer-Tropsch synthesis tail gas separation and recovery system according to embodiment 1 of the invention;
wherein the figures include the following reference numerals:
10. a membrane separation unit; 20. a decarbonization unit; 30. a drying unit; 401. a deethanizer; 402. demethanizer, 403, flash drum; 404. a methane rectification column; 405. a PSA-CO unit; 406. PSA-H 2 A unit; 407.a heat exchanger; 408-compressor.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Like this application background art analysis, the mode that the ft synthesis tail gas was used for heat supply power generation or directly relaxed to put among the prior art as fuel is handled, has a large amount of valuable resources of extravagant and the problem that causes the pollution to the environment, in order to solve this problem, this application provides a ft synthesis tail gas recovery system and method.
In a first exemplary embodiment of the present application, there is provided a fischer-tropsch synthesis tail gas separation and recovery system, comprising: the membrane separation unit 10 is used for separating Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas; the decarbonization unit 20 is connected with the membrane separation unit 10, and is used for removing carbon dioxide in the first tail gas to obtain a second tail gas; the drying unit 30, the drying unit 30 is connected to the decarbonization unit 20, and is used for removing moisture from the second tail gas to obtain a third tail gas; a cryogenic separation unit connected to the drying unit 30 for separating the third tail gas into LPG, LNG, fuel gas, and light components including hydrogen and carbon monoxide; and the PSA unit is respectively connected with the cryogenic separation unit and the membrane separation unit 10 and is used for adsorbing carbon monoxide and hydrogen in light components and hydrogen in hydrogen-rich gas to obtain a desorbed gas, and respectively recovering the carbon monoxide and the hydrogen in a desorption mode.
The above-mentioned LPG is represented by liquefied petroleum gas; the LNG is represented by liquefied natural gas; the PSA is represented by pressure swing adsorption.
Use the technical scheme of this application, the ft synthesis tail gas separation recovery system that this application provided, through with ft synthesis tail gas in proper order through membrane separation unit 10, decarbonization unit 20, drying unit 30, cryrogenic separation unit and PSA unit processing, realized hydrogen, carbon monoxide, methane, the reasonable cutting of more than three components of carbon and carbon two components, reduced equipment investment and energy consumption when guaranteeing the product pluralism, improved the economic nature of ft synthesis tail gas recovery technology.
The specific type of the membrane separation unit 10 is not limited, and any device capable of separating hydrogen-rich gas from the fischer-tropsch synthesis tail gas may be used. The specific type of the decarbonization unit 20 is not limited, and any device capable of removing carbon dioxide from the first tail gas can be used, including but not limited to an MDEA (N-methyldiethanolamine) decarbonization device. The specific type of the drying unit 30 is not limited, and any device capable of removing moisture from the second tail gas may be used, including but not limited to a molecular sieve drying device.
In order to improve the efficiency of separating the third tail gas into LPG, LNG, fuel gas and light components, the cryogenic separation unit preferably comprises a deethanizer 401, a demethanizer 402, a flash drum 403 and a methane rectification tower 404 which are sequentially connected, wherein the deethanizer 401 is used for separating the third tail gas into LPG and fourth tail gas; the demethanizer 402 is configured to separate the fourth tail gas into a fuel gas and a fifth tail gas; the flash drum 403 is used for separating the fifth tail gas into a first light component and a crude methane product; the methane rectification column 404 is used to separate the crude methane into LNG and a second light component; the first light component and the second light component are mixed to obtain the light component.
The deethanizer 401 is configured to separate more than three carbon components in the third tail gas from the third tail gas to obtain a fourth tail gas, the more than three carbon components are discharged from the bottom of the tower and used as LPG, and the fourth tail gas is discharged from the top of the deethanizer 401. The demethanizer 402 is configured to separate the carbon dioxide component from the fourth tail gas to obtain a fifth tail gas, the carbon dioxide component is discharged from the top of the demethanizer 402 as a fuel gas, and the fifth tail gas includes gases such as hydrogen, methane, carbon monoxide, and nitrogen. The flash tank 403 is configured to separate a crude methane product in the fifth tail gas to obtain a first light component, where the crude methane product is discharged from the bottom of the flash tank 403, and the first light component is discharged from the top of the flash tank 403, and the first light component includes gases such as hydrogen, methane, and nitrogen. The methane rectifying tower 404 is used for rectifying the crude methane product, the methane with high purity is discharged from the bottom of the methane rectifying tower 404 and is used as LNG, and the second light component is discharged from the top of the methane rectifying tower 404. The mixture of the first light component and the second light component is collectively referred to as the light component.
In order to further improve the separation efficiency of the flash tank 403, a heat exchanger 407 is preferably disposed on the pipeline between the flash tank 403 and the demethanizer 402, and the temperature of the fifth tail gas is adjusted to a suitable flash temperature by the heat exchanger 407 and then introduced into the flash tank 403 for separation treatment.
To further increase the efficiency of the PSA unit for adsorbing carbon monoxide as well as hydrogen, it is preferred that the PSA unit comprises a PSA-CO unit 405 and a PSA-H 2 The unit 406 and the PSA-CO unit 405 are connected with a cryogenic separation unit and used for adsorbing carbon monoxide in light components to obtain crude hydrogen, and then the carbon monoxide is recovered from the PSA-CO unit 405 in a desorption mode; PSA-H 2 Unit 406 is connected to PSA-CO unit 405 and membrane separation unit 10, respectively, for adsorbing hydrogen-rich gas and hydrogen from the crude hydrogen to obtain a desorbed gas, which is subsequently desorbed from PSA-H 2 Hydrogen is recovered in unit 406.
In order to further improve the adsorption efficiency of the PSA unit, a compressor 408 is preferably provided in the line between the methane rectifier 404 and the PSA unit to facilitate the pressure increase of the light components to a pressure range suitable for pressure swing adsorption, and then the light components are introduced into the PSA unit for adsorption treatment.
In order to further improve the energy utilization efficiency, preferably, the desorption gas can be directly merged into a fuel gas pipe network for recycling, and when the drying unit 30 is a molecular sieve drying device, the desorption gas can be further connected with the molecular sieve drying device, introduced into the molecular sieve drying device for use as a regeneration gas, and merged into a fuel gas pipe for recycling after regeneration.
In a second exemplary embodiment of the present application, there is also provided a fischer-tropsch synthesis tail gas separation and recovery method, including: s1, performing membrane separation treatment on Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas; s2, performing carbon dioxide removal treatment on the first tail gas to obtain a second tail gas; s3, drying the second tail gas to obtain a third tail gas; s4, carrying out cryogenic separation treatment on the third tail gas to obtain LPG, LNG, fuel gas and light components, wherein the light components comprise carbon monoxide and hydrogen; and S5, adsorbing carbon monoxide and hydrogen in the light components, adsorbing hydrogen in the hydrogen-rich gas to obtain a resolved gas, and respectively recovering the hydrogen and the carbon monoxide in a desorption manner to obtain the carbon monoxide and the hydrogen.
Use the technical scheme of this application, the ft synthesis tail gas separation recovery method that this application provided carries out membrane separation, carbon dioxide desorption, drying, cryogenic separation and pressure swing adsorption with ft synthesis tail gas in proper order and handles, has realized the reasonable cutting of hydrogen, carbon monoxide, methane, the more than three components of carbon and carbon two components, has reduced equipment investment and energy consumption when guaranteeing the product pluralism, has improved the economic nature of ft synthesis tail gas recovery technology.
In order to improve the efficiency of the cryogenic separation treatment of the third tail gas, it is preferable that the step S4 includes: s41, separating more than three carbon components from the third tail gas to obtain LPG and a fourth tail gas; s42, separating the carbon dioxide component of the fourth tail gas to obtain fuel gas and fifth tail gas; step S43, carrying out flash evaporation treatment on the fifth tail gas to obtain a first light component and a methane crude product; and S44, rectifying the crude methane product to obtain LNG and a second light component, wherein the first light component and the second light component are mixed to obtain the light component.
In order to further improve the efficiency of the separation treatment of the carbon three or more components in step S41, it is preferable that the separation treatment of the carbon three or more components is performed in deethanizing carbon, the pressure at the top of the deethanizer 401 is controlled to be 2.2 to 2.4MPa, the temperature at the top of the deethanizer 401 is controlled to be-80 to-100 ℃, and the temperature at the bottom of the deethanizer 401 is controlled to be 80 to 90 ℃, so that the carbon three or more components are discharged from the bottom of the deethanizer 401 as LPG, and the fourth tail gas is discharged from the top of the deethanizer 401.
In order to further improve the efficiency of the separation treatment of the carbon two components in the step S42, it is preferable that the separation treatment of the carbon two components is performed in the demethanizer 402, the pressure at the top of the demethanizer 402 is controlled to be 1.8 to 2.0MPa, the temperature at the top of the demethanizer 402 is controlled to be-120 to-150 ℃, and the temperature at the bottom of the demethanizer 402 is controlled to be-2 to-10 ℃, so that the carbon two components are discharged from the bottom of the demethanizer 402 as a fuel gas, and the fifth tail gas is discharged from the top of the demethanizer 402.
In order to further improve the efficiency of the flash process in step S43, it is preferable that the flash process is performed in the flash drum 403, the fifth tail gas is firstly heat-exchanged to-170 to-190 ℃ and then is introduced into the flash drum 403 for flash process, the pressure in the flash drum 403 is controlled to be 0.2 to 0.5MPa, so as to facilitate the crude methane to be discharged from the bottom of the flash drum 403, and the first light component containing hydrogen, carbon monoxide and optionally nitrogen is discharged from the top of the flash drum 403.
In order to further improve the rectification efficiency of the crude methane in step S44, the rectification is preferably performed in the methane rectification tower 404, the pressure at the top of the methane rectification tower 404 is controlled to be 0.2-0.4 MPa, the temperature at the top of the methane rectification tower 404 is-150 to-170 ℃, and the temperature at the bottom of the methane rectification tower 404 is controlled to be-140 to-160 ℃, so as to facilitate the discharge of high-purity methane from the bottom of the methane rectification tower 404, and the second light component containing carbon monoxide and hydrogen is discharged from the top of the methane rectification tower 404 as an LNG product to be further recovered and separated.
In order to further improve the separation and recovery efficiency of the first light component and the second light component, the first light component and the second light component are mixed to be used as the light component for subsequent separation and utilization.
In order to further improve the pressure swing adsorption efficiency of the above light components and hydrogen-rich gas, it is preferable that step S5 includes: step S51, performing carbon monoxide adsorption treatment on the light components to obtain crude hydrogen, and recovering carbon monoxide from the PSA-CO unit 405 in a desorption manner; step S52, mixing the crude hydrogen with the hydrogen-rich gas separated by the membrane separation unit 10 for adsorption treatment to obtain a desorption gas, and then performing desorption treatment on the desorption gas from the PSA-H 2 Unit 406 recovers hydrogen.
In order to further improve the efficiency of the adsorption treatment of carbon monoxide and hydrogen, it is preferable that the carbon monoxide adsorption treatment is performed in the PSA-CO unit 405, the light component is introduced into the PSA-CO unit 405, and then the carbon monoxide gas in the light component is adsorbed by the PSA-CO unit 405 to obtain crude hydrogen gas, which is then subjected to the membrane separation treatmentHydrogen adsorption from hydrogen-rich mixture separated from unit 10 to PSA-H 2 In unit 406, crude hydrogen is mixed with hydrogen rich gas and fed to PSA-H 2 Hydrogen is adsorbed in unit 406 to produce a desorbed gas. The carbon monoxide absorbed in the PSA-CO unit 405 is subsequently desorbed by a desorption method commonly used in the art to obtain a carbon monoxide product, wherein the volume fraction of the carbon monoxide in the carbon monoxide product is more than or equal to 98%. PSA-H can also be desorbed using methods commonly used in the art 2 The hydrogen adsorbed in unit 406 is desorbed to yield a hydrogen product having a volume fraction of hydrogen of > 99.9%.
In order to further enhance the effect of the carbon monoxide adsorption treatment in step S51, it is preferable to increase the pressure of the light component to 3.0 to 3.2MPa and then introduce the light component into the PSA — CO unit 405 to perform the carbon monoxide adsorption treatment.
Typically, but not by way of limitation, in the fischer-tropsch synthesis tail gas separation and recovery method provided by the present application, the overhead pressure of the deethanizer 401 is, for example, 2.2MPa, 2.25MPa, 2.3MPa, 2.35MPa, 2.4MPa, or a range of any two values; the temperature at the top of the deethanizer 401 is, for example, minus 80 ℃, minus 85 ℃, minus 90 ℃, minus 95 ℃, minus 100 ℃ or a range consisting of any two values; the temperature at the top of the deethanizer 401 is, for example, 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, or a range of any two values; the pressure at the top of the demethanizer 402 is, for example, 1.8MPa, 1.85MPa, 1.9MPa, 1.95MPa, 2.0MPa or a range of any two values; the temperature at the top of the demethanizer 402 is, for example, -120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or a range consisting of any two values; the temperature of the bottom of the demethanizer 402 is in a range of-2 ℃, 5 ℃, 8 ℃, 10 ℃ or any two values; the temperature of the fifth tail gas before entering the flash tank 403 is-170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ or a range value consisting of any two values; the pressure in the flash tank 403 is, for example, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa or a range of any two of these values; the pressure at the top of the methane rectifying tower 404 is 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa or a range value formed by any two values; the top temperature of the methane rectifying tower 404 is-150 ℃, 152 ℃, 160 ℃, 165 ℃ and 170 ℃ or the range value formed by any two values; the temperature of the bottom of the methane rectifying tower 404 is in a range of-140 ℃, 142 ℃, 150 ℃, 158 ℃ and 160 ℃ or any two values; the pressure of the light component entering the PSA-CO unit 405 for the adsorption treatment is, for example, 3.0MPa, 3.05MPa, 3.1MPa, 3.15MPa, 3.2MPa or a range of any two values.
In order to further improve the energy utilization rate of the above-mentioned solution gas, the above-mentioned solution gas can be used as the regeneration gas of the drying unit 30 after being heated by steam, and can be merged into the fuel gas pipe network after being regenerated, or can be merged into the fuel gas pipe network after being directly pressurized by the compressor 408.
The following examples are provided to further illustrate the benefits of the present application.
Example 1
The embodiment provides a separation and recovery system for fischer-tropsch synthesis tail gas, as shown in fig. 1, the separation and recovery system for fischer-tropsch synthesis tail gas includes a membrane separation unit 10, a decarbonization unit 20, a drying unit 30, a cryogenic separation unit and a PSA unit, which are connected in sequence, wherein the membrane separation unit 10 is used for separating the fischer-tropsch synthesis tail gas to obtain hydrogen-rich gas and a first tail gas; the decarbonization unit 20 is connected with the membrane separation unit 10 and is used for removing carbon dioxide in the first tail gas to obtain a second tail gas; the drying unit 30 is connected with the decarbonization unit 20 and is used for removing moisture in the second tail gas to obtain a third tail gas; the cryogenic separation unit comprises a deethanizer 401, a demethanizer 402, a flash tank 403 and a methane rectifying tower 404 which are connected in sequence, wherein the deethanizer 401 is connected with the drying unit 30 and is used for separating more than three carbon components in the third tail gas to obtain a fourth tail gas, and the more than three carbon components are recycled as LPG; the demethanizer 402 is used for separating the carbon two components in the fourth tail gas to obtain a fifth tail gas, and the carbon two components are recycled as fuel gas; the flash tank 403 is used for separating a crude methane product in the fifth tail gas to obtain a first light component; the methane rectifying tower 404 is used for rectifying methane to obtain a second light component and a methane product; the PSA unit comprises a PSA-CO unit 405 and a PSA-H unit connected in sequence 2 Unit 406, first light fraction and second light fraction inMixing in a pipeline to obtain light components; the PSA-CO unit 405 is used for adsorbing CO in the light component to obtain crude hydrogen, and then desorbing and recovering the CO adsorbed in the PSA-CO through desorption; the crude hydrogen is mixed with the hydrogen-rich gas separated from the membrane separation unit 10 in a pipeline and then is introduced into PSA-H 2 In unit 406, PSA-H 2 Unit 406 is used to adsorb hydrogen from the crude hydrogen and hydrogen-rich gas to obtain a desorbed gas, which is subsequently desorbed to PSA-H 2 Recovering the hydrogen adsorbed in the step (2).
In order to further improve the separation efficiency of the flash tank 403, a heat exchanger 407 is disposed on the pipeline between the flash tank 403 and the demethanizer 402, and the fifth tail gas is heated to a temperature suitable for flash evaporation through the heat exchanger 407 and then is introduced into the flash tank 403 for separation treatment.
In order to further improve the adsorption efficiency of the PSA unit, a compressor 408 is disposed on a pipeline between the methane rectifier 404 and the PSA unit, so as to facilitate the pressure raising of the light components to a range suitable for pressure swing adsorption, and then the light components are introduced into the PSA unit for adsorption treatment.
In this embodiment, drying unit 30 is molecular sieve drying equipment, and analytic gas links to each other with molecular sieve drying equipment to do benefit to the regeneration gas that is regarded as molecular sieve drying equipment with analytic gas after the heating to use, further energy saving, the direct fuel gas pipe network recycle that merges after the follow-up analytic gas regeneration.
Example 2
The embodiment provides a fischer-tropsch synthesis tail gas separation and recovery method, which is implemented by using the fischer-tropsch synthesis tail gas separation and recovery system provided in embodiment 1, and comprises the following steps:
(1) The first tail gas and the hydrogen-rich gas obtained by the Fischer-Tropsch synthesis tail gas through the membrane separation unit 10;
(2) Decompressing the first tail gas, introducing the first tail gas into a decarburization unit 20, and removing carbon dioxide in the first tail gas to obtain a second tail gas;
(3) Removing moisture in the second tail gas through a drying unit 30 to obtain a third tail gas;
(4) Introducing the third tail gas into the deethanizer 401, controlling the pressure at the top of the deethanizer 401 to be 2.3MPa, the temperature at the top of the deethanizer 401 to be-90 ℃, and the temperature at the bottom of the deethanizer 401 to be 85 ℃, so that more than three carbon components are discharged from the bottom of the deethanizer 401 as LPG, and the rest components are discharged from the top of the deethanizer as fourth tail gas;
(5) Introducing the fourth tail gas into the demethanizer 402, controlling the pressure at the top of the demethanizer 402 to be 1.9MPa, the temperature at the top of the demethanizer 402 to be-142 ℃ and the temperature at the bottom of the demethanizer to be-5 ℃, so that the carbon two components are discharged from the bottom of the demethanizer and are recycled as fuel gas, and the rest components are discharged from the top of the demethanizer as fifth tail gas;
(6) Cooling the fifth tail gas to-180 ℃ through a heat exchanger 407, introducing the fifth tail gas into a flash tank 403, and controlling the pressure of the flash tank 403 to be 0.3MPa, so that a crude methane product is discharged from the bottom of the flash tank 403, and the rest of components are discharged from the top of the flash tank 403 as a first light component;
(7) Introducing the crude methane product into a methane rectifying tower 404 for refining, controlling the temperature at the top of the methane rectifying tower 404 to be 0.3MPa, the temperature at the top of the methane rectifying tower 404 to be-161 ℃ and the temperature at the bottom of the methane rectifying tower to be-147 ℃, so that the refined methane product is discharged from the bottom of the methane rectifying tower and is recycled as LPG, and the rest components are discharged from the top of the methane rectifying tower as second light components;
(8) Mixing the first light component and the second light component in a pipeline to form a light component, increasing the pressure of the light component to 3.1MPa by a compressor 408, introducing the light component into a PSA-CO unit 405 for carbon monoxide adsorption to obtain crude hydrogen, and obtaining a CO product from the PSA-CO unit 405 through desorption;
(9) Mixing the crude hydrogen and the hydrogen-rich gas separated by the membrane separation unit 10 in a pipeline and then introducing the mixture into PSA-H 2 Unit 406 performs hydrogen adsorption to obtain a desorbed gas, which is desorbed from PSA-H 2 Unit 406 gets H 2 And (5) producing the product.
Example 3
This example is different from example 2 in that in step (4), the overhead pressure of the deethanizer 401 is controlled to 2.2 MPa; in the step (5), the pressure at the top of the demethanizer 402 is 2.0 MPa; in the step (6), the pressure of the flash tank 403 is 0.5MPa; in the step (7), the temperature at the top of the methane rectifying tower 404 is 0.2 MPa.
Example 4
This example differs from example 2 in that in step (5), the pressure in the demethanizer 402 is 1.5MPa.
Example 5
This example is different from example 2 in that the temperature at the top of the methane rectifying column 404 was 0.15MPa.
Test examples
The molar contents of more than three carbon components in LPG separated by the fischer-tropsch synthesis tail gas separation and recovery method provided in embodiments 2 to 5, the molar contents of two carbon components in the fuel gas obtained from the demethanizer 402, the molar content of methane in the methane product, the molar contents of CO in the CO product, and the molar contents of H in the CO product were measured respectively 2 In the product H 2 The results are shown in Table 1 below.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the application provides a ft synthesis tail gas separation recovery system handles through passing through membrane separation unit, decarbonization unit, drying unit, cryrogenic separation unit and PSA unit with ft synthesis tail gas in proper order, has realized the reasonable cutting of hydrogen, carbon monoxide, methane, more than three components of carbon and carbon two components, has reduced equipment investment and energy consumption when guaranteeing the product pluralism, has improved the economic nature of ft synthesis tail gas recovery technology.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The Fischer-Tropsch synthesis tail gas separation and recovery system is characterized by comprising:
the membrane separation unit (10) is used for separating Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas;
the decarbonization unit (20) is connected with the membrane separation unit (10) and is used for removing carbon dioxide in the first tail gas to obtain a second tail gas;
the drying unit (30) is connected with the decarburization unit (20) and is used for removing moisture in the second tail gas to obtain a third tail gas;
the cryogenic separation unit is connected with the drying unit (30) and is used for separating the third tail gas into LPG, LNG, fuel gas and light components, and the light components comprise hydrogen and carbon monoxide;
and the PSA unit is respectively connected with the cryogenic separation unit and the membrane separation unit (10) and used for adsorbing carbon monoxide and hydrogen in the light component and hydrogen in the hydrogen-rich gas to obtain the desorbed gas, and respectively recovering the carbon monoxide and the hydrogen in a desorption mode.
2. Fischer-Tropsch synthesis tail gas separation and recovery system according to claim 1, characterized in that the cryogenic separation unit comprises a deethanizer (401), a demethanizer (402), a flash tank (403) and a methane rectification column (404) which are sequentially connected, the deethanizer (401) being used to separate the third tail gas into the LPG and a fourth tail gas; the demethanizer (402) is to separate the fourth tail gas into the fuel gas and a fifth tail gas; the flash drum (403) is used for separating the fifth tail gas into a first light component and a crude methane product; the methane rectification column (404) is used for separating the crude methane into the LNG and a second light component; and mixing the first light component and the second light component to obtain the light component.
3. The Fischer-Tropsch synthesis tail gas separation and recovery system of claim 1, wherein the PSA unit comprises a PSA-CO unit (405) and a PS unitA-H 2 A unit (406), wherein the PSA-CO unit (405) is connected with the cryogenic separation unit and is used for adsorbing carbon monoxide in the light component to obtain crude hydrogen, and then recovering carbon monoxide from the PSA-CO unit (405) by means of desorption; the PSA-H 2 The unit (406) is respectively connected with the PSA-CO unit (405) and the membrane separation unit (10) and is used for adsorbing hydrogen in the hydrogen-rich gas and the crude hydrogen to obtain the desorption gas, the PSA-H2 unit (406) recovers hydrogen by means of desorption, and the PSA-CO unit (405) recovers carbon monoxide by means of desorption.
4. A fischer-tropsch synthesis tail gas separation and recovery system according to any one of claims 1 to 3, wherein the resolved gas is associated with the drying unit (30) for use as a regeneration gas for the drying unit (30).
5. The Fischer-Tropsch synthesis tail gas separation and recovery method is characterized by comprising the following steps:
s1, performing membrane separation treatment on the Fischer-Tropsch synthesis tail gas to obtain hydrogen-rich gas and first tail gas;
s2, performing carbon dioxide removal treatment on the first tail gas to obtain a second tail gas;
s3, drying the second tail gas to obtain a third tail gas;
s4, performing cryogenic separation treatment on the third tail gas to obtain LPG, LNG, fuel gas and light components, wherein the light components comprise carbon monoxide and hydrogen;
and S5, performing adsorption treatment on the carbon monoxide and the hydrogen in the light component, performing adsorption treatment on the hydrogen in the hydrogen-rich gas to obtain a resolved gas, and respectively recovering the hydrogen and the carbon monoxide in a desorption manner to obtain the carbon monoxide and the hydrogen.
6. A Fischer-Tropsch tail gas separation and recovery method according to claim 5, wherein the step S4 comprises the following steps:
step S41, separating more than three carbon components from the third tail gas to obtain LPG and a fourth tail gas;
s42, separating the carbon dioxide component of the fourth tail gas to obtain the fuel gas and a fifth tail gas;
step S43, carrying out flash evaporation treatment on the fifth tail gas to obtain a first light component and a methane crude product;
s44, rectifying the crude methane product to obtain the LNG and a second light component;
wherein the first light component and the second light component are mixed to obtain the light component.
7. A Fischer-Tropsch tail gas separation and recovery method according to claim 6, characterized in that in the step S41, the separation treatment of the components with more than three carbon atoms is carried out in a deethanizer (401), the pressure at the top of the deethanizer (401) is 2.2-2.4 MPa, the temperature at the top of the deethanizer (401) is-80-100 ℃, and the temperature at the bottom of the deethanizer (401) is 80-90 ℃;
preferably, in the step S42, the separation treatment of the carbon two components is carried out in a demethanizer (402), the pressure at the top of the demethanizer (402) is 1.8 to 2.0MPa, the temperature at the top of the demethanizer (402) is-120 to-150 ℃, and the temperature at the bottom of the demethanizer (402) is-2 to-10 ℃;
preferably, in the step S43, the flash evaporation treatment is performed in a flash evaporation tank (403), the fifth tail gas is firstly subjected to heat exchange to-170 to-190 ℃ and then introduced into the flash evaporation tank (403) to perform the flash evaporation treatment, and the pressure in the flash evaporation tank (403) is 0.2 to 0.5MPa;
preferably, in the step S44, the rectification is performed in a methane rectification tower (404), the pressure at the top of the methane rectification tower (404) is 0.2-0.4 MPa, the temperature at the top of the methane rectification tower (404) is-150 to-170 ℃, and the temperature at the bottom of the methane rectification tower (404) is-140 to-160 ℃.
8. A Fischer-Tropsch tail gas separation and recovery method according to claim 5, wherein the step S5 comprises the following steps:
step S51, performing carbon monoxide adsorption treatment on the light components to obtain crude hydrogen, and recovering carbon monoxide from a PSA-CO unit (405) in a desorption manner;
and S52, mixing the crude hydrogen and the hydrogen-rich gas to perform hydrogen adsorption treatment to obtain the decomposed gas, and recovering hydrogen from the PSA-H2 unit (406) in a desorption manner.
9. A Fischer-Tropsch tail gas separation and recovery method according to claim 8, characterized in that in the step S51, the carbon monoxide adsorption treatment is carried out in a PSA-CO unit (405), and the light components are firstly pressurized to 3.0-3.2 MPa and then are introduced into the PSA-CO unit (405) to carry out the carbon monoxide adsorption treatment.
10. Fischer-tropsch tail gas separation and recovery process according to any one of claims 5 to 9, the drying unit (30) being a molecular sieve drying plant, the stripping gas being used as regeneration gas for the molecular sieve drying plant.
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