CN109970029B - Membrane separation reinforced pressure swing adsorption hydrogen purification process for refinery gas with high hydrogen content - Google Patents
Membrane separation reinforced pressure swing adsorption hydrogen purification process for refinery gas with high hydrogen content Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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Abstract
The invention provides a membrane separation reinforced pressure swing adsorption hydrogen purification process for refinery gas with high hydrogen content, belonging to the field of petrochemical industry. According to the process, an organic steam membrane separation unit is introduced into a pretreatment system of a pressure swing adsorption device, hydrocarbon heavy components of five or more carbons are efficiently and deeply removed, the content is reduced to below 0.3 vol%, the regeneration condition of an adsorbent is improved, the service life of the adsorbent is prolonged, and the long-term operation stability of the device is improved; introducing a hydrogen membrane separation unit into a post-treatment system, and further recovering low-concentration hydrogen in the organic vapor membrane permeation gas and the pressure swing adsorption tail gas, so that the hydrogen content of the fuel gas is less than 15 vol%, and the total yield of the hydrogen is over 95%. By prolonging the service life of the adsorbent, improving the hydrogen recovery rate and adopting the membrane separation enhanced pressure swing adsorption purification process of the high-hydrogen-content refinery gas, the hydrogen separation and purification cost can be reduced by 10-20% compared with the traditional adsorption process.
Description
Technical Field
The invention relates to a membrane separation enhanced pressure swing adsorption hydrogen purification process for refinery gas with high hydrogen content (more than 75 vol%), belonging to the field of petrochemical industry. According to the process, an organic steam membrane separation unit is introduced into a pretreatment system of the pressure swing adsorption device, heavy hydrocarbon components of five or more carbons are efficiently and deeply removed, the regeneration condition of the adsorbent is improved, the service life of the adsorbent is prolonged, and the long-term operation stability of the adsorption device is improved; introducing a hydrogen membrane separation unit into the post-treatment system, and further recovering low-concentration hydrogen in the organic vapor membrane permeation gas and the pressure swing adsorption tail gas. The pressure swing adsorption purification process of the refinery gas with high hydrogen content and enhanced membrane separation has lower hydrogen separation and purification cost by prolonging the service life of the adsorbent and improving the hydrogen recovery rate.
Background
Crude oil deterioration (high acid, high sulfur and heavy weight) is more serious, and the requirement on cleanliness of fuel products is higher, which are two major challenges facing the global refining industry in recent years. To address these challenges, hydrogenation techniques such as hydrocracking, residuum hydrogenation, coal-diesel hydrogenation, gasoline hydrogenation, hydrodesulfurization, hydrosaturation, and the like, are increasingly being employed in refinery processes. The hydrogen consumption level for processing crude oil into qualified refinery products is about 200Nm as calculated by the average level of global refining at the present stage3T crude oil. The cost of hydrogen production has inevitably become the second largest cost expenditure of refinery business to crude oil. Meanwhile, a large amount of refinery gas with high hydrogen content is also produced as a byproduct in the refining process, for example, the hydrogen content of the catalytic reforming tail gas exceeds 90 vol%, the hydrogen content of the diesel hydrogenation tail gas can reach 88 vol%, the hydrogen content of the residual oil hydrogenation low-molecular gas can reach 80 vol%, and the hydrogen content of the hydrocracking low-molecular gas can reach 75 vol%. In view of large-scale consumption of hydrogen in the modern oil refining process, the efficient and low-cost recovery of hydrogen in refinery gas becomes an important way for greatly reducing the oil refining cost and improving the production competitiveness of refinery enterprises.
Pressure swing adsorption is the main means of separating and purifying hydrogen by taking high-hydrogen-content refinery gas as raw material at present, and products with hydrogen concentration more than 99 vol% can be obtained in most cases. The most typical application of pressure swing adsorption is the separation and purification of catalytic reforming tail gas, which has become the standard configuration and main source for obtaining hydrogen by most refining enterprises. In recent years, many domestic refinery enterprises gradually use the high-hydrogen-content refinery gas as a byproduct of devices for diesel hydrogenation, gasoline hydrogenation, wax oil hydrogenation, residual oil hydrogenation, hydrocracking and the like as a raw material for pressure swing adsorption, and the economic benefit is very considerable. However, pressure swing adsorption units often face two key bottlenecks in processing high hydrogen content refinery gases: 1) the refinery gas contains more heavy hydrocarbon components of five carbon atoms and above, is difficult to regenerate and desorb after being adsorbed, is easy to cause the failure of the adsorbent after long-term accumulation, has short service life, and obviously increases the operation and maintenance cost of the adsorption device; 2) the tail gas of the pressure swing adsorption contains a large amount of hydrogen, the content of the hydrogen generally exceeds 50 vol%, and even exceeds 65 vol% when the performance of the adsorbent is attenuated. Due to the aboveFor this reason, the separation and purification of hydrogen from refinery gas with high hydrogen content by pressure swing adsorption is costly. Taking the separation of the catalytic reforming byproduct tail gas as an example, the converted hydrogen separation cost exceeds 0.10kgEO/Nm3Hydrogen gas. In summary, one of the key points of the improvement of the pressure swing adsorption hydrogen purification device for refinery gas with high hydrogen content is how to prolong the service life of the adsorbent and improve the hydrogen recovery rate.
Disclosure of Invention
The invention aims to provide a membrane separation reinforced pressure swing adsorption hydrogen purification process for high-hydrogen-content refinery gas. The process introduces an organic steam membrane separation unit into a pretreatment system of a pressure swing adsorption device, utilizes selective permeation of a membrane to reduce the content of hydrocarbon heavy components of five or more carbons to be less than 0.3 vol%, prolongs the service life of an adsorbent, improves the long-term operation stability of the adsorption device, simultaneously introduces a hydrogen membrane separation unit into a post-treatment system of the pressure swing adsorption device, further recovers low-concentration hydrogen in organic steam membrane permeation gas and pressure swing adsorption tail gas, and ensures that the content of hydrogen in fuel gas is not more than 15 vol%.
The technical scheme of the invention is as follows:
a membrane separation reinforced pressure swing adsorption hydrogen purification process for refinery gas with high hydrogen content,
refinery gases with high hydrogen content are classified into four categories according to composition and pressure:
the first high hydrogen content refinery gas S-1, the pressure is less than 2.5MPaG, and the content of hydrocarbon heavy components of five or more carbon atoms is more than or equal to 1.0 vol%;
the second high hydrogen content refinery gas S-2, the pressure is more than or equal to 2.5MPaG, and the content of hydrocarbon heavy components of five carbon and above is more than or equal to 1.0 vol%;
the third high hydrogen content refinery gas S-3, the pressure is less than 2.5MPaG, and the content of hydrocarbon heavy components of five or more carbon is less than 1.0 vol%;
the fourth high hydrogen content refinery gas S-4, the pressure is more than or equal to 2.5MPaG, and the content of hydrocarbon heavy components of five carbon and above is less than 1.0 vol%;
the first high hydrogen-containing refinery gas S-1 is pressurized to 2.5MPaG by a first compressor 1, then is combined with the second high hydrogen-containing refinery gas S-2, then sequentially passes through a first cooler 2, a first heat exchanger 3 and a second cooler 4, and then enters a first liquid separation tank 5, a first condensate S-5 is extracted from the bottom of the first liquid separation tank 5, a first non-condensable gas S-6 is extracted from the top of the first liquid separation tank 5, and the first non-condensable gas S-6 enters the first heat exchanger 3;
the third high hydrogen-containing refinery gas S-3 is pressurized to 2.5MPaG by a second compressor 6, then is combined with the fourth high hydrogen-containing refinery gas S-4, is cooled by a third cooler 7, is combined with the first noncondensable gas S-6 passing through the first heat exchanger 3, and then enters an organic vapor membrane separation unit 8;
on the high-pressure side of the organic vapor membrane separation unit 8, first permeation residual gas S-7 is obtained, and the content of hydrocarbon heavy components of five carbons and above is reduced to be less than 0.3 vol%; on the low-pressure side of the organic steam membrane separation unit 8, obtaining a first permeating gas S-8, and concentrating hydrocarbon heavy components with five or more carbon atoms;
the first residual gas S-7 and the pressurized/cooled second permeation gas S-14 are combined to form feed gas of a pressure swing adsorption device 9, and the product hydrogen S-9 with the hydrogen concentration higher than 99 vol% and pressure swing adsorption tail gas S-10 are obtained through separation;
the first permeating gas S-8 and the pressure swing adsorption tail gas S-10 enter a third compressor 10 in a combined mode, then sequentially pass through a second heat exchanger 11, a fourth cooler 12 and a fifth cooler 13, then enter a second liquid separation tank 14, a second condensate S-11 is collected from the bottom of the second liquid separation tank 14, a second noncondensable gas S-12 is collected from the top of the second liquid separation tank 14, and the second noncondensable gas S-12 enters a second heat exchanger 11;
the second non-condensable gas S-12 preheated by the second heat exchanger 11 is used as a feed gas of the hydrogen membrane separation unit 15, and is separated to obtain high-pressure second permeation residual gas S-13, wherein the hydrogen content is lower than 15 vol%, the pressure of the second permeation gas S-14 is lower, and the hydrogen is enriched to more than 75 vol% again;
the second permeate gas S-14 passes through a sixth cooler 16, a fourth compressor 17 and a seventh cooler 18 in sequence, and then is combined with the first retentate gas S-7 to be used as a feed gas of the pressure swing adsorption unit 9.
The organic vapor membrane separation unit 8 is a device composed of a high molecular membrane component which can preferentially permeate condensable molecules such as hydrocarbon, water, carbon dioxide and the like, and the adopted membrane component can be a hollow fiber structure, a plate-frame structure and a spiral winding structure.
The hydrogen membrane separation unit 15 is a device composed of a high molecular membrane component which permeates preferentially, and the adopted membrane component can be a hollow fiber structure, a plate-frame structure and a spiral winding structure.
The invention has the beneficial effects that: in a pretreatment system of a pressure swing adsorption device, deep removal of five or more hydrocarbon heavy components in high-hydrogen-content refinery gas is realized through a compression condensation and organic steam membrane separation unit, and the concentration of the heavy components entering the pressure swing adsorption device is lower than 0.3 vol%, so that the regeneration and desorption conditions of an adsorbent can be obviously improved, the long-term operation stability of the adsorption device is improved, the service life of the adsorbent is prolonged, and compared with a normal process, the regeneration and desorption conditions are prolonged by 2-3 years; in the post-treatment system of the pressure swing adsorption device, the low-concentration hydrogen in the organic vapor membrane permeation gas and the pressure swing adsorption tail gas is further recovered through a hydrogen membrane separation unit, so that the hydrogen content of the fuel gas is lower than 15 vol%, and the total yield of the hydrogen is over 95%. In general, the hydrogen separation and purification cost can be reduced by 10-20% by the membrane separation enhanced pressure swing adsorption hydrogen purification process for high-hydrogen-content refinery gas.
Drawings
FIG. 1 is a schematic flow diagram of a membrane separation enhanced process for purifying hydrogen from a refinery gas with high hydrogen content by pressure swing adsorption.
In the figure: 1 a first compressor; 2 a first cooler; 3 a first heat exchanger; 4 a second cooler; 5 a first liquid separation tank; 6 a second compressor; 7 a third cooler; 8 organic vapor membrane separation unit; 9 pressure swing adsorption apparatus; 10 a third compressor; 11 a second heat exchanger; 12 a fourth cooler; 13 a fifth cooler; 14 a second liquid separation tank; 15 a hydrogen membrane separation unit; 16 a sixth cooler; 17 a fourth compressor; 18 a seventh cooler; s-1, first high hydrogen-containing refinery gas; s-2, second high hydrogen content refinery gas; s-3, a third high hydrogen-containing refinery gas; s-4, a fourth high hydrogen content refinery gas; s-5, first condensate; s-6, first non-condensable gas; s-7, first residual gas; s-8, a first permeate gas; s-9 hydrogen product; s-10, adsorbing the tail gas by pressure swing; s-11, second condensate; s-12, second noncondensable gas; s-13, second residual gas; s-14 second permeate gas.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
In example 1, a membrane separation-enhanced pressure swing adsorption process of the present invention is used to purify hydrogen from a high hydrogen content tail gas produced by a 220-million ton continuous catalytic reforming apparatus in a certain refinery. According to the composition and pressure, the catalytic reforming high hydrogen-containing tail gas belongs to a second high hydrogen-containing refinery gas S-2.
Table 1 summary of the composition and operating parameters of the key materials in example 1.
As shown in fig. 1, the high hydrogen-containing tail gas by-produced by the catalytic reforming device sequentially passes through a first cooler 2, a first heat exchanger 3 and a second cooler 4, then enters a first liquid separation tank 5, a first condensate S-5 is produced at the bottom of the tank, a first non-condensable gas S-6 is produced at the top of the tank, and enters an organic vapor membrane separation unit 8 after being preheated in the first heat exchanger 3; on the high-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation residual gas S-7, reducing the content of hydrocarbon heavy components of five carbon and more to below 0.3 vol%, and on the low-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation gas S-8, and concentrating the hydrocarbon heavy components of five carbon and more; the first residual gas S-7 and the pressurized/cooled second permeation gas S-14 are combined to form feed gas of a pressure swing adsorption device 9, and the product hydrogen S-9 with the hydrogen concentration higher than 99 vol% and the pressure swing adsorption tail gas S-10 are obtained through separation; the first permeate gas S-8 and the pressure swing adsorption tail gas S-10 enter a third compressor 10 in a combined mode, then sequentially pass through a second heat exchanger 11, a fourth cooler 12 and a fifth cooler 13, then enter a second liquid separation tank 14, a second condensate S-11 is produced at the bottom of the tank, a second non-condensable gas S-12 is produced at the top of the tank, and then enter the second heat exchanger 11; the second non-condensable gas S-12 preheated by the second heat exchanger 11 is used as a feed gas of the hydrogen membrane separation unit 15, and is separated to obtain high-pressure second permeation residual gas S-13, wherein the hydrogen content is lower than 15 vol%, the pressure of the second permeation gas S-14 is lower, and the hydrogen is enriched to more than 75 vol% again; the second permeate gas S-14 passes through a sixth cooler 16, a fourth compressor 17 and a seventh cooler 18 in sequence, and then is combined with the first retentate gas S-7 to be used as a feed gas of the pressure swing adsorption unit 9.
In this implementation, the main utility consumption: the power consumption of the third compressor 10 and the fourth compressor 17, the total assembly power 5500 kW; the second cooler 4 and the fifth cooler 13 freeze water at 10 ℃ and have a total cooling load of 4000 MJ/h. Through a pretreatment device formed by a compression condensation unit and an organic steam membrane separation unit, the content of five or more hydrocarbon heavy components in the feed gas of the pressure swing adsorption device 9 is only 0.27 vol%, the regeneration and desorption conditions of the adsorbent are obviously improved, the long-term operation stability of the adsorption device is improved, and the service life of the adsorbent is prolonged. The low-concentration hydrogen is further recovered by a hydrogen membrane separation unit in the post-treatment device, and the total recovery rate reaches 99 percent and is far higher than the normal level of a conventional pressure swing adsorption device by 85 to 92 percent.
Example 2
Example 2 aiming at a refinery with a high hydrogen content tail gas as a by-product of 60 ten thousand tons of continuous catalytic reforming devices and a low component gas and a dry gas of 120 ten thousand tons of hydrocracking devices, the hydrogen is purified by adopting the pressure swing adsorption process enhanced by membrane separation. According to the composition and pressure, the catalytic reforming high hydrogen-containing tail gas belongs to a second high hydrogen-containing refinery gas S-2, and the low-component gas and the dry gas of the hydrocracking device belong to a first high hydrogen-containing refinery gas S-1.
Table 2 summary of the composition and operating parameters of the key materials in example 2.
As shown in fig. 1, low-fraction gas and dry gas of a hydrocracking device are pressurized to 2.5MPaG by a first compressor 1, then are combined with high-hydrogen-content tail gas which is a byproduct of a catalytic reforming device, then sequentially pass through a first cooler 2, a first heat exchanger 3 and a second cooler 4, then enter a first liquid separation tank 5, produce a first condensate S-5 at the bottom of the tank, produce a first non-condensable gas S-6 at the top of the tank, and enter an organic vapor membrane separation unit 8 after being preheated in the first heat exchanger 3; on the high-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation residual gas S-7, reducing the content of hydrocarbon heavy components of five carbon and more to below 0.3 vol%, and on the low-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation gas S-8, and concentrating the hydrocarbon heavy components of five carbon and more; the first residual gas S-7 and the pressurized/cooled second permeation gas S-14 are combined to form feed gas of a pressure swing adsorption device 9, and the product hydrogen S-9 with the hydrogen concentration higher than 99 vol% and the pressure swing adsorption tail gas S-10 are obtained through separation; the first permeate gas S-8 and the pressure swing adsorption tail gas S-10 enter a third compressor 10 in a combined mode, then sequentially pass through a second heat exchanger 11, a fourth cooler 12 and a fifth cooler 13, then enter a second liquid separation tank 14, a second condensate S-11 is produced at the bottom of the tank, a second non-condensable gas S-12 is produced at the top of the tank, and then enter the second heat exchanger 11; the second non-condensable gas S-12 preheated by the second heat exchanger 11 is used as a feed gas of the hydrogen membrane separation unit 15, and is separated to obtain high-pressure second permeation residual gas S-13, wherein the hydrogen content is lower than 15 vol%, the pressure of the second permeation gas S-14 is lower, and the hydrogen is enriched to more than 75 vol% again; the second permeate gas S-14 passes through a sixth cooler 16, a fourth compressor 17 and a seventh cooler 18 in sequence, and then is combined with the first retentate gas S-7 to be used as a feed gas of the pressure swing adsorption unit 9.
In this implementation, the main utility consumption: the power consumption of the first compressor 1, the third compressor 10 and the fourth compressor 17, the total assembly power 2350 kW; the second cooler 4 and the fifth cooler 13 freeze water at 10 ℃ for a total cooling load of 1700 MJ/h. Through the pretreatment device formed by the compression condensation and organic steam membrane separation unit, the content of the hydrocarbon heavy components of five or more than five carbon in the feed gas of the pressure swing adsorption device 9 is only 0.30 vol%, the regeneration and desorption conditions of the adsorbent are obviously improved, the long-term operation stability of the adsorption device is improved, and the service life of the adsorbent is prolonged. The low-concentration hydrogen is further recovered by a hydrogen membrane separation unit in the post-treatment device, the total recovery rate reaches 98.5 percent and is far higher than the normal level of a conventional pressure swing adsorption device by 85-92 percent.
Example 3
Example 3 for a high-split gas, a low-split gas, and a dry gas of a 200-million-ton diesel hydrocracking device of a certain refinery, hydrogen purification is performed by using the pressure swing adsorption process enhanced by membrane separation of the present invention. According to the composition and pressure, the diesel hydrocracking high-molecular gas belongs to a fourth high hydrogen-containing refinery gas S-4, and the diesel hydrocracking low-molecular gas and the dry gas belong to a first high hydrogen-containing refinery gas S-1.
Table 3 summary of the composition and operating parameters of the key materials in example 3.
As shown in fig. 1, the low-fraction gas and the dry gas of the hydrocracking unit are pressurized to 2.5MPaG by a first compressor 1, then sequentially pass through a first cooler 2, a first heat exchanger 3 and a second cooler 4, then enter a first liquid separation tank 5, produce a first condensate S-5 at the bottom of the tank, produce a first non-condensable gas S-6 at the top of the tank, and then enter the first heat exchanger 3; passing through a third cooler 7, the diesel hydrocracking high-molecular gas is then combined with a first non-condensable gas S-6 preheated by a first heat exchanger 3, and then enters an organic steam membrane separation unit 8; on the high-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation residual gas S-7, reducing the content of hydrocarbon heavy components of five carbon and more to below 0.3 vol%, and on the low-pressure side of the organic steam membrane separation unit 8, obtaining a first permeation gas S-8, and concentrating the hydrocarbon heavy components of five carbon and more; the first residual gas S-7 and the pressurized/cooled second permeation gas S-14 are combined to form feed gas of a pressure swing adsorption device 9, and the product hydrogen S-9 with the hydrogen concentration higher than 99 vol% and the pressure swing adsorption tail gas S-10 are obtained through separation; the first permeate gas S-8 and the pressure swing adsorption tail gas S-10 enter a third compressor 10 in a combined mode, then sequentially pass through a second heat exchanger 11, a fourth cooler 12 and a fifth cooler 13, then enter a second liquid separation tank 14, a second condensate S-11 is produced at the bottom of the tank, a second non-condensable gas S-12 is produced at the top of the tank, and then enter the second heat exchanger 11; the second non-condensable gas S-12 preheated by the second heat exchanger 11 is used as a feed gas of the hydrogen membrane separation unit 15, and is separated to obtain high-pressure second permeation residual gas S-13, wherein the hydrogen content is lower than 15 vol%, the pressure of the second permeation gas S-14 is lower, and the hydrogen is enriched to more than 75 vol% again; the second permeate gas S-14 passes through a sixth cooler 16, a fourth compressor 17 and a seventh cooler 18 in sequence, and then is combined with the first retentate gas S-7 to be used as a feed gas of the pressure swing adsorption unit 9.
In this implementation, the main utility consumption: the power consumption of the first compressor 1, the third compressor 10 and the fourth compressor 17, the total installation power 1840 kW; the second cooler 4 and the fifth cooler 13 freeze water at 10 ℃ for a total cooling load of 900 MJ/h. Through the pretreatment device formed by the compression condensation and organic steam membrane separation unit, the content of the hydrocarbon heavy components of five or more than five carbon in the feed gas of the pressure swing adsorption device 9 is only 0.30 vol%, the regeneration and desorption conditions of the adsorbent are obviously improved, the long-term operation stability of the adsorption device is improved, and the service life of the adsorbent is prolonged. The low-concentration hydrogen is further recovered by a hydrogen membrane separation unit in the post-treatment device, the total recovery rate reaches 98.0 percent and is far higher than the normal level of a conventional pressure swing adsorption device by 85-92 percent.
Claims (3)
1. A membrane separation enhanced pressure swing adsorption hydrogen purification process for high-hydrogen-content refinery gas is characterized in that the high-hydrogen-content refinery gas is divided into four types according to composition and pressure:
the first high hydrogen content refinery gas (S-1) has the pressure less than 2.5MPaG and the content of hydrocarbon heavy components of five or more carbon atoms more than 1.0 vol%;
second high hydrogen content refinery gas (S-2), pressure is more than or equal to 2.5MPaG, and the content of hydrocarbon heavy components of five or more carbon atoms is more than or equal to 1.0 vol%;
the third high hydrogen content refinery gas (S-3) with pressure less than 2.5MPaG and hydrocarbon heavy component content less than 1.0 vol% of C five and above;
the fourth high hydrogen content refinery gas (S-4) with pressure not less than 2.5MPaG and hydrocarbon heavy component content of C5 and above less than 1.0 vol%;
after being pressurized by a first compressor (1), the first high hydrogen-containing refinery gas (S-1) is combined with the second high hydrogen-containing refinery gas (S-2), then sequentially passes through a first cooler (2), a first heat exchanger (3) and a second cooler (4), and then enters a first liquid separation tank (5), a first condensate (S-5) is collected from the bottom of the first liquid separation tank (5), a first noncondensable gas (S-6) is collected from the top of the first liquid separation tank (5), and the first noncondensable gas (S-6) enters the first heat exchanger (3); the third high hydrogen-containing refinery gas (S-3) is pressurized by a second compressor (6), then is combined with the fourth high hydrogen-containing refinery gas (S-4), is cooled by a third cooler (7), is combined with the first noncondensable gas (S-6) passing through the first heat exchanger (3), and then enters an organic steam membrane separation unit (8); on the high-pressure side of the organic vapor membrane separation unit (8), obtaining a first retentate gas (S-7), and reducing the content of hydrocarbon heavy components of five carbon and above to below 0.3 vol%; on the low-pressure side of the organic vapor membrane separation unit (8), obtaining a first permeate gas (S-8), and concentrating hydrocarbon heavy components with five or more carbon atoms; the first residual gas (S-7) and the pressurized/cooled second permeate gas (S-14) are combined to become feed gas of a pressure swing adsorption device (9), and product hydrogen (S-9) with the hydrogen concentration higher than 99 vol% and pressure swing adsorption tail gas (S-10) are obtained through separation; the first permeate gas (S-8) and the pressure swing adsorption tail gas (S-10) enter a third compressor (10) in a combined mode, then sequentially pass through a second heat exchanger (11), a fourth cooler (12) and a fifth cooler (13), then enter a second liquid separation tank (14), a second condensate (S-11) is collected from the bottom of the second liquid separation tank (14), a second noncondensable gas (S-12) is collected from the top of the second liquid separation tank (14), and the second noncondensable gas (S-12) enters the second heat exchanger (11); the second non-condensable gas (S-12) preheated by the second heat exchanger (11) is used as a feed gas of the hydrogen membrane separation unit (15) to separate to obtain high-pressure second permeation residual gas (S-13), the hydrogen content is lower than 15 vol%, the pressure of the second permeation gas (S-14) is lower, and the hydrogen is enriched to more than 75 vol%; the second permeation gas (S-14) sequentially passes through a sixth cooler (16), a fourth compressor (17) and a seventh cooler (18) and then is combined with the first residual gas (S-7) to be used as a raw material gas of the pressure swing adsorption device (9).
2. The process for purifying hydrogen through pressure swing adsorption of refinery gas with high hydrogen content by membrane separation enhancement according to claim 1, wherein the organic vapor membrane separation unit (8) is a device composed of a high polymer membrane module for permeating hydrocarbons, water and carbon dioxide, and the adopted membrane module is a hollow fiber structure, a plate-frame structure or a spiral winding structure.
3. The process for purifying high-hydrogen-content refinery gas by pressure swing adsorption with enhanced membrane separation according to claim 1 or 2, wherein the hydrogen membrane separation unit (15) is a device composed of permeable polymeric membrane modules, and the membrane modules are hollow fiber structures, plate-frame structures or spiral wound structures.
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