CN114751376B - Separation method of synthetic tail gas - Google Patents
Separation method of synthetic tail gas Download PDFInfo
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- CN114751376B CN114751376B CN202210346054.8A CN202210346054A CN114751376B CN 114751376 B CN114751376 B CN 114751376B CN 202210346054 A CN202210346054 A CN 202210346054A CN 114751376 B CN114751376 B CN 114751376B
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- 238000000926 separation method Methods 0.000 title claims abstract description 143
- 239000007789 gas Substances 0.000 claims abstract description 129
- 239000012528 membrane Substances 0.000 claims abstract description 125
- 239000012466 permeate Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 238000011084 recovery Methods 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000002737 fuel gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005265 energy consumption Methods 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 238000005381 potential energy Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/0405—Purification by membrane separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to the field of hydrogen preparation, in particular to a separation method of synthetic tail gas, which comprises the following steps: sequentially carrying out at least two sections of membrane separation on the synthetic tail gas, wherein non-permeate gas obtained by the N-th section of membrane separation is used as feed of the N+1th section of membrane separation, the feed side pressure of the N-th section of membrane separation is higher than that of the N+1th section of membrane separation, and the temperature of the N-th section of membrane separation is lower than that of the N+1th section of membrane separation; wherein N is more than or equal to 1. The method has the characteristics of low energy consumption, high load, high hydrogen yield and low non-penetrating gas discharge.
Description
Technical Field
The invention relates to the field of hydrogen preparation, in particular to a separation method of synthetic tail gas.
Background
The Fischer-Tropsch tail gas generated in the Fischer-Tropsch synthesis reaction process mainly comprises H 2 CO, lower hydrocarbons (hydrocarbons below C6), CO 2 、N 2 The waste gas is conventionally used as fuel for heating or generating electricity, but with the rising of the price of the international crude oil, the method becomes quite uneconomical, reduces the use value of resources, and can greatly improve the Fischer-Tropsch tail if products such as hydrogen, liquefied gas, low-carbon olefin and the like can be separated from the Fischer-Tropsch tail gas or converted into the synthetic gas for recyclingEconomic value of gas
The Fischer-Tropsch tail gas separation and recovery method is a technology which is applied more at present, and the Fischer-Tropsch tail gas separation device can provide an effective hydrogen source for the whole plant and improve the utilization rate of raw material carbon. The raw material gas enters a membrane separation unit after hydrocarbon is removed, permeation gas with high hydrogen content and non-permeation gas with low hydrogen content are separated, the permeation gas is sent to a pressure swing adsorption device for further purification, and the non-permeation gas is sent to a fuel gas pipe network or the catalytic oxidation technology is adopted for continuously producing hydrogen. The device runs stably and has strong operability, but with the enlargement of the scale of the device, the problems of Fischer-Tropsch tail gas parameter fluctuation, low tail gas separation process load, high non-permeate gas emission, low hydrogen yield and the like restrict the development of the process, and influence the economic benefit.
The outstanding problems are that in the existing process technology, the treatment load of the Fischer-Tropsch tail gas of the membrane separation is low, the non-permeate gas discharge is high, the hydrogen yield and purity are low, and the economic benefit is not high.
Disclosure of Invention
The invention aims to solve the problems of low treatment load, high energy consumption and low hydrogen yield and purity of synthesis tail gas in the prior art, and provides a separation method of synthesis tail gas with low energy consumption, high load and high hydrogen yield and purity.
In order to achieve the above object, the present invention provides a synthetic tail gas separation method, comprising:
sequentially carrying out at least two sections of membrane separation on the synthetic tail gas, wherein non-permeate gas obtained by the N-th section of membrane separation is used as feed of the N+1th section of membrane separation, the feed side pressure of the N-th section of membrane separation is higher than that of the N+1th section of membrane separation, and the temperature of the N-th section of membrane separation is lower than that of the N+1th section of membrane separation; wherein N is more than or equal to 1.
Preferably, the feed side pressure of the N-th stage membrane separation is 0.5-2Mpa higher than that of the N+1-th stage membrane separation.
Preferably, the temperature of the N-th stage membrane separation is 20-30 ℃ lower than the temperature of the N+1-th stage membrane separation.
By adopting the scheme, the invention has the following beneficial effects:
according to the method disclosed by the invention, the synthesis tail gas is separated, the energy consumption is low, and the high-purity and high-yield hydrogen can be obtained.
Drawings
FIG. 1 is a schematic diagram of an apparatus and process according to a preferred embodiment of the present invention.
Description of the reference numerals
1-raw material gas; 2-a gas-liquid separation tank; 3-a filter; 4-a steam heat exchanger; 5-a steam heater; 6-a steam heater; 7-non-permeate gas; 8-permeation and ventilation; 9-impermeability to air; 10-permeation and ventilation; 11-a fuel gas pipe network; a 12-PSA pressure swing adsorption hydrogen production device; V-1/V-2-pressure regulating valve; V-3/V-4-check valve; x-1-membrane separation group; x-2-membrane separation group.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a separation method of synthetic tail gas, which comprises the following steps:
sequentially carrying out at least two sections of membrane separation on the synthetic tail gas, wherein non-permeate gas obtained by the N-th section of membrane separation is used as feed of the N+1th section of membrane separation, the feed side pressure of the N-th section of membrane separation is higher than that of the N+1th section of membrane separation, and the temperature of the N-th section of membrane separation is lower than that of the N+1th section of membrane separation; wherein N is more than or equal to 1.
According to the method disclosed by the invention, the synthesis tail gas is separated, the energy consumption is low, and the high-purity and high-yield hydrogen can be obtained.
According to a preferred embodiment of the present invention, the feed side pressure of the N-th stage membrane separation is 0.5-2Mpa higher than the feed side pressure of the n+1-th stage membrane separation. By adopting the preferable scheme, the energy consumption can be further reduced, and the purity and the yield of the hydrogen can be improved.
According to a preferred embodiment of the invention, the temperature of the N-th stage membrane separation is 10-30 c, preferably 20-30 c, lower than the temperature of the n+1-th stage membrane separation. By adopting the preferable scheme, the energy consumption can be further reduced, and the purity and the yield of the hydrogen can be improved.
According to a preferred embodiment of the invention, the temperature of the membrane separation in any one of the stages is 40 to 100 ℃, preferably 60 to 90 ℃. By adopting the preferable scheme, the energy consumption can be further reduced, and the purity and the yield of the hydrogen can be improved.
According to a preferred embodiment of the invention, the feed side pressure of any one of the membrane separations is in the range of 3.0 to 8.0Mpa, preferably 4 to 6Mpa. By adopting the preferable scheme, the energy consumption can be further reduced, and the purity and the yield of the hydrogen can be improved.
According to a preferred embodiment of the invention, the process further comprises pre-treating said synthesis off-gas such that the water content of the synthesis off-gas is less than 0.01ppmw and the hydrocarbon content is less than 0.01ppmw. By adopting the preferable scheme, the energy consumption can be further reduced, and the purity of the hydrogen can be improved.
According to a preferred embodiment of the invention, the process further comprises separating the n+1-th stage membrane to obtain permeate gas and/or non-permeate gas for heating the synthesis off-gas. By adopting the preferable scheme, the energy consumption can be further reduced.
According to a preferred embodiment of the invention, the hydrogen content of the synthesis off-gas is at least 70% by volume.
According to a preferred embodiment of the invention, the flow rate of the synthesis off-gas is between 1 and 50 ten thousand Nm 3 /hr. According to a preferred embodiment of the present invention, the hydrogen content in the permeate gas obtained by the n+1st stage membrane separation is greater than 90mol%.
According to a preferred embodiment of the invention, the process is carried out in a device,
the device comprises:
the device comprises a pretreatment unit, a heat recovery unit, a multi-stage membrane separation unit, a hydrogen purification unit and a non-permeate gas recovery unit, wherein the pretreatment unit, the heat recovery unit and the multi-stage membrane separation unit are sequentially connected in series; wherein,
the multistage membrane separation units comprise N+1 membrane separation units which are formed by sequentially connecting a heater and a membrane separation group in series, wherein each membrane separation unit is sequentially connected in series, and N is more than or equal to 1;
the permeate gas discharge ports of the 1 st to N th membrane separation units are communicated with the hydrogen purification unit;
the method comprises the following steps:
(1) Introducing the synthesis off-gas into a pretreatment unit to obtain a gas stream having a water content of less than 0.01ppmw and a hydrocarbon content of less than 0.01ppmw;
(2) Introducing the air flow obtained in the step (1) into a heat recovery unit, and exchanging heat with the permeate gas and/or the non-permeate gas obtained from the (n+1) th membrane separation unit;
(3) Carrying out membrane separation on the gas flow subjected to heat exchange in the step (2) by using a 1 st membrane separation unit, taking the obtained non-permeate gas as a feed of a next membrane separation unit, and finally, introducing the non-permeate gas into an (n+1) th membrane separation unit for membrane separation;
(4) Collecting permeate gas obtained by the 1 st to N th membrane separation units and sending the permeate gas to a hydrogen purification unit; collecting the permeate gas obtained by the membrane separation of the (N+1) th section, returning the permeate gas to a recovery heat unit for heating the synthesis tail gas, and then sending the synthesis tail gas to a hydrogen purification unit; and collecting the non-permeate gas obtained by the membrane separation of the n+1th section, returning the non-permeate gas to a recovery heat unit for heating the synthesis tail gas, and then sending the synthesis tail gas to the non-permeate gas recovery unit.
By adopting the above preferred scheme, the pressure potential energy of a single group of membranes during operation is shared, a pressure gradient difference is formed, so that the pressure potential energy born by each group of membranes is reduced, the operation pressure is reduced, working allowance is left, the system load is improved, the processing capacity of raw material gas and the yield and purity of hydrogen are increased, the secondary pressure lifting of the raw material gas is not needed, the power consumption of the device is reduced, and the economic benefit of the device is remarkably improved.
According to a preferred embodiment of the present invention, the hydrogen purification unit is a PSA pressure swing adsorption unit. By adopting the preferable scheme, the device intermodal transportation is realized, the purity of the hydrogen is further improved, higher-purity hydrogen is provided for downstream devices, and the economic benefit is improved.
According to a preferred embodiment of the present invention, the non-permeate gas recovery unit is a fuel gas network.
An embodiment of the present invention is described below in conjunction with the apparatus of fig. 1, which includes: a gas-liquid separation tank 2, a filter 3, a heat exchanger 4, a steam heater 5, a steam heater 6, a membrane separation group X-1, a membrane separation group X-2, a PSA pressure swing adsorption hydrogen production device 12 and a fuel gas pipe network 11;
wherein,
the gas-liquid separation tank 2, the filter 3, the heat exchanger 4, the steam heater 5, the membrane separation group X-1, the steam heater 6 and the membrane separation group X-2 are sequentially connected in series;
the permeate gas outlet and the non-permeate gas outlet of the membrane separation group X-2 are communicated with the heat exchanger 4;
the PSA pressure swing adsorption hydrogen production device 12 is communicated with a permeate gas discharge port of the heat exchanger 4 and is communicated with a permeate gas discharge port of the membrane separation group X-1;
the fuel gas pipe network 11 is communicated with a non-permeation gas discharge port of the heat exchanger 4;
the method comprises the following steps:
(1) Sequentially introducing the synthesis tail gas into a gas-liquid separation tank 2 and a filter 3 to obtain a gas stream with water content lower than 0.01ppmw and hydrocarbon content lower than 0.01ppmw;
(2) Introducing the air flow obtained in the step (1) into a heat exchanger 4, and exchanging heat with permeation air and/or non-permeation air from the membrane separation group X-2;
(3) Introducing the air flow subjected to heat exchange in the step (2) into a membrane separation group X-1 for membrane separation, and introducing the obtained non-permeable air into the membrane separation group X-2 for membrane separation;
(4) Collecting permeate gas obtained by the membrane separation group X-1, and sending the permeate gas into a hydrogen purification unit; the permeate gas obtained by the membrane separation group X-2 is returned to the heat exchanger 4 for heating the gas flow obtained in the step (1) and then is sent to the hydrogen purification unit; and (3) collecting the membrane separation group X-2 to obtain the non-permeable gas, returning the non-permeable gas to the heat exchanger 4 for heating the gas flow obtained in the step (1), and then sending the gas flow to a non-permeable gas recovery unit.
The invention uses the waste heat of the products (permeate gas and non-permeate gas) to exchange heat for the synthesis tail gas, recovers heat energy, and reduces the heat consumption of the membrane separation group X-1; the pressure drop is utilized to provide power for the membrane groups, the operating pressure and the temperature of the two membrane separation groups are different, a certain gradient is formed, the pressure potential energy is fully utilized, and meanwhile, the pressure potential energy of a single membrane group in operation is shared, so that the pressure potential energy born by each membrane group is reduced, the operating pressure is reduced, the working allowance is left, the load of the device is improved, the processing capacity is increased, the energy consumption of the device is reduced, the purity and the yield of hydrogen are improved, and the economic benefit of the device is remarkably improved.
According to a preferred embodiment of the invention, the feed and/or discharge openings of the individual working units of the device are provided with valves, enabling dynamic adjustment of the process.
The invention is further illustrated by the following examples. The following examples were carried out in the apparatus shown in fig. 1.
Example 1
Synthetic tail gas (H) 2 ：70％；N 2 ：10.9％；CH 4 ：8.1％；CO：7％；CO 2 ：1.7％；C 2 + :2.3% by volume) in a gas-liquid separation tank 2, and then entering a filter 3 to reduce the water content in the feed gas to 0 and the hydrocarbon component to below 0.0008 ppmw; then the mixture is introduced into a heat exchanger 4 for heat exchange;
then the mixture enters a steam heater 5 to raise the temperature to 65 ℃, enters a membrane separation group X-1 with the operating pressure of 5.5Mpa to obtain a permeation gas 8 and an impermeable gas 7, the impermeable gas 7 is controlled to be pressed by a pressure regulating valve V-1 to enter a steam heater 6 to raise the temperature to 85 ℃, and then enters a membrane separation group X-2 with the operating pressure of 5.0Mpa to obtain a permeation gas 10 and an impermeable gas 9;
the permeate gas 8 separated by the membrane separation group X-1 is sent to PSA pressure swing adsorption to prepare hydrogen; the permeate gas 10 separated by the membrane separation group X-2 is sent to the heat exchanger 4 for heat exchange and then is sent to the PSA pressure swing adsorption hydrogen production, and the non-permeate gas 9 separated by the membrane separation group X-2 is sent to the heat exchanger 4 for heat exchange and then is sent to the fuel gas pipe network 14.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 2
The difference with the embodiment 1 is that the air flow enters the steam heater 5 to raise the temperature to 60 ℃ after heat exchange and enters the membrane separation group X-1 with the operating pressure of 6.0Mpa to obtain the permeation air 8 and the non-permeation air 7, the non-permeation air 7 enters the steam heater 6 to raise the temperature to 90 ℃ through the pressure control valve V-1, and then enters the membrane separation group X-2 with the operating pressure of 4.0Mpa to obtain the permeation air 10 and the non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 3
The difference with the embodiment 1 is that the air flow enters the steam heater 5 to rise the temperature to 65 ℃ after heat exchange and enters the membrane separation group X-1 with the operating pressure of 5.0Mpa to obtain the permeation air 8 and the non-permeation air 7, the non-permeation air 7 enters the steam heater 6 to rise the temperature to 90 ℃ through the pressure control valve V-1 to control the pressure, and then enters the membrane separation group X-2 with the operating pressure of 4.0Mpa to obtain the permeation air 10 and the non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 4
The difference with the embodiment 1 is that the air flow enters the steam heater 5 to raise the temperature to 60 ℃ after heat exchange and enters the membrane separation group X-1 with the operating pressure of 5.5Mpa to obtain the permeation air 8 and the non-permeation air 7, the non-permeation air 7 enters the steam heater 6 to raise the temperature to 100 ℃ through the pressure control valve V-1, and then enters the membrane separation group X-2 with the operating pressure of 5.0Mpa to obtain the permeation air 10 and the non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 5
The difference with the embodiment 1 is that the air flow enters a steam heater 5 to rise the temperature to 65 ℃ after heat exchange and enters a membrane separation group X-1 with the operating pressure of 8Mpa to obtain permeation air 8 and non-permeation air 7, the non-permeation air 7 enters the steam heater 6 to rise the temperature to 85 ℃ through the pressure control of a pressure regulating valve V-1, and then enters a membrane separation group X-2 with the operating pressure of 3.0Mpa to obtain permeation air 10 and non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 6
The difference with the embodiment 1 is that the air flow enters the steam heater 5 to raise the temperature to 60 ℃ after heat exchange and enters the membrane separation group X-1 with the operating pressure of 8Mpa to obtain the permeation air 8 and the non-permeation air 7, the non-permeation air 7 enters the steam heater 6 to raise the temperature to 100 ℃ through the pressure control valve V-1, and then enters the membrane separation group X-2 with the operating pressure of 3.0Mpa to obtain the permeation air 10 and the non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Comparative example 1
The difference with the embodiment 1 is that after heat exchange, the air flow enters a steam heater 5 to raise the temperature to 100 ℃, enters a membrane separation group X-1 with the operating pressure of 3Mpa to obtain permeation air 8 and non-permeation air 7, the non-permeation air 7 is controlled to be pressed by a pressure regulating valve V-1 and a pump to enter a steam heater 6 to raise the temperature to 60 ℃, and then enters a membrane separation group X-2 with the operating pressure of 8.0Mpa to obtain permeation air 10 and non-permeation air 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
TABLE 1
The results show that the hydrogen of the embodiment adopting the technical scheme of the invention has high purity, the yield reaches more than 93 percent, the energy consumption is low, and the method has obviously better effect compared with the prior art.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of individual specific technical features in any suitable way. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Such simple variations and combinations are likewise to be regarded as being within the scope of the present disclosure.
Claims (9)
1. A method for separating synthesis off-gas, the method comprising:
sequentially carrying out at least two sections of membrane separation on the synthetic tail gas, wherein non-permeate gas obtained by the N-th section of membrane separation is used as feed of the N+1th section of membrane separation, the feed side pressure of the N-th section of membrane separation is higher than that of the N+1th section of membrane separation, and the temperature of the N-th section of membrane separation is lower than that of the N+1th section of membrane separation; wherein N is more than or equal to 1;
the feed side pressure of the membrane separation in any section is 3.0-8.0 MPa, and the feed side pressure of the membrane separation in the N section is 0.5-2MPa higher than the feed side pressure of the membrane separation in the (n+1) th section;
the temperature of the membrane separation in any section is 40-100 ℃, and the temperature of the membrane separation in the N section is 20-30 ℃ lower than the temperature of the membrane separation in the (n+1) section.
2. The separation method according to claim 1, wherein,
the temperature of the membrane separation in any section is 60-90 ℃; and/or
And the feeding side pressure of the membrane separation in any section is 4-6 MPa.
3. The separation method according to claim 1, wherein the method further comprises,
pretreating the synthetic tail gas to make the water content of the synthetic tail gas be less than 0.01ppmw and the hydrocarbon content be less than 0.01ppmw; and/or
And (3) using the permeated gas and/or the non-permeated gas obtained by the separation of the n+1th section membrane to heat the synthesis tail gas.
4. The separation process of claim 1, wherein the hydrogen content of the synthesis off-gas is at least 70% by volume.
5. The separation process according to claim 1, wherein the flow rate of the synthesis off-gas is 1-50 ten thousand Nm 3 /hr。
6. The separation method according to claim 1, wherein the hydrogen content in the permeate gas obtained by the n+1th stage membrane separation is more than 90mol%.
7. The separation process according to any one of claims 1 to 6, wherein the process is carried out in a device,
the device comprises:
the device comprises a pretreatment unit, a heat recovery unit, a multi-stage membrane separation unit, a hydrogen purification unit and a non-permeate gas recovery unit, wherein the pretreatment unit, the heat recovery unit and the multi-stage membrane separation unit are sequentially connected in series; wherein,
the multistage membrane separation units comprise N+1 membrane separation units which are formed by sequentially connecting a heater and a membrane separation group in series, wherein each membrane separation unit is sequentially connected in series, and N is more than or equal to 1;
the permeate gas discharge ports of the 1 st to N th membrane separation units are communicated with the hydrogen purification unit;
the permeate gas outlet and the non-permeate gas outlet of the (n+1) th membrane separation unit are communicated with the heat recovery unit;
the method comprises the following steps:
(1) Introducing the synthesis off-gas into a pretreatment unit to obtain a gas stream having a water content of less than 0.01ppmw and a hydrocarbon content of less than 0.001 ppmw;
(2) Introducing the air flow obtained in the step (1) into a heat recovery unit, and exchanging heat with the permeate gas and/or the non-permeate gas obtained from the (n+1) th membrane separation unit;
(3) Carrying out membrane separation on the gas flow subjected to heat exchange in the step (2) by using a 1 st membrane separation unit, taking the obtained non-permeate gas as a feed of a next membrane separation unit, and finally, introducing the non-permeate gas into an (n+1) th membrane separation unit for membrane separation;
(4) Collecting permeate gas obtained by the 1 st to N th membrane separation units and sending the permeate gas to a hydrogen purification unit; collecting the permeate gas obtained by the membrane separation of the (N+1) th section, returning the permeate gas to a recovery heat unit for heating the synthesis tail gas, and then sending the synthesis tail gas to a hydrogen purification unit; and collecting the non-permeate gas obtained by the membrane separation of the n+1th section, returning the non-permeate gas to a recovery heat unit for heating the synthesis tail gas, and then sending the synthesis tail gas to the non-permeate gas recovery unit.
8. The separation method according to claim 7, wherein the pretreatment unit comprises one or both of a gas-liquid separation tank and a filter.
9. The separation method according to claim 7, wherein,
the hydrogen purification unit is a PSA pressure swing adsorption device, and/or
The non-permeate gas recovery unit is a fuel gas pipe network.
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| CN104030245A (en) * | 2014-05-23 | 2014-09-10 | 四川天采科技有限责任公司 | Hydrogen purifying method and device for refinery dry gas after recovery of light olefins with high yield and high purity |
| WO2020031063A1 (en) * | 2018-08-06 | 2020-02-13 | Sabic Global Technologies B.V. | Process for producing methanol |
| CN111467913A (en) * | 2020-03-27 | 2020-07-31 | 大连海奥膜技术有限公司 | Comprehensive recycling process and equipment for refinery tail gas |
| CN111348623A (en) * | 2020-03-30 | 2020-06-30 | 广西精典化工新材料有限公司 | Hydrogen recovery and purification system in purge tail gas generated in preparation of formaldehyde through methanol oxidation |
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