CN114751376A - Separation method of synthesis tail gas - Google Patents
Separation method of synthesis tail gas Download PDFInfo
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- CN114751376A CN114751376A CN202210346054.8A CN202210346054A CN114751376A CN 114751376 A CN114751376 A CN 114751376A CN 202210346054 A CN202210346054 A CN 202210346054A CN 114751376 A CN114751376 A CN 114751376A
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- 238000000926 separation method Methods 0.000 title claims abstract description 145
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 172
- 239000012528 membrane Substances 0.000 claims abstract description 123
- 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 17
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000012466 permeate Substances 0.000 claims description 32
- 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
- 239000002737 fuel gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000005381 potential energy Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 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
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 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
- 238000004064 recycling Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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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 synthesis tail gas, wherein the non-permeable gas obtained by the N section of membrane separation is used as the feeding material of the (N + 1) th section of membrane separation, the pressure of the feeding side of the N section of membrane separation is higher than that of the feeding side of the (N + 1) th section of membrane separation, and the temperature of the N section of membrane separation is lower than that of the (N + 1) th 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-permeation gas discharge.
Description
Technical Field
The invention relates to the field of hydrogen preparation, in particular to a separation method of synthesis tail gas.
Background
The Fischer-Tropsch synthesis tail gas generated in the Fischer-Tropsch synthesis reaction process mainly consists of H2CO, lower hydrocarbons (hydrocarbons having a carbon number of 6 or less), CO2、N2And the like, the Fischer-Tropsch synthesis tail gas is usually used as fuel for supplying heat or generating power in the prior art, but with the increase of the international crude oil price, the method becomes quite uneconomical, the use value of resources is reduced, and if products such as hydrogen, liquefied gas and low-carbon olefin can be separated from the Fischer-Tropsch synthesis tail gas or converted into synthesis gas for recycling, the economic value of the Fischer-Tropsch synthesis tail gas can be greatly improved
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 hydrocarbons are 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 hydrogen is continuously produced by adopting a catalytic oxidation technology. The device has stable operation and strong operability, but the problems of fluctuation of Fischer-Tropsch tail gas parameters, low load of a tail gas separation process, high non-permeation gas emission, low hydrogen yield and the like restrict the development of the process along with the amplification of the scale of the device, and influence on economic benefit.
The outstanding problems are that in the prior art, the membrane separation Fischer-Tropsch tail gas treatment load is low, the non-permeation gas emission 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 synthetic tail gas in the prior art, and provides a separation method of synthetic tail gas with low energy consumption, high load, high hydrogen yield and high purity.
In order to achieve the above object, the present invention provides a separation method of synthesis tail gas, comprising:
sequentially carrying out at least two sections of membrane separation on the synthesis tail gas, wherein the non-permeable gas obtained by the N-section membrane separation is used as the feed of the (N + 1) th section of membrane separation, the pressure of the feed side of the N-section membrane separation is higher than that of the feed side of the (N + 1) th section of membrane separation, and the temperature of the N-section membrane separation is lower than that of the (N + 1) th section of membrane separation; wherein N is more than or equal to 1.
Preferably, the pressure of the feed side of the N stage membrane separation is 0.5 to 2MPa higher than that of the (N + 1) th stage membrane separation.
Preferably, the temperature of the membrane separation of the Nth stage is 20-30 ℃ lower than that of the membrane separation of the (N + 1) th stage.
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 hydrogen with high purity and high yield 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-steam heater; 7-impermeable gas; 8-permeate gas; 9-impermeable gas; 10-permeate gas; 11-a fuel gas pipe network; 12-PSA pressure swing adsorption hydrogen production unit; V-1/V-2-pressure regulating valve; a V-3/V-4-check valve; x-1-membrane separation group; X-2-Membrane separation group.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a separation method of synthesis tail gas, which comprises the following steps:
sequentially carrying out at least two sections of membrane separation on the synthesis tail gas, wherein the non-permeable gas obtained by the N section of membrane separation is used as the feeding material of the (N + 1) th section of membrane separation, the pressure of the feeding side of the N section of membrane separation is higher than that of the feeding side of the (N + 1) th section of membrane separation, and the temperature of the N section of membrane separation is lower than that of the (N + 1) th 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 hydrogen with high purity and high yield can be obtained.
According to a preferred embodiment of the present invention, the pressure on the feed side of the N-th membrane separation stage is 0.5 to 2MPa higher than the pressure on the feed side of the (N + 1) -th membrane separation stage. By adopting the preferred 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 of the nth stage is 10 to 30 ℃, preferably 20 to 30 ℃ lower than the temperature of the membrane separation of the (N + 1) th stage. By adopting the preferred 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 present invention, the temperature of the membrane separation in any stage is 40 to 100 ℃, preferably 60 to 90 ℃. By adopting the preferred 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 present invention, the feed side pressure of any one section of the membrane separation is 3.0 to 8.0Mpa, preferably 4 to 6 Mpa. 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 present invention, the method further comprises pretreating the synthesis tail gas so that the water content in the synthesis tail gas is less than 0.01ppmw and the hydrocarbon content is less than 0.01 ppmw. By adopting the preferable scheme, the energy consumption can be further reduced, and the hydrogen purity can be improved.
According to a preferred embodiment of the present invention, the method further comprises using the permeate gas and/or the non-permeate gas obtained from the membrane separation of the (N + 1) th stage for heating the synthesis tail gas. By adopting the preferred scheme, the energy consumption can be further reduced.
According to a preferred embodiment of the invention, the synthesis tail gas has a hydrogen content of at least 70% by volume.
According to a preferred embodiment of the invention, the synthesis tail gas has a flow rate of 1 to 50 ten thousand Nm3And/hr. According to a preferred embodiment of the present invention, the hydrogen content of the permeate gas obtained by the membrane separation of the (N + 1) th stage is more than 90 mol%.
According to a preferred embodiment of the invention, the method is carried out in an apparatus,
the device comprises:
the system comprises a pretreatment unit, a heat recovery unit, a multi-stage membrane separation unit, a hydrogen purification unit and a non-permeable 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 content of the first and second substances,
the multistage membrane separation unit comprises N +1 membrane separation units which are formed by sequentially connecting a heater and membrane separation groups in series, all the membrane separation units are sequentially connected in series and communicated, and N is more than or equal to 1;
the permeate gas discharge ports of the 1 st to the Nth membrane separation units are communicated with the hydrogen purification unit;
the method comprises the following steps:
(1) introducing the synthetic tail gas into a pretreatment unit to obtain a gas flow with the water content of less than 0.01ppmw and the hydrocarbon content of less than 0.01 ppmw;
(2) introducing the gas flow obtained in the step (1) into a heat recovery unit, and exchanging heat with the permeable gas and/or the non-permeable gas obtained from the (N + 1) th membrane separation unit;
(3) introducing the gas flow subjected to heat exchange in the step (2) into a 1 st membrane separation unit for membrane separation, taking the obtained non-permeation gas as the feed of the next membrane separation unit, and finally introducing into an N +1 th membrane separation unit for membrane separation;
(4) collecting the permeate gas obtained by the 1 st to the Nth membrane separation units and sending the permeate gas into 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 heat recovery unit for heating the synthesis tail gas, and then sending the synthesis tail gas to a hydrogen purification unit; collecting the non-permeate gas obtained by the (N + 1) th stage membrane separation, returning the non-permeate gas to a heat recovery unit for heating the synthesis tail gas, and then sending the synthesis tail gas to the non-permeate gas recovery unit.
By adopting the preferable scheme, the pressure potential energy generated when a single group of membranes operates is shared, and the pressure gradient difference is formed, so that the pressure potential energy borne by each group of membranes is reduced, the operating pressure is reduced, the working allowance is vacated, the system load is improved, the processing capacity of the feed gas and the yield and purity of hydrogen are increased, the secondary pressure increase of the feed gas is not needed, the power consumption of the device is reduced, and the economic benefit of the device is obviously improved.
According to a preferred embodiment of the present invention, the hydrogen purification unit is a PSA pressure swing adsorption unit. By adopting the preferred scheme, the device intermodal transportation is realized, the hydrogen purity 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 pipe network.
Embodiments of the present invention are described below in conjunction with the apparatus of fig. 1, which includes: the system comprises 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 content of the first and second substances,
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 communicated in series;
the permeable gas discharge port and the non-permeable gas discharge port 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-permeable gas discharge hole of the heat exchanger 4;
the method comprises the following steps:
(1) introducing the synthetic tail gas into a gas-liquid separation tank 2 and a filter 3 in sequence to obtain a gas flow with the water content of less than 0.01ppmw and the hydrocarbon content of less than 0.01 ppmw;
(2) introducing the airflow obtained in the step (1) into a heat exchanger 4, and exchanging heat with the permeation gas and/or the non-permeation gas from the membrane separation group X-2;
(3) introducing the gas flow subjected to heat exchange in the step (2) into a membrane separation group X-1 for membrane separation, and introducing the obtained non-permeation gas into a membrane separation group X-2 for membrane separation;
(4) collecting the permeating gas obtained by the membrane separation group X-1 and sending the permeating gas into a hydrogen purification unit; the permeate gas obtained by the membrane separation group X-2 returns to a heat exchanger 4 for heating the gas flow obtained in the step (1), and then is sent to a hydrogen purification unit; collecting the non-permeate gas obtained by the membrane separation group X-2, returning the non-permeate gas to the heat exchanger 4 for heating the gas flow obtained in the step (1), and sending the gas flow into a non-permeate gas recovery unit.
The invention utilizes the waste heat of products (permeable gas and non-permeable gas) to exchange heat for the synthetic 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 group, the two membrane separation groups have different operating pressures and temperatures and form a certain gradient, the pressure potential energy is fully utilized, and the pressure potential energy generated when a single membrane group operates is shared, so that the pressure potential energy borne by each membrane group is reduced, the operating pressure is reduced, the working allowance is freed, the load of the device is improved, the treatment 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 obviously improved.
According to a preferred embodiment of the invention, the inlet and/or outlet of each working unit of the device is provided with a valve, so that the dynamic adjustment of the process can be realized.
The invention is further illustrated by the following examples. The following examples were carried out in the apparatus shown in FIG. 1.
Example 1
Synthesis of Tail gas (H)2：70％；N2：10.9％；CH4：8.1％；CO：7％；CO2：1.7％；C2 +: 2.3 percent by volume) is subjected to gas-liquid separation in a gas-liquid separation tank 2, and then enters a filter 3 to reduce the water content in the feed gas to 0 and reduce the hydrocarbon component to below 0.0008 ppmw; then the mixture is introduced into a heat exchanger 4 for heat exchange;
then the gas enters a steam heater for 5 liters of temperature to 65 ℃, enters a membrane separation group X-1 with the operation pressure of 5.5Mpa to obtain permeation gas 8 and non-permeation gas 7, the non-permeation gas 7 enters a steam heater for 6 controlled by the pressure of a pressure regulating valve V-1 to be heated to 85 ℃, and then enters a membrane separation group X-2 with the operation pressure of 5.0Mpa to obtain permeation gas 10 and non-permeation gas 9;
the permeating gas 8 separated by the membrane separation group X-1 is sent to PSA pressure swing adsorption to produce hydrogen; the permeating gas 10 separated by the membrane separation group X-2 is sent to a heat exchanger 4 for heat exchange and then sent to PSA pressure swing adsorption for hydrogen production, and the non-permeating gas 9 separated by the membrane separation group X-2 is sent to the heat exchanger 4 for heat exchange and then sent to a fuel gas pipe network 14.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 2
The difference from the example 1 is that after heat exchange, the gas flow enters a steam heater 5 to raise the temperature to 60 ℃, enters a membrane separation group X-1 with the operating pressure of 6.0Mpa to obtain the permeated gas 8 and the non-permeated gas 7, the non-permeated gas 7 enters the steam heater 6 to raise the temperature to 90 ℃ 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 4.0Mpa to obtain the permeated gas 10 and the non-permeated gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 3
The difference from the example 1 is that after heat exchange, the air flow enters a steam heater 5 to raise the temperature to 65 ℃ and enters a membrane separation group X-1 with the operation pressure of 5.0Mpa to obtain the permeated gas 8 and the non-permeated gas 7, the non-permeated gas 7 enters a steam heater 6 to raise the temperature to 90 ℃ through the pressure control of a pressure regulating valve V-1, and then enters a membrane separation group X-2 with the operation pressure of 4.0Mpa to obtain the permeated gas 10 and the non-permeated gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 4
The difference from the example 1 is that after heat exchange, the gas flow enters a steam heater 5 to raise the temperature to 60 ℃, enters a membrane separation group X-1 with the operation pressure of 5.5Mpa to obtain the permeated gas 8 and the non-permeated gas 7, the non-permeated gas 7 enters a steam heater 6 to raise the temperature to 100 ℃ through the pressure control of a pressure regulating valve V-1, and then enters a membrane separation group X-2 with the operation pressure of 5.0Mpa to obtain the permeated gas 10 and the non-permeated gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 5
The difference from the example 1 is that after heat exchange, the air flow enters a steam heater for 5 liters of temperature to 65 ℃, enters a membrane separation group X-1 with the operation pressure of 8Mpa to obtain the permeating gas 8 and the non-permeating gas 7, the non-permeating gas 7 enters a steam heater for 6 temperature rise to 85 ℃ through the pressure control of a pressure regulating valve V-1, and then enters a membrane separation group X-2 with the operation pressure of 3.0Mpa to obtain the permeating gas 10 and the non-permeating gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Example 6
The difference from the example 1 is that after heat exchange, the gas flow enters a steam heater 5 to raise the temperature to 60 ℃, enters a membrane separation group X-1 with the operating pressure of 8MPa to obtain the permeated gas 8 and the non-permeated gas 7, the non-permeated gas 7 enters a steam heater 6 to raise the temperature to 100 ℃ 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 the permeated gas 10 and the non-permeated gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
Comparative example 1
The difference from the example 1 is that after heat exchange, the gas flow enters a steam heater 5, the temperature is raised to 100 ℃, the gas flow enters a membrane separation group X-1 with the operating pressure of 3Mpa to obtain the permeating gas 8 and the non-permeating gas 7, the non-permeating gas 7 enters a steam heater 6 through a pressure regulating valve V-1 and the action of a pump to control the pressure and raise the temperature to 60 ℃, and then the membrane separation group X-2 with the operating pressure of 8.0Mpa is introduced to obtain the permeating gas 10 and the non-permeating gas 9.
The energy consumption, hydrogen yield and purity were calculated and are shown in table 1.
TABLE 1
The results show that the embodiment adopting the technical scheme of the invention has high hydrogen purity, high yield of more than 93 percent, low energy consumption and 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, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A separation method of synthesis tail gas is characterized by comprising the following steps:
sequentially carrying out at least two sections of membrane separation on the synthesis tail gas, wherein the non-permeable gas obtained by the N section of membrane separation is used as the feeding material of the (N + 1) th section of membrane separation, the pressure of the feeding side of the N section of membrane separation is higher than that of the feeding side of the (N + 1) th section of membrane separation, and the temperature of the N section of membrane separation is lower than that of the (N + 1) th section of membrane separation; wherein N is more than or equal to 1.
2. The separation method according to claim 1,
the pressure of the feeding side of the N-stage membrane separation is 0.5-2Mpa higher than that of the feeding side of the (N + 1) -stage membrane separation; and/or
The temperature of the membrane separation of the Nth stage is 10-30 ℃ lower than that of the membrane separation of the (N + 1) th stage, and the temperature is preferably 20-30 ℃.
3. The separation method according to claim 1 or 2, wherein,
the temperature of any section of membrane separation is 40-100 ℃, and preferably 60-90 ℃; and/or
The feed side pressure of any section of membrane separation is 3.0-8.0 Mpa, preferably 4-6 Mpa.
4. The separation method according to any one of claims 1 to 3, wherein the method further comprises,
pretreating the synthesis tail gas to ensure that the water content and the hydrocarbon content in the synthesis tail gas are respectively lower than 0.01ppmw and 0.01 ppmw; and/or
And (3) using the permeation gas and/or the non-permeation gas obtained by the membrane separation of the (N + 1) th stage for heating the synthesis tail gas.
5. The separation method according to any one of claims 1 to 4, wherein the synthesis tail gas has a hydrogen content of at least 70 vol%.
6. The separation method according to any one of claims 1 to 5, wherein the synthesis tail gas flow rate is from 1 to 50 ten thousand Nm3/hr。
7. The separation method according to any one of claims 1 to 6, wherein the hydrogen content in the permeate gas obtained by the membrane separation of the (N + 1) th stage is more than 90 mol%.
8. The separation method according to any one of claims 1 to 7, wherein the method is carried out in an apparatus,
the device comprises:
the system comprises a pretreatment unit, a heat recovery unit, a multi-stage membrane separation unit, a hydrogen purification unit and a non-permeable 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 first and the second end of the pipe are connected with each other,
the multistage membrane separation unit comprises N +1 membrane separation units which are formed by sequentially connecting a heater and membrane separation groups in series, all the membrane separation units are sequentially connected in series and communicated, and N is more than or equal to 1;
the permeate gas discharge ports of the 1 st to the Nth membrane separation units are communicated with the hydrogen purification unit;
the permeate gas discharge port and the non-permeate gas discharge port 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 tail gas into a pretreatment unit to obtain a gas stream with the water content of less than 0.01ppmw and the hydrocarbon content of less than 0.001 ppmw;
(2) introducing the airflow obtained in the step (1) into a heat recovery unit, and exchanging heat with the permeated gas and/or the non-permeated gas obtained from the (N + 1) th membrane separation unit;
(3) introducing the gas flow subjected to heat exchange in the step (2) into a 1 st membrane separation unit for membrane separation, taking the obtained non-permeation gas as the feed of the next membrane separation unit, and finally introducing into an N +1 th membrane separation unit for membrane separation;
(4) collecting the permeate gas obtained by the 1 st to the Nth membrane separation units and sending the permeate gas into 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 heat recovery unit for heating the synthesis tail gas, and then sending the synthesis tail gas to a hydrogen purification unit; collecting the non-permeate gas obtained by the (N + 1) th stage membrane separation, returning the non-permeate gas to a recovery heat unit for heating the synthesis tail gas, and then sending the synthesis tail gas to a non-permeate gas recovery unit.
9. The separation method of claim 8, wherein the pre-treatment unit comprises one or both of a gas-liquid separation tank, a filter.
10. The separation method according to claim 8,
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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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