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CN118687339B - Helium recovery device for non-low-temperature catalytic purification and method for manufacturing helium - Google Patents

Helium recovery device for non-low-temperature catalytic purification and method for manufacturing helium Download PDF

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Publication number
CN118687339B
CN118687339B CN202411162314.1A CN202411162314A CN118687339B CN 118687339 B CN118687339 B CN 118687339B CN 202411162314 A CN202411162314 A CN 202411162314A CN 118687339 B CN118687339 B CN 118687339B
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gas
heat exchanger
helium
catalytic
separation tank
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CN118687339A (en
Inventor
袁士豪
韩小磊
汪晗
朱程浩
沈昕悦
张悦晨
夏雨涵
盛文龙
张成雄
葛仲向
傅宇飞
徐庆松
褚瑞华
管海平
洪梦丽
赵金秧
张云
祝琦祥
何仙来
李冬锋
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Hang Yang Group Co ltd
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Hang Yang Group Co ltd
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Abstract

本发明为一种非低温催化纯化的氦气回收装置及制造氦气的方法，该装置由催化系统和纯化系统组成，所述催化系统由换热器、预压缩机、增压机、一级气液分离罐、二级气液分离罐、抽真空装置组成，相互之间通过管道连接，其中换热器上还设置有冷量系统和冷量循环补充系统，所述换热器与纯化系统连接，该纯化系统由5A分子筛、N2吸附膜Ⅰ、N2吸附膜Ⅱ、CH4、H2、CO催化分解器、10X分子筛、N2吸附膜Ⅲ，相互之间通过管道依次连接。本发明用空分装置ASU中PN（压力氮气）作为本发明装置主要冷量来源，并辅以斯特林制冷循环提供补充冷量，液化天然气。

The present invention is a non-low-temperature catalytic purification helium recovery device and a method for producing helium. The device consists of a catalytic system and a purification system. The catalytic system consists of a heat exchanger, a pre-compressor, a supercharger, a primary gas-liquid separation tank, a secondary gas-liquid separation tank, and a vacuum device, which are connected to each other through pipelines. The heat exchanger is also provided with a cold system and a cold cycle supplement system. The heat exchanger is connected to the purification system. The purification system consists of a 5A molecular sieve, N2 adsorption membrane I, N2 adsorption membrane II, CH4 , H2 , CO catalytic decomposer, 10X molecular sieve, N2 adsorption membrane III, which are sequentially connected to each other through pipelines. The present invention uses PN (pressure nitrogen) in the air separation unit ASU as the main cold source of the device of the present invention, and is supplemented by a Stirling refrigeration cycle to provide supplementary cold, liquefied natural gas.

Description

Helium recovery device for non-low-temperature catalytic purification and method for manufacturing helium
Technical Field
The invention designs a helium recovery device for non-low-temperature catalytic purification and a method for manufacturing helium, and belongs to the field of gas separation.
Background
In recent years, helium is used as a rare gas which is important in the fields of aerospace, scientific research, high-tech industrial production and the like, and has become an important strategic resource which is very important in all countries of the world, the primary application fields of the helium resource in China comprise low-temperature superconduction, balloon carrier gas, semiconductors, optical fiber production, vacuum leak detection and the like, the helium is a rare non-renewable resource, the content of the helium in the atmosphere is rare, the concentration cost is very high, and the content of the helium in natural gas is from a few thousandths to a few percent, so that the helium used at present mainly comes from natural gas, the average value of the helium content in the natural gas is thousands of times higher than that in the air, and therefore, the natural gas deliming is an important means for improving the helium yield and maintaining the helium supply safety in China.
Disclosure of Invention
The invention develops a helium recovery device for non-low-temperature catalytic purification and a method for manufacturing helium, PN (pressure nitrogen) in an ASU (air separation unit) is used as a main cold energy source of the device, and Stirling refrigeration cycle is used for providing supplementary cold energy to liquefy natural gas. The liquefied natural gas is subjected to secondary throttling flash evaporation, helium-rich gas is collected, and the residual LNG is supercooled and then is conveyed to an LNG storage tank. The helium-rich gas passes through a 5A molecular sieve, an N 2 adsorption film I, an N 2 adsorption film II, a CH 4、H2, CO catalytic decomposition, a 10X molecular sieve and an N 2 adsorption film III to obtain 4.5N-5N helium.
The invention provides a helium recovery device for non-low-temperature catalytic purification, which consists of a catalytic system and a purification system, wherein the catalytic system consists of a heat exchanger, a precompressor, a booster, a primary gas-liquid separation tank, a secondary gas-liquid separation tank and a vacuumizing device, which are connected through pipelines, a cooling capacity system and a cooling capacity circulation supplementing system are further arranged on the heat exchanger, the heat exchanger is connected with the purification system, and the purification system consists of a 5A molecular sieve, an N 2 adsorption film I, N 2 adsorption film II, a CH 4、H2 adsorption film, a CO catalytic decomposer, a 10X molecular sieve and an N 2 adsorption film III, which are sequentially connected through pipelines.
Preferably, one end of the precompressor is connected with raw material natural gas, the other end of the precompressor is connected with a heat exchanger, the heat exchanger is connected with a supercharger, the supercharger is connected into the heat exchanger after being supercharged, and then is connected with a primary gas-liquid separation tank through the heat exchanger, wherein a gas outlet above the primary gas-liquid separation tank is connected with the heat exchanger, and then is connected with a purification system for purification, and a liquid outlet below the primary gas-liquid separation tank is connected with a secondary gas-liquid separation tank.
Preferably, the upper gas outlet of the secondary gas-liquid separation tank is connected to the upper gas outlet of the primary gas-liquid separation tank, two gases flow into the heat exchanger together, and the lower liquid outlet of the secondary gas-liquid separation tank is provided with two pipelines, wherein one pipeline is connected to the heat exchanger and then connected to the LNG storage tank for storage after passing through the heat exchanger, and the other pipeline is connected to the natural gas pipe network after passing through the heat exchanger.
Preferably, the refrigeration system consists of an air separation unit ASU and an expander, wherein the air separation unit ASU is firstly connected to a heat exchanger, the heat exchanger is then connected to the expander, and the expander is then connected back to the air separation unit ASU to realize circulation.
Preferably, the cold energy circulation supplementing system is a Stirling refrigerator, and two ends of the Stirling refrigerator are respectively connected to the heat exchanger to realize cold energy circulation supplementing.
A method of manufacturing helium from a non-cryogenically purified helium recovery unit, said method comprising the steps of:
1) Vacuumizing and replacing pipeline air;
2) The bare cooling device is used for starting the cooling capacity system and the cooling capacity circulating and supplementing system to perform bare cooling on the system;
3) Natural gas is introduced to separate coarse helium;
4) Purifying the crude helium to pure helium.
Preferably, the method for vacuumizing and replacing the pipeline air in the step 1 comprises the following steps:
opening a valve, opening a vacuumizing device, vacuumizing for 8-10 hours, waiting for the vacuum degree of the farthest end of a system pipeline from the vacuumizing device to be lower than 10Pa, and closing the vacuumizing device;
step two, purging and replacing residual air in a system pipeline for 6-7 hours by using nitrogen, and stopping purging and replacing the nitrogen when the dew point of a nitrogen outlet is reduced to-100 ℃ and the outlet is free of solid particle impurities;
And thirdly, starting the vacuumizing device again, discharging nitrogen in the system pipeline, waiting for the vacuum degree of the system pipeline at the farthest end from the vacuumizing device to be lower than 10Pa, stopping vacuumizing, and closing all valves of the device after vacuumizing and replacement are completed.
The specific method for starting the refrigeration capacity system and the refrigeration capacity circulation supplementing system in the step 2 is as follows:
After the pipeline vacuumizing in the step 1 is completed, a naked cooling device is needed, a Stirling refrigerator is started, the system cold source is supplemented and started, a refrigerating loop is formed by the heat exchanger and the Stirling refrigerator, the air separation device ASU is slowly opened after the Stirling refrigerator stably operates for 2-3 hours, pressurized nitrogen in the air separation device ASU returns to the air separation device ASU through the heat exchanger and the expander, wherein in the system starting stage, the pressurized nitrogen provides a cold source for naked cooling of the device through the heat exchanger and the Stirling refrigerator, and the expander does not play an expansion role.
The method is characterized in that the bare cooling time in the step 2 is 16-18 h, after the temperature measurement point of the system is reduced to a specified value, a valve is slowly opened, normal-temperature natural gas enters a heat exchanger after being compressed by a precompressor, then enters a booster from the heat exchanger, pressurized natural gas enters the heat exchanger again, after being cooled, the pressurized natural gas enters a primary gas-liquid separation tank through the heat exchanger, wherein the top of the primary gas-liquid separation tank is a gas flow passage, the bottom of the primary gas-liquid separation tank is a liquid flow passage, the liquid flow passage flows into a secondary gas-liquid separation tank, the gas flow passage above the secondary gas-liquid separation tank and the gas flow passage at the top of the primary gas-liquid separation tank are converged and then flow into the heat exchanger, then the primary gas-liquid separation tank is directly purified in a purification system, and part of liquid below the secondary gas-liquid separation tank is delivered to a LNG storage tank after passing through the heat exchanger, and the other part of the liquid enters a natural gas pipe network.
Preferably, the specific purification method of the purification system in the step 4 is as follows:
The crude helium gas from the heat exchanger enters a purification system, firstly passes through a 5A molecular sieve to remove H 2 O and most CO, then enters an N 2 adsorption film I, the helium content in the outlet gas of the N 2,N2 adsorption film I is 65% (V/V), the helium content in the outlet gas of the N 2 adsorption film I enters an N 2 adsorption film II, the helium content in the outlet gas of the N 2,N2 adsorption film II is 87% V/V, and after the majority of N 2 is removed, the outlet gas of the N 2 adsorption film II enters CH 4、H2, CO catalytic decomposition, wherein the catalyst for the catalytic decomposition of CH 4、H2 and CO is Pd & CuO, the working temperature is 270-320 ℃, the outlet gas of the N 2 adsorption film II contains CH 4、H2 and CO, and trace N 2, and enters CH 4、H2, After CO catalytic decomposition, under the action of oxygenation catalysis, CH 4、H2, CO react with oxygen to generate H 2 O and CO 2,CH4、H2, and impurities at the outlet of CO catalytic decomposition are H 2O、CO2 and O 2,CH4、H2, the CO catalytic decomposition outlet gas enters a 10X molecular sieve to remove H 2 O and CO 2, helium content in the 10X molecular sieve outlet gas is 99.9% V/V, the 10X molecular sieve outlet gas enters an N 2 adsorption film III, and the adsorbed trace N 2,N2 adsorption film III outlet gas is 4.5N-5N He.
The invention relates to a helium recovery device for non-low-temperature catalytic purification and a method for manufacturing helium, which utilize PN (pressure nitrogen) in an ASU (air separation unit) as a main cold source of the device and assist Stirling refrigeration cycle to provide supplementary cold and liquefied natural gas. The liquefied natural gas is subjected to secondary throttling flash evaporation, helium-rich gas is collected, and the residual LNG is supercooled and then is conveyed to an LNG storage tank. The method comprises the steps of ① conducting heat exchange and rewarming from an ASU (air separation unit) PN (pressure nitrogen), then conducting expansion, using the expansion function as cooling natural gas for secondary compression, conducting secondary throttling flash evaporation on ② high-pressure natural gas after heat exchange and liquefaction, generating helium-rich gas, conducting heat exchange and rewarming, then removing a helium purification module, conducting throttling on a part of LNG liquid after ③ throttling and cooling, taking the part of LNG liquid as a part of system cold, conducting heat exchange and vaporization, then merging the LNG liquid into a natural gas pipe network, conducting supercooling on the other part of LNG liquid, then conveying the LNG liquid to an LNG storage tank, conducting the transfer of ④ rewarming, and conducting catalytic decomposition on the helium-rich gas through a 5A molecular sieve, an N 2 adsorption membrane I, an N 2 adsorption membrane II, a CH 4、H2, a CO, a 10X molecular sieve and an N 2 adsorption membrane III to obtain 4.5n-5n. On the basis of fully utilizing an air separation cold source, the method utilizes a low-temperature gas separation means to efficiently enrich helium in natural gas, compared with low-temperature rectification helium enrichment, the method has compact and small equipment, small occupied area and quick equipment starting, and the production scale elastic change (30% -150%) is much larger (60% -120%) than that of low-temperature rectification under the condition of unchanged energy consumption.
Drawings
FIG. 1 is a schematic diagram of the construction of the present invention;
FIG. 2 is a schematic diagram of the purification system according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings: as shown in figures 1-2, the helium recovery device for non-low-temperature catalytic purification comprises a catalytic system and a purification system, wherein the catalytic system comprises a heat exchanger 9, a precompressor 4, a booster 7, a primary gas-liquid separation tank 11, a secondary gas-liquid separation tank 15 and a vacuumizing device, which are connected with each other through pipelines, wherein the heat exchanger 9 is also provided with a cold energy system and a cold energy circulating and supplementing system, the heat exchanger 9 is connected with the purification system, the purification system comprises a 5A molecular sieve 20, an N 2 adsorption film I21, an N 2 adsorption film II22, a CH 4、H2, a CO catalytic decomposer 23, a 10X molecular sieve 24 and an N 2 adsorption film III25, which are sequentially connected with each other through pipelines, one end of the precompressor 4 is connected with raw material natural gas, and the other end is connected with the heat exchanger 9, the heat exchanger 9 is connected with the supercharger 7, after the supercharger 7 is supercharged and then connected into the heat exchanger 9, the supercharger 7 is connected with the primary gas-liquid separation tank 11 through the heat exchanger 9, wherein a gas outlet above the primary gas-liquid separation tank 11 is connected with the heat exchanger 9, the heat exchanger 9 is connected into a purification system for purification, a liquid outlet below the heat exchanger 9 is connected with the secondary gas-liquid separation tank 15, a gas outlet above the secondary gas-liquid separation tank 15 is connected to a gas outlet above the primary gas-liquid separation tank 11, two gases flow into the heat exchanger 9 together, two pipelines are arranged at a liquid outlet below the secondary gas-liquid separation tank 15, the two pipelines are respectively connected into the heat exchanger 9, one pipeline is connected into an LNG storage tank after passing through the heat exchanger 9, and the other pipeline is connected into a natural gas pipe network after passing through the heat exchanger 9.
The cold energy system consists of an air separation device ASU and an expander 3, wherein the air separation device ASU is firstly connected to a heat exchanger 9, the heat exchanger 9 is then connected to the expander 3, the expander 3 is then connected back to the air separation device ASU to realize circulation, the cold energy circulation supplementing system is a Stirling refrigerator 41, and two ends of the Stirling refrigerator 41 are respectively connected to the heat exchanger 9 to realize cold energy circulation supplementing.
The specific implementation method comprises the following steps:
The helium recovery device for non-low-temperature catalytic purification and the method for manufacturing helium are used for removing helium from natural gas, collecting LNG helium-rich flash gas, and then obtaining 4.5 n-5 n helium through molecular sieve adsorption, catalytic cracking and nitrogen removal adsorption.
And (3) closing all valves of the device, wherein the device is required to vacuumize and replace pipeline air before starting, namely opening a valve L6, a valve C8, a valve M10, a valve D12, a valve F14, a valve G16, a valve H17 and a valve J18, opening a vacuumizing device, vacuumizing for 8-10 hours, and closing the vacuumizing device when the vacuum degree of the system pipeline at the farthest end from the vacuumizing device is lower than 10 Pa. And secondly, purging and replacing residual air in a system pipeline for 6-7 hours by using nitrogen, and stopping purging and replacing the nitrogen when the dew point of a nitrogen outlet is reduced to-100 ℃ and the outlet is free of solid particle impurities. And thirdly, starting the vacuumizing device again, discharging nitrogen in the system pipeline, and stopping vacuumizing when the vacuum degree of the system pipeline at the farthest end from the vacuumizing device is lower than 10 Pa. After the vacuum pumping and replacement are completed, all valves of the device are closed.
When the pipeline vacuumizing is completed, a bare cooling device is needed, the Stirling refrigerator 41 is started, the system cold source supplement starts to be started, and a refrigerating loop is formed by the cold end outlet 32 of the heat exchanger 9, the cold end inlet 39 of the heat exchanger 9 and the Stirling refrigerator 41. After the Stirling refrigerator 41 stably operates for 2-3 hours, the valve A2 is slowly opened, PN pressure nitrogen in the air separation device ASU1 returns to the air separation device ASU1 through the cold end inlet 38 of the heat exchanger 9, the cold end outlet 31 of the heat exchanger 9, the valve A2 and the expander 3. It should be noted that during the system start-up phase, PN pressure nitrogen passes through the heat exchanger 9 and together with the Stirling refrigerator 41 provides a cold source for the bare cooling of the device of the invention, and the expander 3 does not perform an expansion function.
After the temperature measurement point of the system is cooled for 16-18 hours, after the temperature measurement point of the system is reduced to a specified value, slowly opening a valve B5, compressing normal-temperature natural gas through a precompressor 4, then entering a hot end inlet 26 of a heat exchanger 9, cooling, then entering a booster 7 through a hot end outlet 33 of the heat exchanger 9, slowly opening a valve C8, entering the pressurized natural gas into a hot end inlet 27 of the heat exchanger 9, opening a valve M10, cooling, then entering the pressurized natural gas into a primary gas-liquid separation tank 11 through a hot end outlet 34 of the heat exchanger 9 and the valve M10. It should be noted that the primary gas-liquid separation tank 11 and the secondary gas-liquid separation tank 15 have no accumulated liquid in the system starting stage, and the throttled natural gas is discharged from the gas outlets at the tops of the primary gas-liquid separation tank 11 and the secondary gas-liquid separation tank 15. It is pointed out here that during the start-up phase of the device, the expander 3 is not active, no work of expansion is output, and the work of input of the supercharger 7 is derived from the work of expansion of the expander 3, so that the supercharger 7 is not active if the expander 3 is not active.
Valve E13, valve D12, valve F14, valve G16, valve K19, valve H17, valve J18 and throttle valve 40 are opened, and the cryogenic natural gas passes through heat exchanger 9 and then is collected into the natural gas pipe network through the process pipeline. In the equipment starting stage, low-temperature natural gas is in the system pipeline, and continuous cooling is realized by means of a process pipeline.
The device of the invention continuously reduces the temperature until the temperature of the hot end outlet 34 of the heat exchanger 9 reaches a set value through the low-temperature natural gas in the pipeline. Closing the valve D12, the valve K19, the valve H17 and the valve J18, and beginning to generate effusion at the bottom of the primary gas-liquid separation tank 11.
When the bottom of the primary gas-liquid separation tank 11 reaches a specified liquid level, the valve D12 and the valve K19 are slowly opened, and the liquid accumulation at the bottom of the primary gas-liquid separation tank 11 enters the secondary gas-liquid separation tank 15. And opening a valve K19, merging the gas at the top of the secondary gas-liquid separation tank 15 with the gas at the top of the primary gas-liquid separation tank 11, and entering the cold end inlet 35 of the heat exchanger 9.
After the bottom of the secondary gas-liquid separation tank 15 reaches a specified liquid level, a valve H17 is slowly opened, the liquid at the bottom of the secondary gas-liquid separation tank 15 enters a cold end inlet 37 of the heat exchanger 9 after being throttled and cooled by a throttle valve 40, and then exits from a cold end outlet 30 of the heat exchanger 9 after being re-warmed and vaporized by the heat exchanger 9 and is converged into a natural gas pipe network.
And opening a valve J18, allowing a part of liquid at the bottom of the secondary gas-liquid separation tank 15 to enter a hot end inlet 29 of the heat exchanger 9, supercooling the liquid by the heat exchanger 9, and then discharging the supercooled liquid from a hot end outlet 36 of the heat exchanger 9 to the LNG storage tank.
The bottom of the primary gas-liquid separation tank 11 starts to generate effusion, the expander 3 starts to start, expansion work is output to the supercharger 7, the liquefaction rate of the natural gas after supercharging is obviously improved through the throttle valve M10 and the valve D12, and meanwhile, the helium removal rate is also improved. The top gas of the primary gas-liquid separation tank 11 and the top gas of the secondary gas-liquid separation tank 15 are rich in helium, and after merging, the helium is rewarmed by the heat exchanger 9 and then goes to the helium adsorption purification system. It is important to note here that after the device of the invention has been operated steadily, if the helium content of the gas at the cold end outlet 28 of the heat exchanger 9 does not reach the design value of 95% or less, it is led into the natural gas line via the process line, if it reaches the design value of 95% or it is led into the purification system.
The crude helium gas at the cold end outlet 28 of the heat exchanger 9 mainly contains CH 4、N2、H2、H2 O, CO and other impurities, and needs to be correspondingly removed, the crude helium gas at the cold end outlet 28 of the heat exchanger 9 enters a purification system, firstly passes through a 5A molecular sieve 20 to remove H 2 O and most CO, then enters an N 2 adsorption film I21, and the helium content of the outlet gas of the N 2,N2 adsorption film I21 is 65% V/V.
The outlet gas of the N 2 adsorption film I21 enters the N 2 adsorption film II22 to adsorb a small amount of N 2,N2 adsorption film II22, and the helium content of the outlet gas of the N 2 adsorption film II is 87% V/V. After most of N 2 is removed, the gas at the outlet of the N 2 adsorption film II22 enters CH 4、H2 and CO for catalytic decomposition 23. The catalyst of CH 4、H2 and CO catalytic decomposition 23 is Pd & CuO, and the working temperature is 270-320 ℃.
The outlet gas of the N 2 adsorption film II22 contains CH 4、H2, CO and trace N 2, and after entering CH 4、H2 and CO catalytic decomposition 23, CH 4、H2 and CO react with oxygen to generate H 2 O and CO 2.CH4、H2 under the action of oxygen-adding catalysis, and the outlet impurities of the CO catalytic decomposition 23 are H 2O、CO2 and O 2.
The outlet gas of CH 4、H2 and CO catalytic decomposition 23 enters a 10X molecular sieve 24 to remove H 2 O and CO 2, and the helium content of the outlet gas of the 10X molecular sieve 24 is 99.9% V/V. The outlet gas of the 10X molecular sieve 24 enters an N 2 adsorption film III25, and the outlet gas of the adsorption film III25 for adsorbing trace N 2,N2 is 4.5-5N He.
The invention relates to a helium recovery device for non-low-temperature catalytic purification and a method for manufacturing helium, which utilize PN (pressure nitrogen) in an ASU (air separation unit) as a main cold source of the device and assist Stirling refrigeration cycle to provide supplementary cold and liquefied natural gas. The liquefied natural gas is subjected to secondary throttling flash evaporation, helium-rich gas is collected, and the residual LNG is supercooled and then is conveyed to an LNG storage tank. The method comprises the steps of ① conducting heat exchange and rewarming on PN (pressure nitrogen) from an air separation device ASU (air separation device), expanding, using the expansion function as cooling natural gas for secondary compression, conducting secondary throttling flash evaporation on ② high-pressure natural gas after heat exchange and liquefaction to generate helium-rich gas, conducting heat exchange and rewarming on the helium-rich gas, removing a helium purification module, conducting throttling on a part of LNG liquid after ③ is throttled and cooled, conducting heat exchange and vaporization, then merging the LNG liquid into a natural gas pipe network, conducting supercooling on the other part of LNG liquid, and then conveying the LNG liquid to an LNG storage tank, conducting 5A molecular sieve, N 2 adsorption membrane I, N 2 adsorption membrane II, CH 4、H2, CO catalytic decomposition, 10X molecular sieve and N 2 adsorption membrane III on the helium-rich gas after ④ rewarming, and obtaining 4.5N-5N helium. On the basis of fully utilizing an air separation cold source, the method utilizes a low-temperature gas separation means to efficiently enrich helium in natural gas, compared with low-temperature rectification helium enrichment, the method has compact and small equipment, small occupied area and quick equipment starting, and the production scale elastic change (30% -150%) is much larger (60% -120%) than that of low-temperature rectification under the condition of unchanged energy consumption.

Claims (9)

1. The helium recovery device for non-low-temperature catalytic purification comprises a catalytic system and a purification system, and is characterized in that the catalytic system comprises a heat exchanger (9), a precompressor (4), a booster (7), a first-stage gas-liquid separation tank (11), a second-stage gas-liquid separation tank (15) and a vacuumizing device, wherein the two are connected through pipelines, a cold energy system and a cold energy circulating supplementing system are further arranged on the heat exchanger (9), the heat exchanger (9) is connected with the purification system, the purification system comprises a 5A molecular sieve (20), an N 2 adsorption film I (21), an N 2 adsorption film II (22), a CH 4、H2, a CO catalytic decomposer (23), a 10X molecular sieve (24) and an N 2 adsorption film III (25), the two are sequentially connected through pipelines, one end of the precompressor (4) is connected with raw material natural gas, the other end of the precompressor (9) is connected with the booster (7), the booster (7) is pressurized and then connected with the heat exchanger (9), the heat exchanger (9) is connected with the second-stage gas-liquid separation tank (11) through the heat exchanger (9), and the gas-liquid separation tank (11) is connected with the second-stage gas-liquid separation tank (9), and the second-stage gas-liquid purification system is connected with the second-stage gas separator (11) through the heat exchanger (9), and the second-stage gas separator is connected with the second-stage gas separator (11.
2. The non-cryogenic catalytic purified helium recovery unit according to claim 1, wherein the upper gas outlet of the secondary gas-liquid separation tank (15) is connected to the upper gas outlet of the primary gas-liquid separation tank (11), two gases flow together into the heat exchanger (9), and the lower liquid outlet of the secondary gas-liquid separation tank (15) is provided with two pipelines, one of which is connected to the heat exchanger (9) and then connected to the LNG storage tank for storage, and the other of which is connected to the natural gas pipe network after passing through the heat exchanger (9).
3. The non-cryogenically purified helium recovery unit according to claim 1 wherein said refrigeration system is comprised of an air separation unit ASU (1) and an expander (3), wherein the air separation unit ASU (1) is first connected to a heat exchanger (9), wherein the heat exchanger (9) is then connected to the expander (3), and wherein the expander (3) is then connected back to the air separation unit ASU (1) for recycling.
4. The non-cryogenic catalytic purified helium recovery unit of claim 1, wherein the cold energy circulation supplementing system is a Stirling refrigerator (41), and two ends of the Stirling refrigerator (41) are respectively connected to the heat exchanger (9) to realize cold energy circulation supplementing.
5. A method of producing helium gas from a non-cryogenic catalytic purified helium recovery unit according to any one of claims 1 to 4, said method comprising the steps of:
1) Vacuumizing and replacing pipeline air;
2) The bare cooling device is used for starting the cooling capacity system and the cooling capacity circulating and supplementing system to perform bare cooling on the system;
3) Natural gas is introduced to separate coarse helium;
4) Purifying the crude helium to pure helium.
6. The method for producing helium gas by using a non-cryogenic catalytic purification helium recovery unit according to claim 5, wherein the method for evacuating and replacing pipeline air in step 1 is as follows:
opening a valve, opening a vacuumizing device, vacuumizing for 8-10 hours, waiting for the vacuum degree of the farthest end of a system pipeline from the vacuumizing device to be lower than 10Pa, and closing the vacuumizing device;
step two, purging and replacing residual air in a system pipeline for 6-7 hours by using nitrogen, and stopping purging and replacing the nitrogen when the dew point of a nitrogen outlet is reduced to-100 ℃ and the outlet is free of solid particle impurities;
And thirdly, starting the vacuumizing device again, discharging nitrogen in the system pipeline, waiting for the vacuum degree of the system pipeline at the farthest end from the vacuumizing device to be lower than 10Pa, stopping vacuumizing, and closing all valves of the device after vacuumizing and replacement are completed.
7. The method for producing helium gas by using a non-cryogenic catalytic purification helium recovery unit according to claim 5, wherein the specific method for starting the refrigeration system and the refrigeration cycle replenishment system in step 2 is as follows:
After the pipeline vacuumizing in the step 1 is completed, a naked cooling device is needed, a Stirling refrigerator (41) is started, a system cold source is started to be used, a refrigerating loop is formed by the heat exchanger (9) and the Stirling refrigerator (41), the air separation device ASU (1) is slowly opened after the Stirling refrigerator (41) stably operates for 2-3 hours, pressurized nitrogen in the air separation device ASU (1) returns to the air separation device ASU (1) through the heat exchanger (9) and the expander (3), wherein in a system starting stage, the pressurized nitrogen and the Stirling refrigerator (41) provide cold sources for naked cooling of the device together, and the expander (3) does not play an expansion role.
8. The method for producing helium by using the non-cryogenic catalytic purification helium recovery unit according to claim 5, wherein the bare cooling time in the step 2 is 16-18 h, after the system temperature measurement point is reduced to a specified value, a valve is slowly opened, normal-temperature natural gas enters a heat exchanger (9) after being compressed by a precompressor (4), then enters a booster (7) from the heat exchanger (9), pressurized natural gas enters the heat exchanger (9) again after being cooled, the pressurized natural gas enters a primary gas-liquid separation tank (11) through the heat exchanger (9), wherein the top of the primary gas-liquid separation tank (11) is a gas flow passage, the bottom of the primary gas-liquid separation tank is a liquid flow passage, the liquid flow passage flows into a secondary gas-liquid separation tank (15), the top of the secondary gas-liquid separation tank (15) and the gas flow passage are converged, then flow into the heat exchanger (9), then the secondary gas-liquid is purified by being directly introduced into the purification system, and the LNG is collected after the other part of the secondary gas-liquid separation tank (15) passes through the heat exchanger (9).
9. The method for producing helium gas by using a non-cryogenic catalytic purification helium recovery unit according to claim 5, wherein the specific purification method of the purification system in step 4 is as follows:
the crude helium gas from the heat exchanger (9) enters a purification system, firstly passes through a 5A molecular sieve (20) to remove H 2 O and most CO, then enters an N 2 adsorption film I (21), the outlet gas of the N 2,N2 adsorption film I (21) is removed to contain 65 percent (V/V) of helium, the outlet gas of the N 2 adsorption film I (21) enters an N 2 adsorption film II (22), the outlet gas of the N 2,N2 adsorption film II (22) is adsorbed to contain 87 percent (V/V) of helium, and after the N 2 is removed to the majority, the outlet gas of the N 2 adsorption film II (22) enters CH 4、H2, The CO catalytic decomposer (23), the CH 4、H2 and the catalyst of the CO catalytic decomposer (23) are Pd and CuO, the working temperature is 270-320 ℃, and the outlet gas of the N 2 adsorption film II (22) contains CH 4、H2, CO and trace N 2 enter a CH 4、H2 and CO catalytic decomposer (23), and under the action of oxygen adding catalysis, CH 4、H2 and CO react with oxygen to generate H 2 O and CO 2,CH4、H2, The impurities at the outlet of the CO catalytic decomposer (23) are H 2O、CO2 and O 2,CH4、H2, The outlet gas of the CO catalytic decomposer (23) enters a 10X molecular sieve (24) to remove H 2 O and CO 2, helium is contained in the outlet gas of the 10X molecular sieve (24) at 99.9% V/V, the outlet gas of the 10X molecular sieve (24) enters an N 2 adsorption film III (25), and the outlet gas of the adsorption film III (25) for adsorbing trace N 2,N2 is 4.5N-5N He.
CN202411162314.1A 2024-08-23 2024-08-23 Helium recovery device for non-low-temperature catalytic purification and method for manufacturing helium Active CN118687339B (en)

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