A device for removing hydrogen, nitrogen and nitrogen from crude neon and helium gas and a method for using the device

Abstract

The present invention is a device and a method for using crude neon-helium gas for dehydrogenation, denitrification and nitrogen purification. The device is composed of a nitrogen deoxygenation purification system, a crude neon-helium gas dehydrogenation system and a nitrogen removal system. The nitrogen deoxygenation purification system and the crude neon-helium gas dehydrogenation system are both connected to an air separation unit AUS. The crude neon-helium gas dehydrogenation system is coupled and connected to the nitrogen deoxygenation purification system and the nitrogen removal system, respectively. The crude neon-helium gas dehydrogenation system is composed of a crude neon-helium gas booster, a crude neon-helium gas storage tank, a heat exchanger A, a dehydrogenation tower and an electric heater, which are connected to each other through a pipeline. A valve is provided on the pipeline, and the flow direction is controlled by opening and closing the valve. The nitrogen deoxygenation purification system is composed of a deoxygenation tower, a nitrogen booster, a heat exchanger B and a nitrogen buffer tank. The present invention realizes the deep coupling of the crude neon-helium gas deep dehydrogenation process and the nitrogen purification process, improves the production capacity of neon-helium gas and ultra-high purity nitrogen, and reduces the production cost at the same time.

Description

Technical Field

[0001] The invention discloses a device for removing hydrogen and nitrogen from crude neon and helium gas and a method for using the device, and belongs to the field of gas separation. Background Art

[0002] At present, the removal of hydrogen and nitrogen from crude neon and helium mainly relies on deep cryogenic distillation. Neon and helium have extremely low boiling points (He: 4K, Ne: 20K), which results in extremely high pressure required for cryogenic distillation process, which results in large volume of equipment for deep purification and refining of crude neon and helium, and extremely high requirements for equipment insulation and heat insulation. The volume purity of electronic grade ultra-high purity nitrogen needs to be higher than 99.9999%, which is usually obtained by purifying high-purity nitrogen from air separation (volume purity ≥ 99.999%) through a purifier. The purifier is expensive, the working condition is high temperature, and the getter needs to be replaced regularly, which has a high cost of use. The non-cryogenic method is an emerging gas separation method that has been developed since the 1990s. Compared with the cryogenic distillation method, the non-cryogenic gas separation method has the advantages of 1. fast response speed, 2. room temperature operation, 3. compact equipment structure, 4. high separation coefficient between different components of the gas, and 5. more suitable for the separation of precision systems than cryogenic distillation. The invention combines the deep dehydrogenation and denitrification of crude neon-helium gas and the purification of nitrogen, and proposes a device and a method for using the dehydrogenation and denitrification of crude neon-helium gas. Summary of the invention

[0003] The invention discloses a device for dehydrogenation, denitrification and nitrogen purification of crude neon-helium gas and a method for using the device. By coupling a deep dehydrogenation process of crude neon-helium gas with a regeneration process of a nitrogen purification tower, and coupling the regeneration process of the crude neon-helium gas dehydrogenation tower with nitrogen purification, deep coupling of the deep dehydrogenation process of crude neon-helium gas and the nitrogen purification process is achieved, thereby increasing the production capacity of neon-helium gas and ultra-high purity nitrogen gas and reducing the production cost at the same time.

[0004] The present invention provides a device for dehydrogenating, denitrogenating and purifying crude neon-helium gas. The device is composed of a nitrogen deoxygenation purification system, a crude neon-helium dehydrogenation system and a nitrogen removal system. The nitrogen deoxygenation purification system and the crude neon-helium dehydrogenation system are both connected to an air separation device AUS. The crude neon-helium dehydrogenation system is coupled and connected to the nitrogen deoxygenation purification system and the nitrogen removal system respectively. The crude neon-helium dehydrogenation system is composed of a crude neon-helium gas booster, a crude neon-helium gas storage tank, a heat exchanger A, a dehydrogenation tower and an electric heater, which are connected to each other through a pipeline. A valve is arranged on the pipeline, and the flow direction is controlled by opening and closing the valve. The nitrogen deoxygenation purification system is composed of a deoxygenation tower, a nitrogen booster, a heat exchanger B and a nitrogen buffer tank. The nitrogen removal system is composed of a primary nitrogen removal membrane, a secondary nitrogen removal membrane, a crude neon-helium gas booster pump, a heat exchanger C and a TSA tower.

[0005] Preferably, the crude neon-helium product outlet of the air separation unit AUS is connected to a crude neon-helium booster, which is connected to a crude neon-helium storage tank, and a dehydrogenation tower, a heat exchanger A, and an electric heater are respectively connected to the rear of the crude neon-helium storage tank, wherein the electric heater is connected to the deoxygenation tower of the nitrogen deoxygenation purification system, one branch of the dehydrogenation tower is connected to the heat exchanger A, and the other branch is connected to the nitrogen booster of the nitrogen deoxygenation purification system, the pressurized nitrogen flows to an external collection tank, and the heat exchanger A is connected to the denitrification system.

[0006] Preferably, two routes are arranged behind the deoxygenation tower of the nitrogen deoxygenation purification system, one of which is connected to the heat exchanger A and then flows into the denitrification system, and the other is connected to the heat exchanger B and then connected to the one in the heat exchanger A and connected to the denitrification system together, the heat exchanger B is also connected to the nitrogen buffer tank, the nitrogen buffer tank is connected to the air separation nitrogen product extraction port, and the nitrogen buffer tank is also provided with a blower.

[0007] Preferably, the rear of the heat exchanger A is connected in sequence to the primary nitrogen removal membrane, crude neon-helium booster pump, secondary nitrogen removal membrane, heat exchanger C, and TSA tower of the nitrogen removal system, wherein the rear of the TSA tower is connected to the heat exchanger C, and the gas after passing through the TSA tower is again heat exchanged through the heat exchanger C and flows to the external neon-helium separation system. The other part of the heat exchanger C is connected to the freeze dryer to provide the required cooling capacity for the TSA tower to adsorb impurities by cooling the outlet raw gas of the secondary nitrogen removal membrane.

[0008] Preferably, two dehydrogenation towers, two TSA towers and two deoxygenation towers are provided (not limited to, multiple towers can be provided in parallel), wherein the dehydrogenation tower consists of a first dehydrogenation tower and a second dehydrogenation tower, the TSA tower consists of a first TSA tower and a second TSA tower, and the deoxygenation tower consists of a first deoxygenation tower and a second deoxygenation tower, and the two dehydrogenation towers or two TSA towers or two deoxygenation towers are connected by pipelines, and valves are installed on the pipelines to control the flow direction.

[0009] A method for using a device for removing hydrogen, nitrogen and nitrogen from crude neon and helium gas, the method comprising the following steps:

[0010] 1) Equipment purging and tower body preheating through the first dehydrogenation tower and the second dehydrogenation tower / precooling through the first TSA tower and the second TSA tower;

[0011] 2) The raw material crude neon and helium gas enters the nitrogen deoxygenation purification system to adsorb and remove oxygen from the raw material nitrogen;

[0012] 3) starting the crude neon-helium gas dehydrogenation device to remove hydrogen from the crude neon-helium gas from which oxygen has been removed in step 2);

[0013] 4) Finally, the crude neon-helium gas with oxygen and hydrogen removed enters the nitrogen removal system to remove nitrogen.

[0014] As a preferred method, the specific method for removing oxygen from the raw nitrogen by adsorption in step 2) is:

[0015] The raw crude neon-helium gas enters the second deoxidation tower through the nitrogen buffer tank and heat exchanger B, and adsorbs and removes oxygen in the raw nitrogen. The volume concentration of oxygen component at the outlet of the second deoxidation tower is ≤0.1ppm. The nitrogen booster is started, and the purified nitrogen at the outlet of the second deoxidation tower V / V ≥99.9999%. It is pressurized to 8ata (A) by the nitrogen booster and then sent to the use occasion. After 1.5 to 2 hours of nitrogen deoxidation and purification, the crude neon-helium gas dehydrogenation device is started.

[0016] As a preferred method: the specific method of starting the crude neon-helium gas dehydrogenation device in step 3) is:

[0017] Before activation, it is necessary to preheat for 0.5 to 1 hour to raise the temperature of the dehydrogenating agent in the first dehydrogenation tower and the second dehydrogenation tower to 200℃±5℃ and stabilize it for 10min to 15min. Then the crude neon helium dehydrogenation device starts to operate. The crude neon helium booster pressurizes the crude neon helium raw material to 150ata and stores it in the crude neon helium storage tank. When the temperature of the dehydrogenating agent in the dehydrogenation tower in the crude neon helium dehydrogenation device is stabilized at 200℃±5℃, the crude neon helium enters the first dehydrogenation tower and starts to remove the impurity hydrogen component in the crude neon helium. The dehydrogenated crude neon helium at the outlet of the first dehydrogenation tower passes through the heat exchanger A and enters the nitrogen removal system; the crude neon helium The crude neon helium gas from the storage tank is used as the regeneration gas for deoxidizer passivation in the second deoxidizer. It enters the second deoxidizer and removes the oxygen adsorbed by the deoxidizer through the hydrogen in the crude neon helium gas. When the crude neon helium gas from the nitrogen removal system enters the second deoxidizer, the temperature of the second deoxidizer will rise rapidly. At this time, it is necessary to control the flow rate of the crude neon helium gas entering the second deoxidizer and stabilize the temperature of the second deoxidizer at 300℃~330℃. The crude neon helium gas is dehydrogenated in the second deoxidizer and removes the oxygen adsorbed by the deoxidizer at the same time to complete the passivation of the deoxidizer. The dehydrogenated crude neon helium gas at the outlet of the second deoxidizer passes through the hot end passage of heat exchanger A or the hot end passage of heat exchanger B to remove the nitrogen system.

[0018] Preferably, the method for removing nitrogen in the nitrogen removal system in step 4) is as follows: the crude neon-helium gas after deoxygenation and dehydrogenation, with a hydrogen volume concentration of ≤1ppm and an oxygen volume concentration of ≤0.1ppm, first enters the primary nitrogen removal membrane, and obtains the crude neon-helium gas with some nitrogen removed on the permeate side; the outlet gas of the primary nitrogen removal membrane enters the secondary nitrogen removal membrane through a crude neon-helium booster pump, and obtains the crude neon-helium gas with a nitrogen volume concentration of not more than 0.3% on the permeate side of the secondary nitrogen removal membrane; the crude neon-helium gas with a nitrogen volume concentration of not more than 0.3% on the permeate side of the secondary nitrogen removal membrane enters the first TSA tower and the second TSA tower through the hot end flow path of heat exchanger C, deeply adsorbs nitrogen in the crude neon-helium gas, and the outlet nitrogen of the first TSA tower and the second TSA tower is reheated through the cold end flow path of heat exchanger C and then removed from the neon-helium separation system.

[0019] The present invention achieves deep coupling of the crude neon-helium deep dehydrogenation process and the nitrogen purification process by coupling the crude neon-helium deep dehydrogenation process with the nitrogen purification tower regeneration process, thereby increasing the neon-helium and ultra-high purity nitrogen production capacity and reducing the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a schematic diagram of the composition of the present invention. DETAILED DESCRIPTION

[0021] The present invention will be described in detail below with reference to the accompanying drawings: Figure 1As shown, the crude neon-helium dehydrogenation device and the nitrogen deoxygenation purification device in the present invention are logically connected in parallel, wherein the raw gas of the crude neon-helium dehydrogenation device comes from the crude neon-helium product of air separation, the outlet of the crude neon-helium product of air separation is connected to the inlet of the crude neon-helium booster 1, the outlet of the crude neon-helium booster 1 is connected to the inlet of the stop valve A2, and the outlet of the stop valve A2 is connected to the inlet of the crude neon-helium storage tank 3. The outlet of the crude neon-helium storage tank 3 is connected to the inlet of the stop valve B4, and the outlet of the stop valve B4 is simultaneously connected to the inlet of the stop valve C-X5, the inlet of the stop valve C-Y6, the inlet of the stop valve D17, the inlet of the stop valve E-X15, the inlet of the pressure reducing valve E-Y16, and the cold end outlet of the heat exchanger A18, the outlet of the stop valve D17 is connected to the cold end inlet of the heat exchanger A18, the outlet of the stop valve C-X5 is simultaneously connected to the inlet of the first dehydrogenation tower 9 and the outlet of the stop valve F-X7; the outlet of the stop valve C-Y6 is simultaneously connected to the inlet of the second dehydrogenation tower 10 and the outlet of the stop valve F-Y8. The inlet of the stop valve F-X7 and the inlet of the stop valve F-Y8 are commonly connected to the outlet of the stop valve G51 and the outlet of the blower 52. The inlet of the blower 52 is connected to the side outlet of the nitrogen buffer tank 38. The outlet of the first dehydrogenation tower 9 is connected to the inlet of the stop valve H-X11, and the outlet of the stop valve H-X11 is simultaneously connected to the inlet of the stop valve I-X13 and the hot end inlet 57 of the heat exchanger A18; the outlet of the second dehydrogenation tower 10 is connected to the inlet of the stop valve H-Y11, and the outlet of the stop valve H-Y12 is simultaneously connected to the inlet of the stop valve I-Y14 and the hot end inlet 57 of the heat exchanger A18. The outlet of the stop valve I-X13 and the outlet of the stop valve I-Y14 are simultaneously connected to the outlet of the stop valve J-X58, the outlet of the stop valve J-Y48, and the inlet of the nitrogen booster 50. The outlet of the stop valve E-X15 and the outlet of the pressure reducing valve E-Y16 are commonly connected to the inlet of the electric heater 19. The outlet of the electric heater 19 is simultaneously connected to the inlet of the stop valve K-X42 and the inlet of the stop valve K-Y43. The outlet of the stop valve K-X42 is simultaneously connected to the outlet of the stop valve L-X41 and the inlet of the second deoxidation tower 45; the outlet of the stop valve K-Y43 is simultaneously connected to the outlet of the stop valve L-Y40 and the inlet of the first deoxidation tower 44, and the outlet of the second deoxidation tower 45 is simultaneously connected to the inlet of the stop valve M-X47 and the inlet of the stop valve J-X58; the outlet of the first deoxidation tower 44 is simultaneously connected to the inlet of the stop valve M-Y46 and the inlet of the stop valve J-Y48; the outlet of the stop valve M-X47 and the outlet of the stop valve M-Y46 are commonly connected to the inlet of the stop valve M49. The outlet of the stop valve M49 is connected to the hot end inlet of the heat exchanger B59 and the hot end inlet 55 of the heat exchanger A18 at the same time. The hot end outlet of the heat exchanger B59 is connected to the hot end outlet 54 of the heat exchanger A18, and the gas at the hot end outlet 56 of the heat exchanger A18 is dehydrogenated; the gas at the hot end outlet 54 of the heat exchanger A18 converges with the gas at the hot end outlet of the heat exchanger B59 to remove the hydrogen, and the inlet of the stop valve L-X41 and the inlet of the stop valve L-Y40 are connected to the cold end outlet of the heat exchanger B59. The cold end inlet of the heat exchanger B59 is connected to the outlet of the stop valve O39, and the inlet of the stop valve O39 is connected to the outlet of the nitrogen buffer tank 38.The inlet of nitrogen buffer tank 38 is connected to the outlet of stop valve 37, and the inlet of stop valve 37 is connected to the air separation nitrogen product extraction port. The outlet of crude neon-helium dehydrogenation device dehydrogenates the crude neon-helium to remove the hydrogen, and removes the nitrogen component in the crude neon-helium. The dehydrogenated crude neon-helium at the outlet of the crude neon-helium dehydrogenation device enters the dehydrogenation device through stop valve P20, and the outlet of stop valve P20 is connected to the inlet of the primary denitrification membrane 21, and the outlet of the primary denitrification membrane 21 is connected to the inlet of the stop valve Q22, and the outlet of the stop valve Q22 is simultaneously connected to the inlet of the crude neon-helium booster pump 23 and the inlet of the stop valve R25. The outlet of the crude neon-helium booster pump 23 is connected to the inlet of the secondary denitrification membrane 24. The outlet of the permeate side of the secondary denitrification membrane 24 and the outlet of the stop valve R25 are simultaneously connected to the hot end inlet of the heat exchanger C28, and the hot end outlet of the heat exchanger C28 is connected to the inlet of the stop valve S29, and the outlet of the stop valve S29 is simultaneously connected to the inlet of the stop valve T-X31 and the inlet of the stop valve T-Y30. The outlet of the stop valve T-X31 is simultaneously connected to the inlet of the stop valve U-X33 and the inlet of the second TSA tower 63; the outlet of the stop valve T-Y30 is simultaneously connected to the inlet of the stop valve U-Y32 and the inlet of the first TSA tower 36. The outlets of the stop valve U-X33 and the stop valve U-Y32 are jointly connected to the suction port of the vacuum pump 37, and the exhaust port of the vacuum pump 37 is connected to the atmosphere.

[0022] The outlet of the second TSA tower 63 is connected to the inlet of the stop valve X-X34, and the outlet of the first TSA tower 36 is connected to the inlet of the stop valve X-Y35. The outlet of the stop valve X-X34 and the outlet of the stop valve X-Y35 are connected to the cold end inlet 61 of the heat exchanger C28, and the cold end outlet 60 of the heat exchanger C28 is connected to the neon-helium separation system. The cold end flow path 64→65 of the heat exchanger C28 provides the required cooling capacity for TSA adsorption through the freeze dryer 62.

[0023] The non-permeation side outlet of the primary denitrification membrane 21 is connected to the inlet of the stop valve V-X27 and the outlet of the stop valve V-Y26; the non-permeation side outlet of the secondary denitrification membrane 24 is connected to the outlet of the stop valve V-Y26. The non-permeation gas of the primary denitrification membrane 21 and the non-permeation gas of the secondary denitrification membrane 24 at the outlet of the stop valve V-X27 are refluxed to the crude neon and helium product outlet of the air separation.

[0024] The present invention achieves deep coupling of the crude neon-helium deep dehydrogenation process and the nitrogen purification process by coupling the crude neon-helium dehydrogenation tower regeneration process with the nitrogen purification process, thereby increasing the production capacity of neon-helium and ultra-high purity nitrogen and reducing the production cost. The deoxygenation tower regeneration gas in the nitrogen deoxygenation purification device uses part of the raw gas in the crude neon-helium dehydrogenation device, eliminating the regeneration cost of the deoxygenation tower in the nitrogen deoxygenation purification device and increasing the dehydrogenation crude neon-helium dehydrogenation capacity in the crude neon-helium dehydrogenation device; B. The dehydrogenation tower regeneration gas in the crude neon-helium dehydrogenation device uses part of the raw gas in the nitrogen deoxygenation purification device. A certain amount of oxygen needs to be added to part of the raw gas in the deoxygenation purification device. The oxygen volume concentration of the dehydrogenation tower regeneration gas in the crude neon-helium dehydrogenation device is usually controlled to be 3% to 10%, eliminating the regeneration cost of the dehydrogenation tower in the crude neon-helium dehydrogenation device and increasing the ultra-pure nitrogen capacity in the nitrogen deoxygenation purification device.

[0025] Specific usage:

[0026] Before starting the device of the present invention, the entire system pipeline needs to be purged to remove air and solid particle impurities in the system pipeline. The purge gas before the system is started uses high-purity nitrogen with a pressure of ~500KPaG and V / V≥99.999%. The entire device pipeline is purged for 6 to 8 hours to ensure that the high-purity nitrogen completely replaces the air in the system pipeline.

[0027] After the device is purged, the equipment starts to start. Due to the difference in the operating temperatures of the first deoxidation tower 44 and the second deoxidation tower 45 in the nitrogen deoxidation purification device and the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device, the nitrogen deoxidation purification device and the crude neon-helium dehydrogenation device are in logical parallel connection. The first deoxidation tower 44 and the second deoxidation tower 45 in the nitrogen deoxidation purification device can operate at room temperature, and the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device can operate at 180°C to 220°C.

[0028] The working temperature range of the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device is 180°C to 220°C. Therefore, the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device need to be preheated before the system. The preheating method of the first dehydrogenation tower 9 and the second dehydrogenation tower 10 can be but is not limited to heating with electric heating rods built into the tower, heating with heated nitrogen, etc.

[0029] The volume concentration of the impurity oxygen component in the raw nitrogen of the nitrogen deoxygenation purification device is generally not more than 100ppm, and the volume concentration of the impurity hydrogen component in the raw gas of the crude neon-helium dehydrogenation device fluctuates dynamically between 1.89% and 3%. Therefore, under common working conditions, the adsorption period of the first deoxygenation tower 44 and the second deoxygenation tower 45 in the nitrogen deoxygenation purification device is longer than the dehydrogenation period of the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device. During the startup of the device of the present invention, the first deoxygenation tower 44 and the second deoxygenation tower 45 of the nitrogen deoxygenation purification device are allowed to work before the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device, and the time difference is not limited to 2 to 3 hours.

[0030] Specifically, after the system pipeline is purged and the air is replaced, the stop valve 37, stop valve O39 and stop valve L-X41 are slowly opened, and the raw material crude neon and helium gas enters the second deoxidation tower 45 through the nitrogen buffer tank 38 and the heat exchanger B59, and the oxygen in the raw nitrogen is adsorbed and removed. The volume concentration of the oxygen component at the outlet of the second deoxidation tower 45 is ≤0.1ppm. It should be noted that there is no rigid rule to start the second deoxidation tower 45 or the deoxidation tower 45 first when the nitrogen deoxidation purification device is started.

[0031] Slowly open the stop valve J-X58 and start the nitrogen booster 50 at the same time. The purified nitrogen V / V≥99.9999% at the outlet of the second deoxidation tower 45 is pressurized to 8ataA by the nitrogen booster 50 and then sent to the use place. After the nitrogen deoxidation and purification device has worked for 1.5 to 2 hours, start the crude neon helium dehydrogenation device.

[0032] Before the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon helium dehydrogenation device are put into use, they need to be preheated for 0.5 to 1h to raise the temperature of the dehydrogenant in the first dehydrogenation tower 9 and the second dehydrogenation tower 10 to 200℃±5℃ and stabilize for 10min to 15min. Then the crude neon helium dehydrogenation device starts to operate. Slowly open the stop valve A2, the crude neon helium booster 1 pressurizes the crude neon helium raw material to 150ata and stores it in the crude neon helium storage tank 3. When the temperature of the dehydrogenant in the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the denitrification system crude neon helium dehydrogenation device is stable at 200℃±5℃, slowly open the stop valve C-X5, the crude neon helium enters the first dehydrogenation tower 9, and starts to remove the impurity hydrogen component in the crude neon helium. It is pointed out here that when the crude neon helium dehydrogenation device is put into use, the first dehydrogenation tower 9 or the second dehydrogenation tower 10 is used first, and there is no rigid regulation.

[0033] Slowly open the stop valve H-X11, and the dehydrogenated crude neon and helium gas at the outlet of the first dehydrogenation tower 9 enters the nitrogen removal system through the hot end passage 57→56 of the heat exchanger A18.

[0034] For the nitrogen deoxidation purification device, when it is necessary to switch between the first deoxidation tower 44 and the second deoxidation tower 45, first, close the stop valve L-X41 and the stop valve J-X58, and at the same time, open the stop valve L-Y40 and the stop valve J-Y48. The nitrogen deoxidation is switched from the deoxidation tower 45 to the first deoxidation tower 44. Thereafter, the second deoxidation tower 45 switches to the passivation process, i.e., the deoxidation of the deoxidizer in the deoxidation tower 45.

[0035] For deoxidation of the deoxidizer in the deoxidizer 45, first open the stop valve K-X42 and the stop valve M-X47, and then open the stop valve E-X15 or the pressure reducing valve E-Y16. The crude neon helium gas in the crude neon helium gas storage tank 3 is used as the deoxidizer passivation regeneration gas in the deoxidizer 45, and enters the deoxidizer 45, and the hydrogen in the crude neon helium gas removes the oxygen adsorbed by the deoxidizer. It is explained here that when the crude neon helium gas of the denitrification system enters the deoxidizer 45, the tower temperature of the deoxidizer 45 will rise rapidly. At this time, it is necessary to control the flow rate of the crude neon helium gas entering the deoxidizer 45, and stabilize the tower temperature of the deoxidizer 45 at 300℃~330℃. The crude neon helium gas dehydrogenates in the deoxidizer 45 and removes the oxygen adsorbed by the deoxidizer, completing the passivation of the deoxidizer. The dehydrogenated crude neon helium gas at the outlet of the deoxidizer 45 passes through the hot end passage 55→54 of the heat exchanger A18, or the hot end passage of the heat exchanger B59, to remove the nitrogen system.

[0036] The crude dehydrogenated neon-helium gas at the outlet of the deoxygenation tower 45 passes through the hot end passage 55→54 of the heat exchanger A18, or the hot end passage of the heat exchanger B59, depending on the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10. If the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10 is lower than 180°C, the crude dehydrogenated neon-helium gas at the outlet of the deoxygenation tower 45 passes through the hot end passage 55→54 of the heat exchanger A18 to preheat the crude neon-helium gas entering the dehydrogenation tower; if the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10 is higher than 200°C, the crude dehydrogenated neon-helium gas at the outlet of the deoxygenation tower 45 passes through the hot end passage of the heat exchanger B59 to increase the nitrogen temperature, which is beneficial to the deoxygenation of the deoxygenation tower. When the nitrogen deoxygenation of the deoxygenation system is switched from the first deoxygenation tower 44 to the second deoxygenation tower 45, the stop valve L-Y40 and the stop valve J-Y48 are closed, and at the same time, the stop valve L-X41 and the stop valve J-X58 are opened. The first deoxidation tower 44 deoxidizes the deoxidizer. First, the stop valve K-Y43 and the stop valve M-Y46 need to be opened, and then the stop valve E-X15 or the pressure reducing valve E-Y16 is opened. The crude neon helium gas in the crude neon helium gas storage tank 3 is used as the deoxidizer passivation regeneration gas of the first deoxidation tower 44, and enters the first deoxidation tower 44. The hydrogen in the crude neon helium gas removes the oxygen adsorbed by the deoxidizer. It is explained here that when the crude neon helium gas of the denitrification system enters the first deoxidation tower 44, the tower temperature of the first deoxidation tower 44 will rise rapidly. At this time, it is necessary to control the flow rate of the crude neon helium gas entering the first deoxidation tower 44, and stabilize the tower temperature of the first deoxidation tower 44 at 300℃~330℃. The crude neon helium gas dehydrogenates in the first deoxidation tower 44 and removes the oxygen adsorbed by the deoxidizer, completing the passivation of the deoxidizer. The dehydrogenated crude neon helium gas at the outlet of the second deoxidation tower 45 passes through the hot end passage 55→54 of the heat exchanger A18, or the hot end passage of the heat exchanger B59, to remove the nitrogen system.

[0037] The first deoxidation tower 44 and the second deoxidation tower 45 passivate the regenerated gas crude neon-helium dehydrogenation device raw material crude neon-helium gas flow path electric heater 19 is used to preheat the crude neon-helium raw material crude neon-helium dehydrogenation device raw material crude neon-helium gas to ensure that the temperature of the crude neon-helium raw material crude neon-helium gas entering the first deoxidation tower 44 and the second deoxidation tower 45 is higher than 180°C.

[0038] For the crude dehydrogenation device, the raw crude dehydrogenation helium in the crude dehydrogenation helium storage tank 3 can choose to enter the first dehydrogenation tower 9 or the second dehydrogenation tower 10 through the cold end of the heat exchanger A18, or directly enter the first dehydrogenation tower 9 or the second dehydrogenation tower 10 without passing through the cold end of the heat exchanger A18. Whether to pass through the cold end of the heat exchanger A18 depends on the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10: A. If the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10 of the denitrification system is higher than 250°C, the raw crude dehydrogenation helium in the crude dehydrogenation helium storage tank 3 will directly enter the first dehydrogenation tower 9 or the second dehydrogenation tower 10 without passing through the cold end of the heat exchanger A18; B. If the tower temperature of the first dehydrogenation tower 9 or the second dehydrogenation tower 10 of the denitrification system is lower than 200°C, the raw crude dehydrogenation helium in the crude dehydrogenation helium storage tank 3 will enter the first dehydrogenation tower 9 or the second dehydrogenation tower 10 through the cold end of the heat exchanger A18.

[0039] For the switching operation between the first dehydrogenation tower 9 and the second dehydrogenation tower 10 in the crude neon-helium dehydrogenation device: When the first dehydrogenation tower 9 of the denitrification system is regenerated and the second dehydrogenation tower 10 is working: close the stop valve C-X5, and open the stop valve C-Y6 at the same time, the raw material crude neon-helium gas in the crude neon-helium gas storage tank 3 enters the second dehydrogenation tower 10 to remove the hydrogen component; open the stop valve H-Y12, and the dehydrogenated crude neon-helium gas at the outlet of the second dehydrogenation tower 10 enters the denitrification system through the hot end passage 57→56 of the heat exchanger A18. At the same time, open the stop valve F-X7, the stop valve I-X13, and the stop valve G51, start the blower 52, the raw nitrogen of the nitrogen deoxygenation purification device is mixed with air, and enters the first dehydrogenation tower 9 to complete the oxygen absorption of the dehydrogenation agent in the first dehydrogenation tower 9. After the oxygen absorption of the dehydrogenation agent in the first dehydrogenation tower 9 is completed, close the stop valve F-X7, the stop valve I-X13, and the stop valve G51. The volume concentration of nitrogen at the outlet of the first dehydrogenation tower 9 is ≥99.9999%, which is merged with the nitrogen at the outlets of the first deoxygenation tower 44 and the second deoxygenation tower 45; when the second dehydrogenation tower 10 of the denitrification system is regenerated and the first dehydrogenation tower 9 is working: close the stop valve C-Y6, and open the stop valve C-X5 at the same time, the raw material crude neon helium in the crude neon helium storage tank 3 enters the first dehydrogenation tower 9 to remove the hydrogen component; open the stop valve H-X11, and the dehydrogenated crude neon helium at the outlet of the first dehydrogenation tower 9 enters the denitrification system through the hot end passage 57→56 of the heat exchanger A18. At the same time, open the stop valve F-Y8, stop valve I-Y12, and stop valve G51, the raw nitrogen of the nitrogen deoxygenation purification device is mixed with air and enters the second dehydrogenation tower 10, and the dehydrogenation agent in the second dehydrogenation tower 10 is completed. After the dehydrogenation agent in the second dehydrogenation tower 10 is completed, close the stop valve F-Y8, stop valve I-Y12, and stop valve G51. The nitrogen volume concentration at the outlet of the second dehydrogenation tower 10 is ≥ 99.9999% and merges with the nitrogen at the outlets of the first deoxidation tower 44 and the second deoxidation tower 45. It is noted that after the raw nitrogen is mixed with air, the oxygen volume concentration in the mixed gas is generally controlled at 5%.

[0040] The crude neon-helium gas after dehydrogenation includes the neon-helium gas at the outlet of the first dehydrogenation tower 9 or the second dehydrogenation tower 10, and the regeneration gas nitrogen removal system after regeneration of the first deoxidation tower 44 and the second deoxidation tower 45. The stop valve P20 and the stop valve Q are opened, and the crude neon-helium gas booster pump 23 is turned on. The crude neon-helium gas after dehydrogenation has a hydrogen volume concentration of ≤1ppm and first enters the primary denitrification membrane 21, and the crude neon-helium gas with some nitrogen removed is obtained on the permeation side; the gas at the outlet of the primary denitrification membrane 21 enters the secondary denitrification membrane 24 through the crude neon-helium gas booster 23, and the crude neon-helium gas with a nitrogen volume concentration of not more than 0.3% is obtained on the permeation side of the secondary denitrification membrane 24.

[0041] Open the stop valve S29, and the crude neon-helium gas with a nitrogen volume concentration of no more than 0.3% obtained on the permeate side of the denitrification secondary membrane 24 enters the first TSA tower 36 and the second TSA tower 63 through the hot end flow path of the heat exchanger C28, and deeply adsorbs the nitrogen in the crude neon-helium gas. The second TSA tower 63 and the first TSA tower 36 are used in a switchable manner, one for adsorption and the other for regeneration. In the present example, the second TSA tower 63 is used first: the connecting stop valve T-X31 and the stop valve X-X34 are opened, and the crude neon-helium gas on the permeate side of the denitrification secondary membrane 24 enters the second TSA tower 63 through the hot end flow path of the heat exchanger C28, and deeply adsorbs the nitrogen in the crude neon-helium gas; the nitrogen at the outlet of the second TSA tower 63 passes through the cold end flow path 61→60 of the heat exchanger C28 and then reheats to remove the neon-helium gas. Separation system; regeneration using the first TSA tower 36 and the second TSA tower 63: close the stop valve T-X31 and the stop valve X-X34, and open the stop valve T-Y30 and the stop valve X-Y35 at the same time, the crude neon and helium gas on the permeation side of the nitrogen removal secondary membrane 24 enters the first TSA tower 36 through the hot end flow path of the heat exchanger C28, and deeply adsorbs the nitrogen in the crude neon and helium gas; the nitrogen gas at the outlet of the first TSA tower 36 is reheated through the cold end flow path 61→60 of the heat exchanger C28 and then removed from the neon and helium separation system. Open the stop valve U-X33, start the vacuum pump 37, and at the same time, reheat the second TSA tower 63 to -30℃±3℃, so that the nitrogen adsorbed by the second TSA tower 63 is analyzed and safely discharged to the atmosphere through the vacuum pump 37. After the second TSA tower 63 is decomposed and regenerated, the stop valve U-X33 is closed; the second TSA tower 63 and the first TSA tower 36 are used for regeneration: the stop valve T-Y30 and the stop valve X-Y35 are closed, and the stop valve T-X31 and the stop valve X-X34 are opened at the same time, and the crude neon-helium gas on the permeation side of the nitrogen removal secondary membrane 24 enters the second TSA tower 63 through the hot end flow path of the heat exchanger C28, and deeply adsorbs the nitrogen in the crude neon-helium gas; the nitrogen gas at the outlet of the second TSA tower 63 is reheated through the cold end flow path 61→60 of the heat exchanger C28 to remove the neon-helium separation system. The stop valve U-Y32 is opened, the vacuum pump 37 is started, and the first TSA tower 36 is reheated to -30℃±3℃ at the same time, so that the adsorbed nitrogen gas in the first TSA tower 36 is decomposed and safely discharged to the atmosphere through the vacuum pump 37. After the decomposition and regeneration of the first TSA tower 36 is completed, the stop valve U-Y32 is closed.

[0042] Freeze dryer R22 / -102℃, refrigerant is not limited to R22 to provide cold source for TSA and supplement the cold loss during operation; Whether the secondary denitrification membrane 24 is used or not depends on the actual volume concentration of impurity nitrogen in the crude neon-helium gas. When the volume concentration of nitrogen on the permeate side of the primary denitrification membrane 21 of the denitrification system is not more than 1.3%, the secondary denitrification membrane 24 may not be activated: open the stop valve R25, and the crude neon-helium gas on the permeate side of the primary denitrification membrane 21 directly enters the first TSA tower 36 and the second TSA tower 63 for deep denitrification.

[0043] Open the stop valve V-X27 and the stop valve V-Y26, and the gas on the non-permeate side of the primary nitrogen removal membrane 21 and the gas on the non-permeate side of the secondary nitrogen removal membrane 24 will converge and return to the outlet of the crude neon and helium gas of the air separation.

[0044] The present invention discloses a device and a method for using crude neon-helium gas for dehydrogenation, denitrification and nitrogen purification. By coupling the crude neon-helium gas deep dehydrogenation process with the nitrogen purification tower regeneration process, and coupling the crude neon-helium gas dehydrogenation tower regeneration process with nitrogen purification, the deep coupling of the crude neon-helium gas deep dehydrogenation process and the nitrogen purification process is achieved, thereby increasing the production capacity of neon-helium and ultra-high purity nitrogen and reducing the production cost. The deoxygenation tower regeneration gas in the nitrogen deoxygenation purification device uses part of the raw gas in the crude neon-helium gas dehydrogenation device, thereby eliminating the deoxygenation tower regeneration cost in the nitrogen deoxygenation purification device and increasing the dehydrogenation crude neon-helium gas production capacity in the crude neon-helium gas dehydrogenation device; B. The dehydrogenation tower regeneration gas in the crude neon-helium gas dehydrogenation device uses part of the raw gas in the nitrogen deoxygenation purification device. A certain amount of oxygen needs to be added to part of the raw gas in the deoxygenation purification device. The oxygen volume concentration of the dehydrogenation tower regeneration gas in the crude neon-helium gas dehydrogenation device is usually controlled to be 3% to 10%, thereby eliminating the dehydrogenation tower regeneration cost in the crude neon-helium gas dehydrogenation device and increasing the ultra-pure nitrogen production capacity in the nitrogen deoxygenation purification device.

Claims

1. A device for removing hydrogen and nitrogen from crude neon and helium gas and purifying nitrogen, the device comprising a nitrogen deoxygenation purification system (I), a crude neon and helium gas dehydrogenation system (II), and a nitrogen removal system (III), characterized in that: The nitrogen deoxygenation purification system (I) and the crude neon-helium dehydrogenation system (II) are both connected to the air separation unit AUS (53), and the crude neon-helium dehydrogenation system (II) is coupled to the nitrogen deoxygenation purification system (I) and the denitrification system (III), respectively. The crude neon-helium dehydrogenation system (II) is composed of a crude neon-helium booster (1), a crude neon-helium storage tank (3), a heat exchanger A (18), a dehydrogenation tower, and an electric heater (19), which are connected to each other through pipelines. A valve is provided on the pipeline, and the flow direction is controlled by opening and closing the valve. The nitrogen deoxygenation purification system (I) is composed of a deoxygenation tower, a nitrogen booster (50), a heat exchanger B (59), and a nitrogen buffer tank (38). The denitrification system (III) is composed of a denitrification primary membrane (21), a denitrification secondary membrane (24), a crude neon-helium booster pump (23), a heat exchanger C (28), and a TSA tower. The crude neon-helium product outlet of the air separation unit AUS (53) is connected to a crude neon-helium booster (1), and the crude neon-helium booster (1) is connected to a crude neon-helium storage tank (3). A dehydrogenation tower, a heat exchanger A (18), and an electric heater (19) are connected to the rear of the crude neon-helium storage tank (3), respectively. The electric heater (19) is connected to the deoxygenation tower of the nitrogen deoxygenation purification system (I). The crude neon-helium outlet of the dehydrogenation tower in the crude neon-helium dehydrogenation system (II) is connected to the heat exchanger A (18), and the regeneration gas outlet of the dehydrogenation tower is connected to the nitrogen booster (50) in the nitrogen deoxygenation purification system (I). The pressurized nitrogen flows to an external collection tank. The heat exchanger A (18) is connected to the denitrification primary membrane (21) of the denitrification system (III) and the crude neon-helium booster pump (23). , a denitrification secondary membrane (24), a heat exchanger C (28), and a TSA tower, wherein the rear of the TSA tower is connected to the heat exchanger C (28), and the gas after passing through the TSA tower is again passed through the heat exchanger C (28) for heat exchange and then flows to an external neon-helium separation system. The other path of the heat exchanger C (28) is connected to a freeze dryer (62), and the outlet raw gas of the denitrification secondary membrane (24) is cooled to provide the required cooling capacity for the TSA tower to adsorb impurities; the corresponding valve is opened, and the crude neon-helium gas in the crude neon-helium gas storage tank (3) is used as the deoxidizer purification regeneration gas of the deoxidizer tower, and enters the deoxidizer tower, and the deoxidizer adsorbs oxygen through the hydrogen in the crude neon-helium gas. The regeneration gas of the dehydrogenation tower in the crude neon-helium gas dehydrogenation device uses the raw gas in the nitrogen deoxidation purification device and 3% to 10% oxygen to regenerate the dehydrogenation tower in the crude neon-helium gas dehydrogenation device; Two paths are arranged behind the deoxygenation tower of the nitrogen deoxygenation purification system (I), one of which is connected to the heat exchanger A (18) and then flows into the denitrification system (III), and the other is connected to the heat exchanger B (59), and then connected to the one in the heat exchanger A (18) and connected to the denitrification system (III), the heat exchanger B (59) is also connected to the nitrogen buffer tank (38), the nitrogen buffer tank (38) is connected to the air separation nitrogen product extraction port, and the nitrogen buffer tank (38) is also provided with a blower (52); the corresponding valve is opened, the blower (52) is turned on, the raw nitrogen of the nitrogen deoxygenation purification device is mixed with the air, and enters the dehydrogenation tower, and the dehydrogenation agent in the dehydrogenation tower absorbs oxygen. After the dehydrogenation agent in the dehydrogenation tower absorbs oxygen, the corresponding valve is closed, and the nitrogen volume concentration at the outlet of the dehydrogenation tower (9) is ≥99.9999% and merges with the nitrogen at the outlet of the deoxygenation tower.

2. The device for removing hydrogen, nitrogen and nitrogen from crude neon and helium gas according to claim 1, characterized in that: The dehydrogenation tower, TSA tower and deoxygenation tower are each provided in pairs, wherein the dehydrogenation tower is composed of a first dehydrogenation tower (9) and a second dehydrogenation tower (10), the TSA tower is composed of a first TSA tower (36) and a second TSA tower (63), and the deoxygenation tower is composed of a first deoxygenation tower (44) and a second deoxygenation tower (45). The two dehydrogenation towers or the two TSA towers or the two deoxygenation towers are connected by pipelines, and valves are installed on the pipelines to control the flow direction.

3. The method for using the device for removing hydrogen, nitrogen and nitrogen from crude neon and helium gas according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: 1) Purging of the equipment and preheating of the tower body through the first dehydrogenation tower (9) and the second dehydrogenation tower (10) / precooling through the first TSA tower (36) and the second TSA tower (63); 2) The raw material crude neon and helium gas enters the nitrogen deoxygenation purification system (I) to adsorb and remove oxygen from the raw material nitrogen gas; 3) starting the crude neon-helium gas dehydrogenation device to remove hydrogen from the crude neon-helium gas from which oxygen has been removed in step 2); 4) Finally, the crude neon-helium gas, from which oxygen and hydrogen have been removed, enters the nitrogen removal system (III) to remove nitrogen.

4. The method according to claim 3, characterized in that: The specific method for removing oxygen from the raw nitrogen by adsorption in step 2) is: The raw material crude neon-helium gas enters the second deoxidation tower (45) through the nitrogen buffer tank (38) and the heat exchanger B (59), where oxygen in the raw material nitrogen is removed by adsorption. The volume concentration of the oxygen component at the outlet of the second deoxidation tower (45) is ≤0.1 ppm. The nitrogen booster (50) is started, and the V / V of the purified nitrogen at the outlet of the second deoxidation tower (45) is ≥99.9999%. The nitrogen booster (50) is pressurized and sent to the place of use. After the nitrogen deoxidation and purification work for 1.5 to 2 hours, the crude neon-helium gas dehydrogenation device is started.

5. The method according to claim 3, characterized in that: The specific method of starting the crude neon-helium gas dehydrogenation device in step 3) is: Before activation, it is necessary to preheat for 0.5 to 1 hour to raise the temperature of the dehydrogenating agent in the first dehydrogenation tower (9) and the second dehydrogenation tower (10) to 200°C ± 5°C and stabilize it for 10 to 15 minutes. Then, the crude neon-helium dehydrogenation device starts to operate. The crude neon-helium booster (1) boosts the crude neon-helium raw material to 150ata and stores it in the crude neon-helium storage tank (3). When the temperature of the dehydrogenating agent in the dehydrogenation tower in the crude neon-helium dehydrogenation device stabilizes at 200°C ± 5°C, the crude neon-helium enters the first dehydrogenation tower (9) and starts to remove the impurity hydrogen component in the crude neon-helium. The dehydrogenated crude neon-helium at the outlet of the first dehydrogenation tower (9) passes through the heat exchanger A (18) and then enters the denitrification system (III). The crude neon-helium in the crude neon-helium storage tank (3) is used as The regenerated gas purified by the deoxidizer of the second deoxidizer (45) enters the second deoxidizer (45) and is removed by hydrogen in the crude neon-helium gas. When the crude neon-helium gas from the denitrification system enters the second deoxidizer (45), the temperature of the second deoxidizer (45) rises rapidly. At this time, it is necessary to control the flow rate of the crude neon-helium gas entering the second deoxidizer (45) and stabilize the temperature of the second deoxidizer (45) at 300°C to 330°C. The crude neon-helium gas is dehydrogenated in the second deoxidizer (45) and the oxygen adsorbed by the deoxidizer is removed at the same time, thereby completing the purification of the deoxidizer. The dehydrogenated crude neon-helium gas at the outlet of the second deoxidizer (45) passes through the hot end passage of heat exchanger A (18) or the hot end passage of heat exchanger B (59) to remove the nitrogen in the nitrogen removal system (III).

6. The method according to claim 3, characterized in that: The method for removing nitrogen in the nitrogen removal system (III) in step 4) is as follows: the crude neon-helium gas after deoxygenation and dehydrogenation, with a hydrogen volume concentration of ≤1 ppm and an oxygen volume concentration of ≤0.1 ppm, first enters the primary nitrogen removal membrane (21), and obtains the crude neon-helium gas with a portion of nitrogen removed on the permeate side; the outlet gas of the primary nitrogen removal membrane (21) enters the secondary nitrogen removal membrane (24) through the crude neon-helium gas booster pump (23), and obtains the crude neon-helium gas with a nitrogen volume concentration of not more than 0.3% on the permeate side of the secondary nitrogen removal membrane (24); the crude neon-helium gas with a nitrogen volume concentration of not more than 0.3% on the permeate side of the secondary nitrogen removal membrane (24) enters the first TSA tower (36) and the second TSA tower (63) through the hot end flow path of the heat exchanger C (28), and deeply adsorbs nitrogen in the crude neon-helium gas; the outlet nitrogen of the first TSA tower (36) and the second TSA tower (63) is reheated through the cold end flow path of the heat exchanger C (28) and then removed from the neon-helium separation system.

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