Device system and method for purifying oxygen, nitrogen and crude neon and helium

Abstract

The invention relates to a purification device system and method for oxygen, nitrogen and crude neon and helium, based on a non-low-temperature gas purification technology, hydrogen removal of crude neon and helium is coupled with regeneration of a nitrogen deoxidizing adsorbent, purification of nitrogen is coupled with a regeneration process of removing carbon dioxide and water from oxygen, and linkage purification and impurity removal of oxygen, nitrogen and crude neon and helium can be carried out. Therefore, efficient purification of nitrogen, oxygen and crude neon and helium is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of gas separation, and in particular to a purification device system and method for oxygen, nitrogen and crude neon and helium gases. Background Art

[0002] At present, air separation nitrogen purification, air separation oxygen purification, and air separation crude neon helium dehydrogenation and denitrification are mainly achieved by deep cryogenic distillation means, especially the air separation crude neon helium dehydrogenation and denitrification process. Due to the extremely low boiling points of neon and helium, the pressure required for the cryogenic distillation process is extremely high, which further makes the crude neon helium deep purification and purification equipment bulky, and the equipment insulation and heat insulation requirements are extremely high. As for air separation nitrogen purification and air separation oxygen purification processes, CN112229143A discloses a device for producing oxygen and nitrogen by separating air through cryogenic distillation, which includes a raw air compressor, a precooling system, a purification system, a medium-pressure air booster, a low-pressure air booster, an air separation cold box, and an oxygen booster connected in sequence. The purification cost of this device is relatively high, and its application in industrial production is limited. As for electronic grade ultra-high purity nitrogen whose volume purity needs to be higher than 99.9999%, it is usually purified from air separation high-purity nitrogen, that is, nitrogen with a volume purity ≥99.999% through a purifier. However, there is also the problem of expensive purifiers, and their working conditions are high temperature. In addition, the getter needs to be replaced regularly, and the cost of use is relatively high.

[0003] 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 fast response speed, room temperature operation, compact equipment structure, high separation coefficient between different gas components, and is more suitable for the separation of precision systems than cryogenic distillation.

[0004] CN117566701A discloses a device for purifying crude neon and helium by non-cryogenic method, which includes a buffer tank, a catalytic device, a normal temperature adsorption device, a membrane separation neon and helium enrichment device, and a deep low temperature quantum adsorption device. The inlet of the buffer tank is connected to the outlet of the crude neon and helium gas of air separation, the outlet of the buffer tank is connected to a relay compressor, the rear of the relay compressor is connected to a catalytic device, an oxygenation catalytic device and a hydrogenation catalytic device are respectively installed in the catalytic device, and the outlet of the catalytic device is connected to the crude neon and helium gas and the catalytic device, the crude neon and helium gas and the catalytic device are connected to the heat exchanger after heat exchange and heat recovery, and then connected to a cooler for cooling, the outlet of the cooler is connected to the relay compressor, and after pressurization, it enters the normal temperature adsorption device, and the rear of the normal temperature adsorption device is connected to a membrane separation neon and helium enrichment device and a deep low temperature quantum adsorption device in sequence. However, the device is only applicable to purifying crude neon and helium gas, and cannot realize the coordinated purification and impurity removal of air separation nitrogen, air separation oxygen and crude neon and helium gas of air separation, and has certain application limitations.

[0005] Therefore, in view of the shortcomings of the prior art, there is an urgent need to provide a device system that can achieve coordinated and efficient purification of air-separated nitrogen, air-separated oxygen, and air-separated crude neon and helium. Summary of the invention

[0006] The object of the present invention is to provide a purification device system and method for oxygen, nitrogen and crude neon-helium gases, wherein the nitrogen, oxygen and crude neon-helium gases produced by an air separation device are linked and purified and impurities removed by non-cryogenic gas separation technology, thereby obtaining high-purity nitrogen, high-purity oxygen and a neon-helium mixed gas.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a purification device system for oxygen, nitrogen and crude neon helium, the purification device system comprising a heat exchanger, the heat exchanger being provided with a nitrogen inlet, a nitrogen outlet, an oxygen inlet, an oxygen outlet, a crude neon helium inlet, a crude neon helium outlet, a dehydrogenation neon helium inlet and a dehydrogenation neon helium outlet; the nitrogen outlet and the crude neon helium outlet are both connected to a deoxygenation tower, the deoxygenation tower discharges high-purity nitrogen and dehydrogenation neon helium, the dehydrogenation neon helium enters the heat exchanger from the dehydrogenation neon helium inlet and is discharged from the dehydrogenation neon helium outlet, and then enters a permeation membrane assembly and an impurity adsorption tower in sequence.

[0009] The oxygen outlet is connected to the first supercharger, the hydrocarbon removal device and the heat balancer in sequence. The oxygen discharged from the heat balancer flows through the heat exchanger and enters the carbon dioxide and water adsorption tower and the nitride removal device in sequence. The discharged oxygen flows through the heat exchanger again and enters the oxygen purification tower. The high-purity nitrogen part discharged from the deoxygenation tower enters the carbon dioxide and water adsorption tower for purging, takes out carbon dioxide and water, and returns to the pipeline where the nitrogen outlet is located after carbon dioxide and water are removed by the nitrogen drying device.

[0010] The purification device system also includes an ice dryer, which is used to provide a cold source for the impurity adsorption tower and the oxygen purification tower.

[0011] The oxygen, nitrogen and crude neon-helium purification device system provided by the present invention can purify and remove impurities in nitrogen, oxygen and crude neon-helium produced by an air separation device. Specifically, the air separation nitrogen is reheated through a heat exchanger and then deoxygenated in a deoxygenation tower to obtain high-purity nitrogen; the air separation oxygen is reheated and pressurized by a heat exchanger and a first supercharger, and then hydrocarbons are removed by a hydrocarbon removal device, and then CO2 and H2O are adsorbed by a carbon dioxide and water adsorption tower, and then NO is removed in a nitride removal device. xIt is reduced to N2 and O2, and finally high-purity oxygen is obtained through an oxygen purification tower; the dehydrogenation of crude neon-helium gas from air separation is linked with the purification process of nitrogen from air separation. When the deoxygenation tower is saturated with oxygen, heated crude neon-helium gas is introduced to achieve nitrogen purification and regeneration while removing hydrogen from the crude neon-helium gas; after hydrogen removal, the crude neon-helium gas is passed through a permeable membrane assembly and an impurity adsorption tower to obtain a neon-helium mixed gas; air separation nitrogen purification and air separation oxygen purification are linked, that is, the purified nitrogen part is used as the regeneration gas source for oxygen purification, and the discharged nitrogen merges with the air separation nitrogen.

[0012] Preferably, the crude neon-helium gas outlet is connected to the deoxidation tower via an electric heater.

[0013] The deoxygenation tower includes a first deoxygenation tower and a second deoxygenation tower which are operated and regenerated alternately.

[0014] The "alternating operation and regeneration" means that when the first deoxidation tower is working, the second deoxidation tower is regenerated, and vice versa, when the second deoxidation tower is working, the first deoxidation tower is regenerated.

[0015] Preferably, the permeable membrane assembly comprises a first permeable membrane, a second permeable membrane and a third permeable membrane connected in sequence along the flow direction of the dehydrogenation, neon and helium gas, and the first permeable membrane, the second permeable membrane and the third permeable membrane are independently provided with a permeation side and a non-permeation side.

[0016] The non-permeable side of the first permeable membrane is provided with a waste gas outlet.

[0017] The waste gas discharged from the non-permeation side of the second permeable membrane flows back to the first permeable membrane after passing through the first booster valve, and the pressure gas source of the first booster valve comes from the dehydrogenation neon helium gas inlet.

[0018] The waste gas discharged from the non-permeable side of the third permeable membrane flows through the second booster valve and then returns to the first permeable membrane. The pressure gas source of the second booster valve comes from the waste gas discharged from the non-permeable side of the second permeable membrane.

[0019] The exhaust gas outlet of the present invention is directly connected to the atmosphere or recycled and reused into the Ne enrichment system.

[0020] Preferably, the outlet of the impurity adsorption tower is connected to a neon-helium gas refining system.

[0021] The impurity adsorption tower includes a first impurity adsorption tower and a second impurity adsorption tower which are operated and regenerated alternately.

[0022] The waste gas analyzed by the regenerated impurity adsorption tower after reheating is safely discharged through the impurity adsorption tower exhaust pipeline.

[0023] Preferably, the carbon dioxide and water adsorption tower comprises a first adsorption tower and a second adsorption tower which are alternately operated and regenerated.

[0024] Part of the high-purity nitrogen discharged from the deoxygenation tower enters the high-purity nitrogen system, part enters the first permeable membrane, and part flows through the heat balancer and the second booster to enter the regenerated carbon dioxide and water adsorption tower.

[0025] Part of the high-purity nitrogen gas enters the first permeable membrane to increase the partial pressure of Ne+N2 in the crude neon-helium gas, thereby increasing the recovery rate of Ne+He of the first permeable membrane; part of it enters the regenerated carbon dioxide and water adsorption tower to purge the adsorbent in the carbon dioxide and water adsorption tower to analyze the carbon dioxide and water adsorbed by the adsorbent and take them away.

[0026] Preferably, the oxygen purification tower includes a first purification tower and a second purification tower which are alternately operated and regenerated.

[0027] The outlet of the oxygen purification tower is independently connected to a high-purity oxygen system and a vacuum pump.

[0028] The high-purity oxygen discharged from the oxygen purification tower can enter the high-purity oxygen system, or can enter the vacuum pump and then be directly emptied.

[0029] Preferably, the ice dryer is provided with a refrigerant outlet and a refrigerant inlet, the refrigerant outlet is independently connected to the cold supply chamber inlet of the impurity adsorption tower, the cold supply chamber inlet of the oxygen purification tower and the refrigerant heat exchange pipeline inlet, the refrigerant inlet is independently connected to the cold supply chamber outlet of the impurity adsorption tower, the cold supply chamber outlet of the oxygen purification tower and the refrigerant heat exchange pipeline outlet, and the refrigerant heat exchange pipeline inlet is connected to the refrigerant heat exchange pipeline outlet through the heat exchanger.

[0030] Preferably, the refrigerant inlet is provided with a first pressure sensor and a second pressure sensor.

[0031] The impurity adsorption tower and the oxygen purification tower described in the present invention are cooled by an ice dryer before being put into use to reach the working temperature range.

[0032] In a second aspect, the present invention provides a method for purifying oxygen, nitrogen and crude neon and helium gases. The purification method is performed by the purification device system for oxygen, nitrogen and crude neon and helium gases described in the first aspect. The purification method comprises the following steps:

[0033] (1) After the first heat exchange and reheating, the air separation nitrogen is physically deoxygenated to obtain high-purity nitrogen;

[0034] (2) the crude neon-helium gas from air separation enters the oxygen-saturated environment formed after the physical deoxygenation in step (1) to be dehydrogenated, and the dehydrogenated neon-helium gas is subjected to membrane separation and impurity adsorption in turn after the second heat exchange and rewarming to obtain a neon-helium mixed gas;

[0035] (3) The air-separated oxygen undergoes the third heat exchange and reheating, pressurization, catalytic hydrocarbon removal, the first heat recovery and the second heat recovery, carbon dioxide and water adsorption treatment, and nitride removal treatment in sequence. The obtained oxygen undergoes the fourth heat exchange and reheating and is then purified to obtain high-purity oxygen.

[0036] The high-purity nitrogen gas in step (1) enters the water vapor environment formed after the carbon dioxide and water adsorption treatment in step (3) for purging, then takes out the carbon dioxide and water, and returns to the physical deoxygenation in step (1) after the water vapor removal treatment.

[0037] During the impurity adsorption in step (2) and the purification process in step (3), cold circulation is provided.

[0038] The purification method of oxygen, nitrogen and crude neon and helium provided by the present invention can purify and remove impurities in nitrogen, oxygen and crude neon and helium produced by an air separation device. Specifically, the air separation nitrogen is reheated through a heat exchanger and then physically deoxygenated at room temperature; the air separation oxygen is reheated and pressurized and then C is removed by high-temperature physical catalysis. m H n , and then adsorb CO2 and H2O at room temperature; then, NO x Reduced to N2 and O2, and finally the volume concentration of N2 and O2 is controlled below 0.3ppm by temperature variable adsorption; the dehydrogenation of crude neon-helium gas in air separation is linked with the nitrogen purification process in air separation. When the nitrogen purification tower is saturated with oxygen, heated crude neon-helium gas is introduced to realize nitrogen purification regeneration and remove H2 in the crude neon-helium gas at the same time; after hydrogen is removed, the crude neon-helium gas is combined with membrane separation and low-temperature adsorption to control the volume concentration of impurity nitrogen below 0.1ppm; air separation nitrogen purification and air separation oxygen purification are linked, that is, the purified nitrogen part is used as the regeneration gas source for oxygen purification, and the discharged nitrogen merges with the air separation nitrogen.

[0039] Preferably, the temperature of the air separation nitrogen after the first heat exchange and rewarming in step (1) is 20-30°C, for example, 20°C, 22°C, 25°C, 28°C or 30°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0040] Preferably, the purity of the high-purity nitrogen in step (1) is ≥ 7N, for example, 7N or 99.99999%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] Preferably, the physical deoxygenation in step (1) comprises deoxygenation and regeneration which are performed simultaneously, and oxygen desorption and dehydrogenation of crude neon and helium gas from air separation are performed during the regeneration process.

[0042] Before the dehydrogenation in step (2), the crude neon-helium gas is heated to 180-205°C, for example, 180°C, 185°C, 190°C, 200°C or 205°C, but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] The membrane separation in step (2) includes a first membrane separation, a second membrane separation and a third membrane separation performed in sequence. The waste gas discharged after the first membrane separation is discharged into the atmosphere or recovered for treatment. The waste gas discharged after the second membrane separation is pressurized and returned to the first membrane separation. The waste gas discharged after the third membrane separation is pressurized and returned to the first membrane separation.

[0044] The high-purity nitrogen gas portion of step (1) enters the first membrane separation and merges with the dehydrogenated neon and helium gas.

[0045] The impurity adsorption in step (2) includes adsorption and regeneration performed simultaneously. During the adsorption process, the temperature is controlled at -100 to -84°C, and during the regeneration process, the temperature is controlled at -10 to 0°C, so as to achieve the decomposition of the adsorbed impurity gas.

[0046] During the adsorption process, the temperature is controlled to be -100 to -84°C, for example, -100°C, -95°C, -90°C or -84°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0047] During the regeneration process, the temperature is controlled to be between -10 and 0°C, for example, -10°C, -8°C, -5°C, -2°C or 0°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0048] Preferably, in step (2), the volume concentration of hydrogen in the dehydrogenated neon-helium gas is ≤0.9 ppm, and the volume concentration of nitrogen is ≥72%.

[0049] The volume concentration of hydrogen in the dehydrogenated neon-helium gas is ≤0.9 ppm, for example, it can be 0.9 ppm, 0.8 ppm, 0.7 ppm, 0.6 ppm or 0.5 ppm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] The volume concentration of nitrogen in the dehydrogenated neon helium gas is ≥ 72%, for example, it can be 72%, 73%, 75%, 78% or 80%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] Preferably, the volume concentration of nitrogen in the dehydrogenated neon helium gas after the first membrane separation is ≤33%, the volume concentration of nitrogen in the dehydrogenated neon helium gas after the second membrane separation is ≤4.7%, and the volume concentration of nitrogen in the dehydrogenated neon helium gas after the third membrane separation is ≤0.3%.

[0052] The volume concentration of nitrogen in the dehydrogenated neon and helium gas after the first membrane separation is ≤33%, for example, it can be 33%, 30%, 25%, 20% or 15%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0053] The volume concentration of nitrogen in the dehydrogenated neon and helium gas after the second membrane separation is ≤4.7%, for example, it can be 4.7%, 4.5%, 4%, 3.5% or 3%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0054] The volume concentration of nitrogen in the dehydrogenated neon and helium gas after the third membrane separation is ≤0.3%, for example, it can be 0.3%, 0.25%, 0.2%, 0.15% or 0.1%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0055] Preferably, in step (2), the volume concentration of hydrogen in the neon-helium mixed gas is ≤0.2 ppm, and the volume concentration of nitrogen is ≤0.1 ppm.

[0056] The volume concentration of hydrogen in the neon-helium mixed gas is ≤0.2ppm, for example, it can be 0.2ppm, 0.18ppm, 0.15ppm, 0.12ppm or 0.1ppm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0057] The volume concentration of nitrogen in the neon-helium mixed gas is ≤0.1ppm, for example, it can be 0.1ppm, 0.08ppm, 0.05ppm, 0.02ppm or 0.01ppm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0058] Preferably, the end point of the pressurization in step (3) is 7-18ata(A), for example, it can be 7ata(A), 10ata(A), 12ata(A), 15ata(A) or 18ata(A), but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0059] Preferably, the temperature of the catalytic hydrocarbon removal in step (3) is 270-320°C, for example, 270°C, 280°C, 300°C, 310°C or 320°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0060] The carbon dioxide and water adsorption treatment in step (3) includes adsorption and regeneration performed simultaneously. During the regeneration process, the high-purity nitrogen gas in step (1) is heated at 170-200° C. and then enters the water vapor environment formed after the carbon dioxide and water adsorption treatment for purging. For example, the temperature may be 170° C., 180° C., 185° C., 190° C. or 200° C., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0061] The temperature of the nitride removal treatment in step (3) is 320-350°C, for example, 320°C, 330°C, 340°C, 345°C or 350°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0062] The purification treatment in step (3) includes nitrogen and argon adsorption treatment and regeneration analysis performed simultaneously.

[0063] Preferably, the purity of the high-purity oxygen is ≥6N, and the total volume concentration of nitrogen and argon in the high-purity oxygen is ≤0.3ppm.

[0064] The purity of the high-purity oxygen is ≥ 6N, for example, it can be 6N or 7N, but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0065] The total volume concentration of nitrogen and argon in the high-purity oxygen is ≤0.3ppm, for example, it can be 0.3ppm, 0.25ppm, 0.2ppm, 0.15ppm or 0.1ppm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0066] Compared with the prior art, the present invention has the following beneficial effects:

[0067] The oxygen, nitrogen and crude neon-helium purification device system provided by the present invention can purify and remove impurities in nitrogen, oxygen and crude neon-helium produced by an air separation device. Specifically, the air separation nitrogen is reheated through a heat exchanger and then deoxygenated in a deoxygenation tower to obtain high-purity nitrogen; the air separation oxygen is reheated and pressurized by a heat exchanger and a first supercharger, and then hydrocarbons are removed by a hydrocarbon removal device, and then CO2 and H2O are adsorbed by a carbon dioxide and water adsorption tower, and then NO is removed in a nitride removal device. xThe air separation crude neon-helium gas is reduced to N2 and O2, and finally high-purity oxygen is obtained through an oxygen purification tower; the dehydrogenation of the air separation crude neon-helium gas is linked with the air separation nitrogen purification process, and when the deoxygenation tower is saturated with oxygen, heated crude neon-helium gas is introduced to achieve nitrogen purification and regeneration while removing hydrogen from the crude neon-helium gas; after hydrogen removal, the crude neon-helium gas is introduced into a permeable membrane component and an impurity adsorption tower to obtain a neon-helium mixed gas; air separation nitrogen purification and air separation oxygen purification are linked, that is, the purified nitrogen part is used as the regeneration gas source for oxygen purification, and the discharged nitrogen is merged with the air separation nitrogen; the purification device system is used to purify oxygen, nitrogen and crude neon-helium gas in a linked manner, and nitrogen can be purified to a volume concentration of impurity oxygen below 0.1ppm; oxygen is purified to a total volume concentration of impurity nitrogen and argon below 0.3ppm; crude neon-helium gas is purified to a volume concentration of impurity hydrogen below 0.2ppm, and a volume concentration of nitrogen below 0.1ppm. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 It is a schematic diagram of the structure of the purification device system for oxygen, nitrogen and crude neon and helium provided in Example 1 of the present invention.

[0069] Among them: 1. the first stop valve, 2. the second stop valve, 3. the third stop valve, 4. the fourth stop valve, 5. the fifth stop valve, 6. the second deoxidation tower, 7. the first deoxidation tower, 8. the sixth stop valve, 9. the seventh stop valve, 10. the eighth stop valve, 11. the ninth stop valve, 12. the tenth stop valve, 13. the heat balancer, 14. the second booster, 15. the eleventh stop valve, 16. the twelfth stop valve, 17. the thirteenth stop valve, 18. the fourteenth stop valve, 19. the fifteenth stop valve, 20. the sixteenth stop valve, 21. the second adsorption tower, 22. First adsorption tower, 23. Seventeenth stop valve, 24. Eighteenth stop valve, 25. Nineteenth stop valve, 26. Nitride removal device, 27. Twentieth stop valve, 28. Twenty-first stop valve, 29. Twenty-second stop valve, 30. Second purification tower, 31. First purification tower, 32. Twenty-third stop valve, 33. Twenty-fourth stop valve, 34. Twenty-fifth stop valve, 35. Twenty-sixth stop valve, 36. Vacuum pump, 37. Twenty-seventh stop valve, 38. Twenty-eighth stop valve, 39. Twenty-ninth stop valve, 40. Third 10 stop valves, 41, 31st stop valve, 42-1, first pressure sensor, 42-2, second pressure sensor, 43, nitrogen inlet, 44, oxygen inlet, 45, cold end inlet, 46, crude neon-helium inlet, 47, first hot end inlet, 48, third hot end inlet, 49, second hot end inlet, 50, second hot end outlet, 51, third hot end outlet, 52, first hot end outlet, 53, crude neon-helium outlet, 54, cold end outlet, 55, oxygen outlet, 56, nitrogen outlet, 57, heat exchanger, 58, first booster, 59 , electric heater, 60, hydrocarbon removal device, 61, nitrogen drying device, 62, the thirty-second stop valve, 63, the thirty-third stop valve, 64, the thirty-fourth stop valve, 65, the first permeable membrane, 66, the thirty-fifth stop valve, 67, the first boosting valve, 68, the second boosting valve, 69, the second permeable membrane, 70, the thirty-sixth stop valve, 71, the third permeable membrane, 72, the thirty-seventh stop valve, 73, the thirty-eighth stop valve, 74, the first impurity adsorption tower, 75, the second impurity adsorption tower, 76, the thirty-ninth stop valve, 77, the fortieth stop valve. DETAILED DESCRIPTION

[0070] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0071] The present invention provides a purification device system for oxygen, nitrogen and crude neon-helium gas. The purification device system comprises a heat exchanger. The heat exchanger is provided with a nitrogen inlet, a nitrogen outlet, an oxygen inlet, an oxygen outlet, a crude neon-helium gas inlet, a crude neon-helium gas outlet, a dehydrogenated neon-helium gas inlet and a dehydrogenated neon-helium gas outlet.

[0072] The nitrogen outlet is connected to the deoxygenation tower, and the crude neon-helium outlet is connected to the deoxygenation tower through an electric heater. The deoxygenation tower includes a first deoxygenation tower and a second deoxygenation tower which are operated and regenerated alternately. The deoxygenation tower discharges high-purity nitrogen and dehydrogenated neon-helium gas. The dehydrogenated neon-helium gas enters the heat exchanger through the dehydrogenated neon-helium gas inlet and is discharged from the dehydrogenated neon-helium gas outlet, and then enters the permeable membrane component and the impurity adsorption tower in sequence. The impurity adsorption tower includes a first impurity adsorption tower and a second impurity adsorption tower which are operated and regenerated alternately, and the outlet of the impurity adsorption tower is connected to a neon-helium gas refining system.

[0073] The permeable membrane assembly includes a first permeable membrane, a second permeable membrane and a third permeable membrane connected in sequence along the flow direction of dehydrogenation, neon and helium, wherein the first permeable membrane, the second permeable membrane and the third permeable membrane are independently provided with a permeation side and a non-permeation side, respectively; the non-permeation side of the first permeable membrane is provided with a waste gas outlet; the waste gas discharged from the non-permeation side of the second permeable membrane flows through a first boosting valve and returns to the first permeable membrane, and the pressure gas source of the first boosting valve comes from the dehydrogenation, neon and helium gas inlet; the waste gas discharged from the non-permeation side of the third permeable membrane flows through a second boosting valve and returns to the first permeable membrane, and the pressure gas source of the second boosting valve comes from the waste gas discharged from the non-permeation side of the second permeable membrane.

[0074] The oxygen outlet is connected to the first supercharger, the hydrocarbon removal device and the heat balancer in sequence; the oxygen discharged from the heat balancer flows through the heat exchanger and then enters the carbon dioxide and water adsorption tower and the nitride removal device in sequence; the discharged oxygen flows through the heat exchanger again and then enters the oxygen purification tower; the carbon dioxide and water adsorption tower includes a first adsorption tower and a second adsorption tower which are alternately operated and regenerated; the oxygen purification tower includes a first purification tower and a second purification tower which are alternately operated and regenerated; the outlet of the oxygen purification tower is independently connected to the high-purity oxygen system and the vacuum pump.

[0075] Part of the high-purity nitrogen discharged from the deoxygenation tower enters the high-purity nitrogen system, part enters the first permeable membrane, and part flows through the heat balancer and the second booster, enters the regenerated carbon dioxide and water adsorption tower for purging to remove carbon dioxide and water, and then returns to the pipeline where the nitrogen outlet is located after removing carbon dioxide and water through the nitrogen drying device.

[0076] The purification device system also includes an ice dryer, which is used to provide a cold source for the impurity adsorption tower and the oxygen purification tower; the ice dryer is provided with a refrigerant outlet and a refrigerant inlet, the refrigerant outlet is independently connected to the cold supply chamber inlet of the impurity adsorption tower, the cold supply chamber inlet of the oxygen purification tower and the refrigerant heat exchange pipeline inlet, the refrigerant inlet is independently connected to the cold supply chamber outlet of the impurity adsorption tower, the cold supply chamber outlet of the oxygen purification tower and the refrigerant heat exchange pipeline outlet, the refrigerant heat exchange pipeline inlet is connected to the refrigerant heat exchange pipeline outlet through the heat exchanger; the refrigerant inlet is provided with a first pressure sensor and a second pressure sensor.

[0077] The present invention also provides a method for purifying oxygen, nitrogen and crude neon and helium gases. The purification method is carried out by the purification device system of oxygen, nitrogen and crude neon and helium gases. The purification method comprises the following steps:

[0078] (1) Physically deoxygenating the air separation nitrogen at 20-30°C obtained after the first heat exchange and reheating to obtain high-purity nitrogen with a purity of ≥7N; the physical deoxygenation includes deoxygenation and regeneration performed simultaneously, and oxygen desorption and dehydrogenation of the air separation crude neon and helium gas are performed during the regeneration process;

[0079] (2) The crude neon-helium gas from air separation is heated to 180-205° C. and then enters the oxygen-saturated environment formed after the physical deoxidation in step (1) to remove hydrogen. The obtained dehydrogenated neon-helium gas is subjected to membrane separation and impurity adsorption in sequence after the second heat exchange and rewarming to obtain a neon-helium mixed gas; the volume concentration of hydrogen in the dehydrogenated neon-helium gas is ≤0.9 ppm, and the volume concentration of nitrogen is ≥72%; the volume concentration of hydrogen in the neon-helium mixed gas is ≤0.2 ppm, and the volume concentration of nitrogen is ≤0.1 ppm;

[0080] The membrane separation comprises a first membrane separation, a second membrane separation and a third membrane separation performed in sequence, the waste gas discharged after the first membrane separation is discharged into the atmosphere or recycled, the waste gas discharged after the second membrane separation is pressurized and returned to the first membrane separation, and the waste gas discharged after the third membrane separation is pressurized and returned to the first membrane separation; the high-purity nitrogen part of step (1) enters the first membrane separation and merges with the dehydrogenated neon helium gas; the volume concentration of nitrogen in the dehydrogenated neon helium gas after the first membrane separation is ≤33%, the volume concentration of nitrogen in the dehydrogenated neon helium gas after the second membrane separation is ≤4.7%, and the volume concentration of nitrogen in the dehydrogenated neon helium gas after the third membrane separation is ≤0.3%;

[0081] The impurity adsorption includes adsorption and regeneration performed simultaneously, the temperature is controlled at -100 to -84°C during the adsorption process, and the temperature is controlled at -10 to 0°C during the regeneration process, so as to achieve the decomposition of the adsorbed impurity gas;

[0082] (3) The air-separated oxygen is sequentially subjected to the third heat exchange reheating, pressurized to 7-18ata(A), catalytic hydrocarbon removal at 270-320°C, the first heat recovery and the second heat recovery, carbon dioxide and water adsorption treatment, and nitride removal treatment at 320-350°C. The obtained oxygen is purified after the fourth heat exchange reheating to obtain high-purity oxygen; the purity of the high-purity oxygen is ≥6N, and the total volume concentration of nitrogen and argon in the high-purity oxygen is ≤0.3ppm;

[0083] The carbon dioxide and water adsorption treatment includes adsorption and regeneration which are performed simultaneously. During the regeneration process, the high-purity nitrogen gas in step (1) is heated at 170-200° C. and then enters the water vapor environment formed after the carbon dioxide and water adsorption treatment for purging, and then takes out the carbon dioxide and water, and returns to the physical deoxygenation in step (1) after the water vapor removal treatment.

[0084] The purification process includes nitrogen and argon adsorption and regeneration analysis performed simultaneously;

[0085] During the impurity adsorption in step (2) and the purification process in step (3), cold circulation is provided.

[0086] The technical solution of the present invention is further illustrated by specific embodiments below.

[0087] Example 1

[0088] This embodiment provides a purification device system for oxygen, nitrogen and crude neon and helium, such as Figure 1 As shown, the nitrogen, oxygen and crude neon and helium gases come from air separation product gas.

[0089] The nitrogen inlet pipeline is connected to the nitrogen inlet 43 of the heat exchanger 57 through the first stop valve 1, and the nitrogen outlet 56 of the heat exchanger 57 is simultaneously connected to the inlet of the fourth stop valve 4, the inlet of the fifth stop valve 5, and the outlet of the nitrogen drying device 61; the outlet of the fourth stop valve 4 is simultaneously connected to the outlet of the eighth stop valve 10 and the inlet of the first deoxygenation tower 7; the outlet of the fifth stop valve 5 is simultaneously connected to the outlet of the ninth stop valve 11 and the inlet of the second deoxygenation tower 6.

[0090] The inlet of the eighth stop valve 10 and the inlet of the ninth stop valve 11 are connected to the outlet of the electric heater 59; the inlet of the electric heater 59 is connected to the crude neon-helium gas outlet 53 of the heat exchanger 57, the crude neon-helium gas inlet 46 of the heat exchanger 57 is connected to the outlet of the third stop valve 3, and the inlet of the third stop valve 3 is connected to the crude neon-helium gas inlet pipeline.

[0091] The outlet of the first deoxygenation tower 7 is simultaneously connected to the inlet of the seventh stop valve 9 and the inlet of the thirty-third stop valve 63; the outlet of the second deoxygenation tower 6 is simultaneously connected to the inlet of the sixth stop valve 8 and the inlet of the thirty-second stop valve 62; the outlet of the sixth stop valve 8 and the outlet of the seventh stop valve 9 are simultaneously connected to the first hot end inlet 47 of the heat exchanger 57; the outlet of the thirty-second stop valve 62 and the outlet of the thirty-third stop valve 63 are simultaneously connected to the inlet of the tenth stop valve 12, the high-purity nitrogen system and the inlet of the thirty-fourth stop valve 64; the outlet of the tenth stop valve 12 is connected to the cold end inlet of the heat balancer 13, the cold end outlet of the heat balancer 13 is connected to the inlet of the second booster compressor 14, and the outlet of the second booster compressor 14 is simultaneously connected to the inlet of the eleventh stop valve 15 and the inlet of the twelfth stop valve 16.

[0092] The outlet of the eleventh stop valve 15 is simultaneously connected to the outlet of the fifteenth stop valve 19 and the inlet of the first adsorption tower 22; the outlet of the twelfth stop valve 16 is simultaneously connected to the outlet of the sixteenth stop valve 20 and the inlet of the second adsorption tower 21; the outlet of the first adsorption tower 22 is simultaneously connected to the inlet of the thirteenth stop valve 17 and the inlet of the eighteenth stop valve 24; the outlet of the second adsorption tower 21 is simultaneously connected to the inlet of the fourteenth stop valve 18 and the inlet of the seventeenth stop valve 23; the outlet of the thirteenth stop valve 17 and the outlet of the fourteenth stop valve 18 are commonly connected to the inlet of the nitrogen drying device 61.

[0093] The first hot end outlet 52 of the heat exchanger 57, the outlet of the thirty-fourth stop valve 64, the outlet of the first boosting valve 67, and the outlet of the second boosting valve 68 are commonly connected to the inlet of the first permeable membrane 65; the outlet of the first permeable membrane 65 is connected to the inlet of the thirty-fifth stop valve 66, and the outlet of the thirty-fifth stop valve 66 is connected to the inlet of the second permeable membrane 69; the outlet of the second permeable membrane 69 is connected to the inlet of the thirty-sixth stop valve 70, and the outlet of the thirty-sixth stop valve 70 is connected to the inlet of the third permeable membrane 71, and the outlet of the third permeable membrane 71 is simultaneously connected to the inlet of the thirty-seventh stop valve 72 and the inlet of the thirty-eighth stop valve 73; the outlet of the thirty-seventh stop valve 72 is connected to the inlet of the first impurity adsorption tower 74, and the outlet of the first impurity adsorption tower 74 is connected to the inlet of the thirty-ninth stop valve 76; the outlet of the thirty-eighth stop valve 73 is connected to the inlet of the second impurity adsorption tower 75, and the outlet of the second impurity adsorption tower 75 is connected to the inlet of the fortieth stop valve 77; the outlet of the thirty-ninth stop valve 76 and the outlet of the fortieth stop valve 77 are commonly connected to the neon-helium refining system.

[0094] The exhaust outlet of the second permeable membrane 69 is connected to the inlet of the first boosting valve 67 , and the exhaust outlet of the third permeable membrane 71 is connected to the inlet of the second boosting valve 68 .

[0095] The oxygen intake pipeline is connected to the oxygen inlet 44 of the heat exchanger 57 through the second stop valve 2, the oxygen outlet 55 of the heat exchanger 57 is connected to the inlet of the first supercharger 58, the outlet of the first supercharger 58 is connected to the inlet of the hydrocarbon removal device 60, the outlet of the hydrocarbon removal device 60 is connected to the hot end inlet of the heat balancer 13, and the hot end outlet of the heat balancer 13 is connected to the second hot end inlet 49 of the heat exchanger 57; the second hot end outlet 50 of the heat exchanger 57 is simultaneously connected to the inlet of the fifteenth stop valve 19 and the inlet of the sixteenth stop valve 20; the outlet of the seventeenth stop valve 23 and the outlet of the eighteenth stop valve 24 are commonly connected to the inlet of the nineteenth stop valve 25, and the outlet of the nineteenth stop valve 25 is connected to the inlet of the nitride removal device 26; the outlet of the nitride removal device 26 is connected to the inlet of the twentieth stop valve 27, the outlet of the twentieth stop valve 27 is connected to the third hot end inlet 48 of the heat exchanger 57, and the third hot end outlet 51 of the heat exchanger 57 is simultaneously connected to the inlet of the twenty-first stop valve 28 and the inlet of the twenty-second stop valve 29.

[0096] The outlet of the twenty-first stop valve 28 is connected to the inlet of the first purification tower 31, and the inlet of the twenty-second stop valve 29 is connected to the inlet of the second purification tower 30; the outlet of the second purification tower 30 is simultaneously connected to the inlet of the twenty-third stop valve 32 and the inlet of the twenty-fifth stop valve 34; the outlet of the first purification tower 31 is simultaneously connected to the inlet of the twenty-fourth stop valve 33 and the inlet of the twenty-sixth stop valve 35; the outlet of the twenty-third stop valve 32 and the outlet of the twenty-fourth stop valve 33 are jointly connected to the high-purity oxygen system; the outlet of the twenty-fifth stop valve 34 and the outlet of the twenty-sixth stop valve 35 are jointly connected to the suction port of the vacuum pump 36, and the exhaust port of the vacuum pump 36 is safely emptied.

[0097] The ice dryer in the device of the present invention provides a cold source supplement for the system, wherein A-1 and A-2 represent refrigerants; the refrigerant outlet of the ice dryer is simultaneously connected to the inlet of the 30th stop valve 40, the inlet of the 31st stop valve 41, the first purification tower 31 and the second purification tower 30 cold supply chamber inlet; the outlet of the 30th stop valve 40 is connected to the cold end inlet 45 of the heat exchanger 57, and the outlet of the 31st stop valve 41 is simultaneously connected to the cold supply chamber inlet of the second impurity adsorption tower 75 and the cold supply chamber inlet of the first impurity adsorption tower 74.

[0098] The outlet of the cold supply chamber of the first impurity adsorption tower 74 is connected to the inlet of the twenty-seventh stop valve 37, and the outlet of the cold supply chamber of the second impurity adsorption tower 75 is connected to the inlet of the twenty-eighth stop valve 38; the outlets of the cold supply chambers of the first purification tower 31 and the second purification tower 30, the outlets of the twenty-seventh stop valve 37, the outlets of the twenty-eighth stop valve 38, and the outlets of the twenty-ninth stop valve 39 are commonly connected to the refrigerant inlet of the ice dryer; the inlet of the twenty-ninth stop valve 39 is connected to the cold end outlet 54 of the heat exchanger 57; the refrigerant inlet of the ice dryer is provided with a first pressure sensor 42-1 and a second pressure sensor 42-2.

[0099] The method for purifying oxygen, nitrogen and crude neon and helium using the purification device system specifically comprises the following steps:

[0100] Before starting the purification device system, the pipelines in the purification device system need to be purged and replaced under the following conditions: 4atm nitrogen purge for 5.5h, and then vacuumize for 3 times until the oxygen content at the outlet of the purification device system pipeline drops below 0.1ppm; after the purification device system pipeline is replaced, the pipeline pressure is maintained first, and the nitrogen in the pipeline is not emptied temporarily to test whether the system instrument and electronic control display is normal. After the instrument and electronic control components are tested, the nitrogen in the pipeline is emptied and vacuumized to below 10Pa.

[0101] Open the first stop valve 1, and the nitrogen flows through the nitrogen inlet 43 of the heat exchanger 57 and the nitrogen outlet 56 into the second deoxidation tower 6 or the first deoxidation tower 7. The second deoxidation tower 6 and the first deoxidation tower 7 are used alternately, that is, when the second deoxidation tower 6 is working, the first deoxidation tower 7 is regenerated, and vice versa, when the first deoxidation tower 7 is working, the second deoxidation tower 6 is regenerated. The following takes the first deoxidation tower 7 working and the second deoxidation tower 6 regenerating as an example:

[0102] The fourth stop valve 4 and the thirty-third stop valve 63 are opened successively. After the nitrogen passes through the first deoxidation tower 7 to remove trace oxygen, the volume purity of the nitrogen reaches 7N, which is used as high-purity nitrogen. After the first deoxidation tower 7 works for 0.9T, the third stop valve 3 is opened, and the crude neon-helium gas flows through the crude neon-helium gas inlet 46 of the heat exchanger 57 and the crude neon-helium gas outlet 53 into the electric heater 59. The crude neon-helium gas is heated to 190°C by the electric heater 59. After the working time of the first deoxidation tower 7 is over, the eighth stop valve 10 is opened, and the heated crude neon-helium gas is passed into the first deoxidation tower 7 to remove the impurity hydrogen in the crude neon-helium gas while consuming the oxygen adsorbed by the deoxidizer. At this time, the volume concentration of hydrogen in the dehydrogenated crude neon-helium gas is ≤0.9ppm.

[0103] The crude neon-helium gas dehydrogenated passes through the first hot end inlet 47 of the heat exchanger 57 and flows through the first hot end outlet 52 into the first permeable membrane 65, and the nitrogen with a volume concentration of ≥72% in the crude neon-helium gas is initially removed. It is pointed out here that 95% of He and 73% of Ne in the crude neon-helium gas enter the permeation side of the first permeable membrane 65 through the dissolution and diffusion of the membrane, and the volume concentration of nitrogen on the permeation side is reduced to ≤33%; the waste gas on the non-permeation side of the first permeable membrane 65 can be directly discharged into the atmosphere, and the volume concentration of nitrogen in the waste gas is 82%. In addition, the thirty-fourth stop valve 64 is opened, and the high-purity nitrogen part after nitrogen purification merges with the crude neon-helium gas dehydrogenated.

[0104] Open the thirty-fifth stop valve 66, and the gas at the outlet of the permeation side of the first permeable membrane 65 enters the second permeable membrane 69. 83% of He and 48% of Ne in the gas at the outlet of the permeation side of the first permeable membrane 65 enter the permeation side of the second permeable membrane 69 through dissolution and diffusion through the membrane; the exhaust gas at the non-permeation side of the second permeable membrane 69 is pressurized by the first booster valve 67 and then returned to the gas inlet of the first permeable membrane 65.

[0105] Further, the thirty-sixth stop valve 70 is opened, and the outlet gas of the second permeable membrane 69 enters the third permeable membrane 71, and 71% of He and 32% of Ne in the outlet gas of the low-pressure side of the second permeable membrane 69 enter the permeable side of the third permeable membrane 71 through dissolution and diffusion through the membrane; the waste gas on the non-permeable side of the third permeable membrane 71 is pressurized by the second booster valve 68 and then returns to the gas inlet of the first permeable membrane 65. It should be noted here that the pressure gas source AM-1 of the first booster valve 67 comes from the first hot end inlet 47 of the heat exchanger 57, and the pressure gas source AM-2 of the second booster valve 68 comes from the waste gas on the non-permeable side of the second permeable membrane 69.

[0106] The impurity nitrogen volume concentration of the gas at the outlet of the permeation side of the third permeable membrane 71 is 0.3%, and enters the first impurity adsorption tower 74 or the second impurity adsorption tower 75. It is explained here that the first impurity adsorption tower 74 and the second impurity adsorption tower 75 are used alternately. When the first impurity adsorption tower 74 is working, the second impurity adsorption tower 75 is regenerated. On the contrary, the second impurity adsorption tower 75 is working and the first impurity adsorption tower 74 is regenerated. The first impurity adsorption tower 74 and the second impurity adsorption tower 75 are set to work at -90°C and regenerate at 0°C.

[0107] Furthermore, the first impurity adsorption tower 74 and the second impurity adsorption tower 75 are cooled before being activated. Open the twenty-seventh stop valve 37, the twenty-eighth stop valve 38, the twenty-ninth stop valve 39, the thirtieth stop valve 40, and the thirty-first stop valve 41, start the ice dryer, and cool the first impurity adsorption tower 74 and the second impurity adsorption tower 75 to -90°C; at the same time, the second purification tower 30 and the first purification tower 31 are also cooled and used to adsorb trace impurity gases in the air separation oxygen. It is pointed out here that it takes 45 minutes for the first impurity adsorption tower 74, the second impurity adsorption tower 75, the second purification tower 30, and the first purification tower 31 to cool to below -90°C. Therefore, the ice dryer is started first according to the actual situation of on-site debugging. This embodiment takes the operation of the first impurity adsorption tower 74 and the regeneration of the second impurity adsorption tower 75 as an example:

[0108] After the first impurity adsorption tower 74 and the second impurity adsorption tower 75 are cooled to -90°C, the thirty-seventh stop valve 72 and the thirty-ninth stop valve 76 are opened, and the gas at the outlet of the permeation side of the third permeable membrane 71 enters the first impurity adsorption tower 74 to adsorb and remove trace amounts of N2 and other impurity gases in the dehydrogenated neon-helium gas, and the neon-helium mixed gas at the outlet of the first impurity adsorption tower 74 goes to the neon-helium refining system. It is explained here that when the first impurity adsorption tower 74 is working, the second impurity adsorption tower 75 is reheated by its own electric heating belt, and the waste gas analyzed by reheating is safely discharged through the adsorption tower exhaust pipeline.

[0109] Further, when the working conditions of the nitrogen purification and crude neon-helium dehydrogenation and denitrification process of the present invention are stable, the second stop valve 2 is opened, and oxygen flows through the oxygen inlet 44 of the heat exchanger 57 and the oxygen outlet 55 into the first supercharger 58. After the oxygen is pressurized to 7ata (A), it enters the hydrocarbon removal device 60 to catalytically remove the trace hydrocarbons in the oxygen at 300°C. It is pointed out here that the trace hydrocarbons are decomposed into CO2, H2O and NO in the hydrocarbon removal device 60. x , CO2 and H2O are removed by adsorption through the subsequent second adsorption tower 21 or the first adsorption tower 22, and N2 and Ar are removed by adsorption through the second purification tower 30 or the first purification tower 31.

[0110] Furthermore, the oxygen at the outlet of the hydrocarbon removal device 60 exchanges heat with part of the high-purity nitrogen through the hot end flow path of the heat balancer 13, and the heat of the oxygen at the outlet of the hydrocarbon removal device 60 is recovered once; the oxygen at the hot end of the heat balancer 13 flows through the second hot end inlet 49 of the heat exchanger 57 and the second hot end outlet 50, and the heat of the oxygen at the outlet of the hydrocarbon removal device 60 is recovered twice.

[0111] The second adsorption tower 21 and the first adsorption tower 22 are used alternately, that is, when the second adsorption tower 21 is working, the first adsorption tower 22 is regenerated; conversely, when the first adsorption tower 22 is working, the second adsorption tower 21 is regenerated, and the regeneration gas source is high-purity nitrogen. This embodiment takes the first adsorption tower 22 working and the second adsorption tower 21 regenerating as an example:

[0112] The fifteenth stop valve 19 and the eighteenth stop valve 24 are opened, and the oxygen at the second hot end outlet 50 of the heat exchanger 57 enters the first adsorption tower 22 to adsorb and remove trace hydrocarbon decomposition products CO2 and H2O. At the same time, the tenth stop valve 12 is opened, the second booster 14 is started, the twelfth stop valve 16 and the fourteenth stop valve 18 are opened, and the high-purity nitrogen gas of 170°C after heating is purged to purge the adsorbent in the second adsorption tower 21, and the CO2 and H2O adsorbed by the adsorbent are analyzed and taken away. The nitrogen purged at the outlet of the second adsorption tower 21 is purified by the nitrogen drying device 61 and then refluxed to the second deoxygenation tower 6 or the inlet of the first deoxygenation tower 7.

[0113] Further, the nineteenth stop valve 25 is opened, and the oxygen after removing CO2 and H2O passes through the nitride removal device 26 to decompose NO at 320°C. x For N2 and O2, open the twentieth stop valve 27, and the high-temperature gas at the outlet of the nitride removal device 26 flows through the third hot end inlet 48 of the heat exchanger 57, flows through the third hot end outlet 51, exchanges heat with other process streams, and cools down before entering the second purification tower 30 or the first purification tower 31. It is pointed out here that the second purification tower 30 and the first purification tower 31 are used alternately, that is, when the second purification tower 30 works, the first purification tower 31 is regenerated, and vice versa, the first purification tower 31 works and the second purification tower 30 is regenerated. This embodiment takes the second purification tower 30 working and the first purification tower 31 regenerating as an example:

[0114] Open the twenty-second stop valve 29 and the twenty-third stop valve 32, and the oxygen at the third hot end outlet 51 of the heat exchanger 57 enters the second purification tower 30 to remove N2 and Ar, and then goes to the high-purity oxygen use occasion.

[0115] In this embodiment, the purification device system is used to purify oxygen, nitrogen and crude neon and helium in a linked manner, and the nitrogen is purified to a volume concentration of impurity oxygen below 0.1ppm; the oxygen is purified to a total volume concentration of impurity nitrogen and argon below 0.3ppm; the crude neon and helium are purified to a volume concentration of impurity hydrogen below 0.2ppm, and a volume concentration of nitrogen below 0.1ppm, thereby achieving efficient purification of air-separated oxygen, air-separated nitrogen and air-separated crude neon and helium.

[0116] Example 2

[0117] This embodiment provides a purification device system for oxygen, nitrogen and crude neon and helium. The difference from Embodiment 1 is that the second permeable membrane 69 and the third permeable membrane 71 are not provided, and the outlet gas on the permeation side of the first permeable membrane 65 directly enters the first impurity adsorption tower 74 or the second impurity adsorption tower 75, and the rest is the same as Embodiment 1.

[0118] In this embodiment, since the permeable membrane assembly is only provided with the first permeable membrane 65, the nitrogen in the dehydrogenated neon-helium gas cannot be effectively separated and removed, and thus the volume concentration of the impurity nitrogen in the obtained neon-helium mixed gas is too high.

[0119] Example 3

[0120] This embodiment provides a purification device system for oxygen, nitrogen and crude neon and helium. The difference from Embodiment 1 is that the thirty-fourth stop valve 64 and the pipeline where it is located are not provided, and the rest are the same as Embodiment 1.

[0121] In this embodiment, the thirty-fourth stop valve and the pipeline where it is located are not provided, so that the high-purity nitrogen gas and the crude neon and helium gas after hydrogen removal cannot be merged, thereby reducing the recovery rate of Ne+He of the first permeable membrane.

[0122] Comparative Example 1

[0123] This comparative example provides a purification device for oxygen, nitrogen and crude neon and helium. The purification of the oxygen and nitrogen is carried out by using the device disclosed in CN112229143A for producing oxygen and nitrogen by separating air through cryogenic distillation. The purification of the crude neon and helium is carried out by using the device disclosed in CN117566701A for purifying crude neon and helium by non-cryogenic method. The two devices are operated separately.

[0124] The purification devices for oxygen, nitrogen and crude neon and helium provided in this comparative example cannot achieve linked purification and impurity removal. Purifying oxygen, nitrogen and crude neon and helium separately by different devices will increase production costs and limit their application in industrial production.

[0125] In summary, the oxygen, nitrogen and crude neon-helium purification device system provided by the present invention can purify and remove impurities in the nitrogen, oxygen and crude neon-helium produced by the air separation device. Specifically, the air separation nitrogen is reheated through a heat exchanger and then deoxygenated in a deoxygenation tower to obtain high-purity nitrogen; the air separation oxygen is reheated and pressurized by a heat exchanger and a first booster, and then hydrocarbons are removed by a hydrocarbon removal device, and then CO2 and H2O are adsorbed by a carbon dioxide and water adsorption tower, and then NO is removed in a nitride removal device. x The air separation crude neon-helium gas is reduced to N2 and O2, and finally high-purity oxygen is obtained through an oxygen purification tower; the dehydrogenation of the air separation crude neon-helium gas is linked with the air separation nitrogen purification process, and when the deoxygenation tower is saturated with oxygen, heated crude neon-helium gas is introduced to achieve nitrogen purification and regeneration while removing hydrogen from the crude neon-helium gas; after hydrogen removal, the crude neon-helium gas is introduced into a permeable membrane component and an impurity adsorption tower to obtain a neon-helium mixed gas; air separation nitrogen purification and air separation oxygen purification are linked, that is, the purified nitrogen part is used as the regeneration gas source for oxygen purification, and the discharged nitrogen is merged with the air separation nitrogen; the purification device system is used to purify oxygen, nitrogen and crude neon-helium gas in a linked manner, and nitrogen can be purified to a volume concentration of impurity oxygen below 0.1ppm; oxygen is purified to a total volume concentration of impurity nitrogen and argon below 0.3ppm; crude neon-helium gas is purified to a volume concentration of impurity hydrogen below 0.2ppm, and a volume concentration of nitrogen below 0.1ppm.

[0126] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A purification device system for oxygen, nitrogen and crude neon and helium, characterized in that: The purification device system comprises a heat exchanger, and the heat exchanger is provided with a nitrogen inlet, a nitrogen outlet, an oxygen inlet, an oxygen outlet, a crude neon-helium inlet, a crude neon-helium outlet, a dehydrogenation neon-helium inlet and a dehydrogenation neon-helium outlet; the nitrogen outlet and the crude neon-helium outlet are both connected to a deoxidation tower, and the deoxidation tower discharges high-purity nitrogen and dehydrogenation neon-helium, and the dehydrogenation neon-helium enters the heat exchanger from the dehydrogenation neon-helium inlet and is discharged from the dehydrogenation neon-helium outlet, and then enters the permeation membrane assembly and the impurity adsorption tower in sequence; The oxygen outlet is connected to the first supercharger, the hydrocarbon removal device and the heat balancer in sequence. The oxygen discharged from the heat balancer flows through the heat exchanger and then enters the carbon dioxide and water adsorption tower and the nitride removal device in sequence. The discharged oxygen flows through the heat exchanger again and then enters the oxygen purification tower. The high-purity nitrogen part discharged from the deoxygenation tower enters the carbon dioxide and water adsorption tower to be purged and then takes out carbon dioxide and water. After the carbon dioxide and water are removed by the nitrogen drying device, it returns to the pipeline where the nitrogen outlet is located. The purification device system also includes an ice dryer, which is used to provide a cold source for the impurity adsorption tower and the oxygen purification tower.

2. The purification device system according to claim 1, characterized in that: The crude neon-helium gas outlet is connected to the deoxidation tower via an electric heater; The deoxygenation tower includes a first deoxygenation tower and a second deoxygenation tower which are operated and regenerated alternately.

3. The purification device system according to claim 1, characterized in that: The permeable membrane assembly comprises a first permeable membrane, a second permeable membrane and a third permeable membrane connected in sequence along the flow direction of the hydrogen-neon-helium removal gas, wherein the first permeable membrane, the second permeable membrane and the third permeable membrane are independently provided with a permeation side and a non-permeation side; The non-permeable side of the first permeable membrane is provided with a waste gas outlet; The waste gas discharged from the non-permeation side of the second permeable membrane flows back to the first permeable membrane after passing through the first booster valve, and the pressure gas source of the first booster valve comes from the dehydrogenation, neon and helium gas inlet; The waste gas discharged from the non-permeable side of the third permeable membrane flows through the second booster valve and then returns to the first permeable membrane. The pressure gas source of the second booster valve comes from the waste gas discharged from the non-permeable side of the second permeable membrane.

4. The purification device system according to claim 1, characterized in that: The outlet of the impurity adsorption tower is connected to a neon-helium gas refining system; The impurity adsorption tower includes a first impurity adsorption tower and a second impurity adsorption tower which are operated and regenerated alternately.

5. The purification device system according to claim 3, characterized in that: The carbon dioxide and water adsorption tower comprises a first adsorption tower and a second adsorption tower which are operated and regenerated alternately; Part of the high-purity nitrogen discharged from the deoxygenation tower enters the high-purity nitrogen system, part enters the first permeable membrane, and part flows through the heat balancer and the second booster to enter the regenerated carbon dioxide and water adsorption tower.

6. The purification device system according to claim 1, characterized in that: The oxygen purification tower includes a first purification tower and a second purification tower which are operated and regenerated alternately; The outlet of the oxygen purification tower is independently connected to a high-purity oxygen system and a vacuum pump.

7. The purification device system according to claim 1, characterized in that: The ice dryer is provided with a refrigerant outlet and a refrigerant inlet, the refrigerant outlet is independently connected to the cold supply chamber inlet of the impurity adsorption tower, the cold supply chamber inlet of the oxygen purification tower and the refrigerant heat exchange pipeline inlet, the refrigerant inlet is independently connected to the cold supply chamber outlet of the impurity adsorption tower, the cold supply chamber outlet of the oxygen purification tower and the refrigerant heat exchange pipeline outlet, and the refrigerant heat exchange pipeline inlet is connected to the refrigerant heat exchange pipeline outlet through the heat exchanger.

8. A method for purifying oxygen, nitrogen and crude neon and helium, characterized in that: The purification method is carried out by the purification device system of oxygen, nitrogen and crude neon and helium according to any one of claims 1 to 7, and the purification method comprises the following steps: (1) After the first heat exchange and reheating, the air separation nitrogen is physically deoxygenated to obtain high-purity nitrogen; (2) the crude neon-helium gas from air separation enters the oxygen-saturated environment formed after the physical deoxygenation in step (1) to be dehydrogenated, and the dehydrogenated neon-helium gas is subjected to membrane separation and impurity adsorption in turn after the second heat exchange and rewarming to obtain a neon-helium mixed gas; (3) The air-separated oxygen undergoes the third heat exchange and reheating, pressurization, catalytic hydrocarbon removal, the first heat recovery and the second heat recovery, carbon dioxide and water adsorption treatment, and nitride removal treatment in sequence. The obtained oxygen undergoes the fourth heat exchange and reheating and is then purified to obtain high-purity oxygen. The high-purity nitrogen gas in step (1) enters the water vapor environment formed after the carbon dioxide and water adsorption treatment in step (3) for purging, then takes out the carbon dioxide and water, and returns to the physical deoxygenation in step (1) after the water vapor removal treatment; During the impurity adsorption in step (2) and the purification process in step (3), cold circulation is provided.

9. The purification method according to claim 8, characterized in that The physical deoxygenation in step (1) includes deoxygenation and regeneration performed simultaneously, wherein oxygen desorption and dehydrogenation of crude neon and helium gas from air separation are performed during the regeneration process; In step (2), the crude neon-helium gas from the air separation is heated to 180-205° C. before the dehydrogenation; The membrane separation in step (2) includes a first membrane separation, a second membrane separation and a third membrane separation performed in sequence, wherein the waste gas discharged after the first membrane separation is discharged into the atmosphere or recycled, the waste gas discharged after the second membrane separation is pressurized and returned to the first membrane separation, and the waste gas discharged after the third membrane separation is pressurized and returned to the first membrane separation; The high-purity nitrogen gas portion of step (1) enters the first membrane separation and merges with the dehydrogenated neon and helium gas; The impurity adsorption in step (2) includes adsorption and regeneration performed simultaneously. During the adsorption process, the temperature is controlled at -100 to -84°C, and during the regeneration process, the temperature is controlled at -10 to 0°C, so as to achieve the decomposition of the adsorbed impurity gas.

10. The purification method according to claim 8, characterized in that The temperature of the catalytic hydrocarbon removal in step (3) is 270-320°C; The carbon dioxide and water adsorption treatment in step (3) includes adsorption and regeneration performed simultaneously. During the regeneration process, the high-purity nitrogen gas in step (1) is heated at 170-200° C. and then enters the water vapor environment formed after the carbon dioxide and water adsorption treatment for purging. The temperature of the nitride removal treatment in step (3) is 320-350°C; The purification treatment in step (3) includes nitrogen and argon adsorption treatment and regeneration analysis performed simultaneously.

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