Laser gas recovery and separation method and device
Through the laser gas recovery and separation method, excessive oxygen dilution and double pressure dual temperature separator are used, combined with low-temperature adsorption and distillation processes, the problem of xenon and krypton gas curing and difficulty in separation during neon gas purification is solved, and the recycling of high-purity neon gas is achieved, which improves the recycling efficiency and reliability.
Patent Information
- Application Number
- CN202510160427.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-13
- Publication Date
- 2025-04-04
AI Technical Summary
In the prior art During neon purification process, xenon and krypton gas tend to cure and block the heat exchanger at low temperatures, and krypton, xenon and argon at high boiling points are not easy to separate, resulting in low neon recovery efficiency.
The laser gas recovery and separation method is adopted to dilute the concentrations of krypton and xenon in the gas-liquid separator for excessive oxygen to prevent their low-temperature freezing. Two gas source separators of double pressure and double temperature are used to separate krypton, xenon, oxygen and argon under different pressures, and combine low-temperature adsorption, deep freezing and ultra-low-temperature liquefaction and distillation separation processes to achieve high purity recovery of neon gas.
It effectively prevents the low-temperature freezing of krypton and xenon, and improves the recovery and extraction rate of neon gas to reach more than 93%. It is similar to the extraction rate of neon helium raw materials in the space separation device, which improves the reliability of neon gas recovery and separation.
Smart Images
Figure CN119755918A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of neon gas recovery, and in particular relates to a laser gas recovery and separation method and device. Background Art
[0002] Neon gas is used in scientific research, chips, medicine and high-tech industries, especially with the rapid development of chip and other industries, which consume a lot of it. Neon gas can be used to produce neon lasers, which are used in scientific research, medical treatment and material processing.
[0003] After the use of the photolithography machine, the laser gas is not only enriched with neon, krypton, xenon, and argon, but also with some air and hydrogen. In order to obtain high-purity neon, it is necessary to remove other substances such as neon, krypton, xenon, and argon. In the relevant technology, xenon solidifies at around -112°C and krypton solidifies at around -157°C under normal pressure. In the neon purification process, there is a risk of solidification clogging the heat exchanger due to the high concentration of krypton and xenon at low temperatures, and after the temperature is increased, krypton, xenon, and argon with high boiling points are not easy to separate. Summary of the invention
[0004] The purpose of the present invention is to provide a laser gas recovery and separation method and device to solve the problems in the prior art.
[0005] To this end, the present invention provides a laser gas recovery and separation method and device, comprising: A laser gas recovery and separation method, comprising: S100, the recycled laser gas raw material is mixed with excess oxygen and then enters a hydrogen removal catalyst furnace to remove hydrogen. The mixed gas after hydrogen removal enters an adsorber to remove moisture; S200, the dehydrated mixed gas enters the compressor for compression and then enters the first cold box, the mixed gas enters the heat exchanger for cooling to the liquefaction temperature, enters the first gas-liquid separator for the first separation of impurity gas, and the first gas-liquid separator transports the roughly dehydrated mixed gas to the second cold box; S300, in the second cold box, the mixed gas after the crude degassing is cooled to a first preset temperature, and then enters the second gas-liquid separation to separate the impurity gas for a second time. After the impurity gas is removed, the crude degassing gas is reheated to room temperature and then discharged from the second cold box; S400, the crude neon gas enters the compressor for compression and then enters the third cold box, the crude neon gas is cooled to a second preset temperature and enters the condenser evaporator after throttling and reducing pressure, the crude neon gas is condensed into liquid, the liquid crude neon gas enters the distillation tower for distillation to obtain high-purity liquid neon, the high-purity liquid neon is reduced in pressure and then enters the condenser evaporator for evaporation and then reheated to room temperature to obtain high-purity neon gas.
[0006] As a further description of the above technical solution, in step S100, the recovered laser gas raw material is recovered into the exhaust chamber and then enters the air storage bag, and the recovered laser raw material gas in the air storage bag is transported to the recovery container through the recovery compressor, and the recovered laser gas raw material in the recovery container is mixed with oxygen.
[0007] As a further description of the above technical solution, in step S300, the first preset temperature is less than -196°C, and in step S400, the second preset temperature is -220°C.
[0008] As a further description of the above technical solution, in step S200, the mixed gas enters the compressor and is compressed to 3-20 MPa, and in step S400, the raw neon gas enters the compressor and is compressed to 6-20 MPa, and is reduced in pressure to less than 3 MPa.
[0009] As a further description of the above technical solution, in step S200, the cold source required for liquefying and separating the mixed gas in the first cold box is external liquid nitrogen and low-temperature nitrogen recovered by the heat exchanger in the second cold box.
[0010] As a further description of the above technical solution, in step S300, the mixed gas after rough degassing is cooled by an immersion heat exchanger in liquid nitrogen or cryogenic nitrogen at negative pressure.
[0011] As a further description of the above technical solution, at least one second cold box is provided.
[0012] As a further description of the above technical solution, in step S100, the adsorber includes a first adsorber and a second adsorber, and in step S300, the gas separated by the second gas-liquid separator enters the denitrification oxygen adsorber.
[0013] A laser gas recovery and separation device is used to execute any of the laser gas recovery and separation methods described above.
[0014] Beneficial effects: 1. The present invention uses excess oxygen to dilute the krypton and xenon concentrations in the liquid of the gas-liquid separator, thereby preventing the krypton and xenon from freezing at low temperatures at high concentrations.
[0015] 2. The present invention adopts dual-pressure and dual-temperature gas source separators to effectively separate krypton, xenon, oxygen and argon at two pressures of 5MPa and 3MPa.
[0016] 3. The present invention liquefies the recovered laser gas through low-temperature adsorption, deep freezing and ultra-low temperature liquefaction and distillation separation process routes, and separates krypton, xenon, oxygen and argon from crude neon through a flash evaporation method, which greatly reduces and improves the recovery and extraction rate of neon gas by more than 93%, reaching the same technical indicators as the extraction rate of air separation devices in separating neon and helium raw materials, and improving the reliability of neon gas recovery and separation. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0018] Figure 1 The present invention provides a flow chart of a laser gas recovery and separation method.
[0019] Figure 2 This is a schematic diagram of a laser gas recovery and separation device provided by the present invention.
[0020] Figure 3 A schematic diagram of a mixed gas dehydration part in a laser gas recovery and separation device provided by the present invention; Figure 4 A schematic diagram of the first separation of impurity gas from mixed gas in a laser gas recovery and separation device provided by the present invention; Figure 5 A schematic diagram of secondary separation of impurity gases from mixed gas in a laser gas recovery and separation device provided by the present invention; Figure 6 A schematic diagram of obtaining high-purity neon gas in a laser gas recovery and separation device provided by the present invention; Figure 7 A schematic diagram of another embodiment of a laser gas recovery and separation device provided by the present invention.
[0021] In the figure: F101, hydrogen removal catalyst furnace; X201, X202, dehydration adsorber; A201, deoxygenation and nitrogen adsorber; E101, E201, E202, E301, E302, E303, heat exchanger; E304, condenser evaporator; S101, S201, gas-liquid separator; CP1, CP2, CP3, compressor; B101, first cold box; B201, second cold box; B301, third cold box; T301, distillation tower; V01-V25, valves. DETAILED DESCRIPTION
[0022] The content of the present invention can be more easily understood by selecting the following detailed description of the preferred implementation method of the present invention and the embodiments included. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those of ordinary skill in the art to which the present invention belongs. When there is a conflict, the definition in this specification shall prevail.
[0023] like Figure 1-5 As shown, a laser gas recovery and separation method comprises: S100, the mixed laser gas after the photolithography machine is recycled to the exhaust chamber and then enters the gas storage bag, which contains (96.5% Ne, 1.75% Ar, 10ppm Xe, 1.23% Kr and O2, N2, H2O, H2 and trace He), and is compressed to 0.4MPa by the recovery compressor CP1 and enters the recovery container. The recovery container continuously provides 40NM3 / h, 0.4MPa of recycled laser gas raw materials and 30NM3 / h of oxygen from the oxygen tank through valve V02, and then mixes with excess oxygen and enters the dehydrogenation catalyst furnace. After hydrogen is removed in the dehydrogenation catalyst furnace, it enters the first adsorber and the second adsorber to remove moisture. By using excess oxygen to dilute the krypton and xenon concentrations in the gas-liquid separator liquid, krypton and xenon can be effectively prevented from freezing at low temperatures at high concentrations.
[0024] S200, the dehydrated recovered laser gas enters the compressor CP2 and is compressed to 5.5MPa, then enters the first cold box B101 through valve V03, and is cooled to -160°C in the heat exchanger E101, and then is depressurized to 5MPa through valve V04 and enters the gas-liquid separator S101 to separate the recovered laser gas in the gas-liquid separator. The separated heavy components (~23.2NM3 / h, 7.5%Ne, 2.2%Ar, 17ppmXe, 1.99%Kr and 88%O2 and trace N2) are depressurized through valve V05 and returned to the heat exchanger E101 to be reheated to room temperature and discharged or recycled; The non-condensable crude neon (79.2% Ne, 0.65% Ar, 0.03ppm Xe, 682ppm Kr and 20.07% O2 and trace amounts of N2 and He) is extracted from the gas phase of the gas-liquid separator S101 and then decompressed to 3MPa through valve V06 and enters the second cold box B201. S300, the laser gas raw material after the rough removal of krypton and xenon is cooled to -206℃ in the immersion heat exchanger E201 in 20KPa liquid nitrogen, and enters the gas-liquid separator S201 to separate most of the high-boiling point impurities such as oxygen, argon, nitrogen, krypton, xenon, etc., and then the crude neon (99.69% Ne, 194ppm Ar, 0.173ppm Kr and 0.283% O2 and trace amounts of N2 and He) is extracted from the gas phase of the gas-liquid separator S201 and enters the adsorber A201 to remove the residual oxygen, argon, nitrogen, krypton, xenon and other impurities, and then is reheated to room temperature through the heat exchanger E202 and exits the second cold box.
[0025] S400, the crude neon gas from the second cold box B201 is combined with the pure neon and impure neon returned from the third cold box B301, compressed to 9.0MPa by compressor CP3 and then enters the third cold box B301, cooled to about -220℃ and throttled to 3MPa by heat exchangers E301, E302 and E303, and enters the condenser evaporator E304. Most of the crude neon is condensed into liquid and decompressed to low pressure by valve V09 and then enters the distillation tower T301 for distillation. High-purity liquid neon (99.9999% Ne) is obtained in the bottom of the tower. The liquid neon is decompressed to 0.05MPa by throttle valve V10 and then enters the condenser evaporator E304 for evaporation. After being reheated to room temperature by heat exchangers E303 and E301, part of the neon gas returns to compressor CP3, and part of the high-purity neon gas passes through valve V11. The 99.9999% Ne high-purity neon gas is compressed and filled and recycled as a raw material for laser gas.
[0026] Optionally, the gas phase from the top of the distillation tower T301 is extracted and reheated to room temperature through the heat exchangers E303 and E301, and then refluxed to the compressor CP3 through the V13 valve for recycling.
[0027] Optionally, liquid nitrogen (-193.6°C, 0.03MPa) is used as a cooling supplement for the third cold box B301, enters the heat exchanger E302 to evaporate, and cools the raw crude neon 304 to below -193°C, supplementing the high-temperature cooling required for neon liquefaction and distillation.
[0028] Optionally, liquid nitrogen is used as a source of low-temperature cooling in the second cold box B201, so that the gas-liquid separator S201 and the adsorber A201 are immersed in liquid nitrogen, and the evaporated nitrogen is evacuated to about 20kPa by the vacuum pump P201 to maintain the liquid nitrogen temperature at -206°C. The liquid nitrogen is discharged through valve V25 during the thawing stage. Normal temperature nitrogen is supplemented through valve V21, and 0.4MPa is used to recover low-temperature cooling. After the nitrogen is cooled to -179°C, the nitrogen enters the heat exchanger E101 in the first cold box C101 and is reheated to room temperature to recover cooling. The reheated nitrogen is supplemented with the heat exchanger E101, and the 0.4MPa liquid nitrogen is reheated to room temperature and then used as the regeneration gas for the adsorber X201 / X202. The excess nitrogen 407 is vented.
[0029] Optionally, the gaseous low-temperature crude neon gas from the gas-liquid separator S101 enters the coil heat exchanger E201 in the second cold box B201 after exiting the first cold box B101. The coil heat exchanger E201 is directly immersed in liquid nitrogen or in low-temperature nitrogen for heat exchange to prevent trace krypton and xenon from freezing and clogging the heat exchanger at low temperatures. The cooled crude helium separates most of the oxygen, nitrogen and argon in the gas-liquid separator S201 and enters the deoxygenation nitrogen adsorber A201 to adsorb the remaining impurities such as oxygen, argon, nitrogen, krypton, and xenon.
[0030] Optionally, in some embodiments, the first cold box B101 and the second cold box B201 may be combined into one cold box. Specifically, the heat exchanger E101 and the gas-liquid separator S101 in the first cold box B101 may be disposed in the second cold box B201.
[0031] Optionally, in some embodiments, the second cold box B201 can be one or more and can be switched to ensure the continuity of the work of removing impurities such as oxygen, argon, nitrogen, krypton, and xenon.
[0032] refer to Figure 7 In some embodiments, a laser gas recovery and separation method is used. When the laser gas recovered by the laser machine is not mixed with helium, high-purity neon gas can be directly obtained in the neon gas pipeline of the heat exchanger in the second cold box B201 through the above method. Therefore, in some embodiments, the third cold box B301 can be eliminated, which can further save the investment in hardware costs.
[0033] refer to Figure 2 , a laser gas recovery and separation device, which is used to perform the above-mentioned laser gas recovery and separation method.
[0034] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A laser gas recovery and separation method, characterized in that: include: S100, the recycled laser gas raw material is mixed with excess oxygen and then enters a hydrogen removal catalyst furnace to remove hydrogen. The mixed gas after hydrogen removal enters an adsorber to remove moisture; S200, the dehydrated mixed gas enters the compressor for compression and then enters the first cold box, the mixed gas enters the heat exchanger for cooling to the liquefaction temperature, enters the first gas-liquid separator for the first separation of impurity gas, and the first gas-liquid separator transports the roughly dehydrated mixed gas to the second cold box; S300, in the second cold box, the mixed gas after crude degassing is cooled to a first preset temperature by a liquid nitrogen immersion heat exchanger, and then enters the second gas-liquid separator for secondary separation of impurity gases, and the crude degassing extracted from the second gas-liquid separator enters the adsorber to remove residual impurity gases, and then the crude degassing gas is reheated to room temperature and discharged from the second cold box; S400, the crude neon gas enters the compressor for compression and then enters the third cold box, the crude neon gas is cooled to a second preset temperature and enters the condenser evaporator after throttling and reducing pressure, the crude neon gas is condensed into liquid, the liquid crude neon gas enters the distillation tower for distillation to obtain high-purity liquid neon, the high-purity liquid neon is reduced in pressure and then enters the condenser evaporator for evaporation and then reheated to room temperature to obtain high-purity neon gas.
2. The laser gas recovery and separation method according to claim 1, characterized in that: In step S100, the recovered laser gas raw material is recovered to the exhaust chamber and then enters the gas storage bag. The recovered laser gas raw material in the gas storage bag is transported to the recovery container through the recovery compressor, and the recovered laser gas raw material in the recovery container is mixed with oxygen.
3. The laser gas recovery and separation method according to claim 1, characterized in that: In step S300, the first preset temperature is less than -196°C, and in step S400, the second preset temperature is -220°C.
4. The laser gas recovery and separation method according to claim 1, characterized in that: In step S200, the mixed gas enters the compressor and is compressed to 3-20 MPa. In step S400, the raw neon gas enters the compressor and is compressed to 6-20 MPa, and is then decompressed to less than 3 MPa.
5. The laser gas recovery and separation method according to claim 4, characterized in that: In step S200, the cold source required for liquefying and separating the mixed gas in the first cold box is external liquid nitrogen and low-temperature nitrogen recovered by the heat exchanger in the second cold box.
6. The laser gas recovery and separation method according to claim 1, characterized in that: In step S300, the mixed gas after rough degassing is cooled by an immersion heat exchanger in liquid nitrogen or cryogenic nitrogen at negative pressure.
7. The laser gas recovery and separation method according to claim 1, characterized in that: The second cold box is provided with at least one.
8. The laser gas recovery and separation method according to claim 1, characterized in that: In step S100, the adsorber includes a first adsorber and a second adsorber. In step S300, the gas separated by the second gas-liquid separator enters the denitrification and oxygen adsorber.
9. A laser gas recovery and separation device, characterized in that: It is used to implement the laser gas recovery and separation method described in any one of claims 1 to 8.