CN102311103B - Helium purifying method and purifying device thereof - Google Patents
Helium purifying method and purifying device thereof Download PDFInfo
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- CN102311103B CN102311103B CN201110198460.6A CN201110198460A CN102311103B CN 102311103 B CN102311103 B CN 102311103B CN 201110198460 A CN201110198460 A CN 201110198460A CN 102311103 B CN102311103 B CN 102311103B
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- 229910052734 helium Inorganic materials 0.000 title claims abstract description 177
- 239000001307 helium Substances 0.000 title claims abstract description 177
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000001179 sorption measurement Methods 0.000 claims abstract description 127
- 239000001257 hydrogen Substances 0.000 claims abstract description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 60
- 239000001301 oxygen Substances 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910001868 water Inorganic materials 0.000 claims abstract description 60
- 239000012535 impurity Substances 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 28
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002594 sorbent Substances 0.000 claims description 22
- 235000011089 carbon dioxide Nutrition 0.000 claims description 20
- 230000008676 import Effects 0.000 claims description 16
- 230000000274 adsorptive effect Effects 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 2
- 230000009466 transformation Effects 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 description 63
- 238000010521 absorption reaction Methods 0.000 description 22
- 238000001816 cooling Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000002826 coolant Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 238000003795 desorption Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000013307 optical fiber Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000001914 calming effect Effects 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002371 helium Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Landscapes
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention provides a method and a device for purifying helium into high purity with a lower cost by effectively reducing the impurity content ratio in recycled helium. The method for purifying helium with impurities at least including such as hydrogen, carbon monoxide, nitrogen and oxygen comprises the steps of making the oxygen, the hydrogen and the carbon monoxide in the helium react with each other and generate carbon dioxide and water, leaving the oxygen as residue; adding hydrogen so as to make the hydrogen mol concentration twice higher than the oxygen mol concentration, then make oxygen react with the hydrogen so as to generate water with the hydrogen remained; making the hydrogen in the helium react with the metal oxide after a dehydration operation and generating water; at least absorbing nitrogen, carbon dioxide and water in the impurities by a transformation adsorption method through zeolite type adsorbents; and then at least absorbing nitrogen by a changing temperature adsorption method with a temperature ranging from -10 DEG to -50 DEG.
Description
Technical field
At least contain hydrogen, carbon monoxide, the nitrogen that derives from air and the oxygen that the present invention relates to be suitable for helium of recovery after for example using in the manufacturing process of optical fiber and so on carry out the method and apparatus of purifying as the helium of impurity.
Background technology
After for example using, using, be distributed to the helium in atmosphere in the wire-drawing process of optical fiber, sometimes by its recycling.Above-mentioned recovery helium contains the hydrogen of sneaking in the wire-drawing process of optical fiber, carbon monoxide, by the nitrogen that derives from air of sneaking in being distributed to atmosphere after using and oxygen etc. as impurity, therefore need to carry out purifying improves purity.
So, known following method: by using liquid nitrogen as refrigeration source cryogenic operations the liquefaction of impurity contained in the helium before purifying is removed, by sorbent material, remaining trace impurity absorption is removed to (with reference to patent documentation 1).Known following method also: add hydrogen in the helium before purifying, make this hydrogen react and generate moisture with the oxygen in air composition as impurity, remove residual impurity (with reference to patent documentation 2) by membrane separating method after removing this moisture.Known following method also: impurity contained in the rare gas such as helium before purifying is contacted with alloy degasser, thereby be removed (with reference to patent documentation 3).
Patent documentation 1: Japanese patent laid-open 10-311674 communique
Patent documentation 2: Japanese Patent Laid-Open 2003-246611 communique
Patent documentation 3: Japanese patent laid-open 4-209710 communique
Summary of the invention
In the method that patent documentation 1 is recorded, because need to carry out cryogenic operations with liquid nitrogen, so cooling energy increases; In the method that patent documentation 2 is recorded, because need membrane sepn module, equipment cost is high; The recovery income of the helium of any method is all less.In addition, in the method that patent documentation 2 is recorded, by adding hydrogen in the helium as purifying object, remove deoxidation, but and reckon without fully removing of hydrogen, may because hydrogen causes the material of deteriorated aggravation, cause detrimentally affect to the meeting of optical fiber starting material and so on.In the method that patent documentation 3 is recorded because alloy degasser ability little, so can only, for being the situation that the low-purity helium of ppm level is purified to ultra-high purity by impurity concentration, cannot be directly used in the more polymictic situation of sneaking into.
Method of the present invention is characterised in that, to at least containing hydrogen, carbon monoxide, when deriving from the nitrogen of air and oxygen and carrying out purifying as the helium of impurity, utilize catalyzer to make the oxygen in described helium, hydrogen, and reaction of carbon monoxide, thereby the state with residual aerobic generates carbonic acid gas and water, then add hydrogen, make the hydrogen volumetric molar concentration in described helium reach the value of 2 times higher than oxygen volumetric molar concentration, then utilize catalyzer to make oxygen and the H-H reaction in described helium, thereby generate water to remain the state of hydrogen, then by dehydration operation, reduce the moisture containing ratio of described helium, then make hydrogen and reactive metal oxide in described helium, thereby generation water, then, by using the pressure swing adsorption process of zeolites sorbent material at least to adsorb the nitrogen in the impurity in described helium, carbonic acid gas and water, then the Temp .-change adsorptive process by-10 ℃～-50 ℃ at least adsorbs the nitrogen in the impurity in described helium.
According to the present invention, first utilize catalyzer to make a part, hydrogen and the reaction of carbon monoxide of the oxygen as impurity contained in helium, with the state of residual aerobic, generate carbonic acid gas and water.By this, the hydrogen in helium and carbon monoxide react with oxygen, thereby are removed.Then, make oxygen and the H-H reaction of adding in helium, thereby generate water to remain the state of hydrogen.The addition of this hydrogen with in theory with helium in the required hydrogen amount of institute's aerobic reaction compare slightly excessive, by this by reducing residual hydrogen amount with reacting of oxygen.Then, by dehydration operation, reduce the moisture containing ratio of helium.By this, oxygen and water in helium are removed, and can reduce the absorption load of moisture.Then make hydrogen and reactive metal oxide in helium, thereby generate water.This hydrogen had been implemented dehydration operation with reacting of metal oxide before reacting, and therefore can prevent that reaction from being suppressed by moisture.By this, the hydrogen in helium is removed, and can tackle the situation that requires to reduce hydrogen.In addition, the major impurity of helium is nitrogen, a small amount of carbonic acid gas and a small amount of water.Therefore, can easily by pressure swing adsorption process, reduce gas concentration lwevel and moisture containing ratio.Because can be by improve the adsorption effect of nitrogen with zeolites sorbent material in this pressure swing adsorption process, so can reduce the nitrogen absorption load in follow-up Temp .-change adsorptive process.And, because can be without adopting Temp .-change adsorptive process to carry out adsorb oxygen, so the temperature in the time of can the adsorption temp of impurity being increased to higher than adsorb oxygen.Therefore, can be in the situation that the cooling energy while not increasing adsorption treatment improves the rate of recovery and the purity of helium.
Device of the present invention be at least containing hydrogen, carbon monoxide, the nitrogen and the oxygen that derive from air carries out the device of purifying as the helium of impurity, it is characterized in that, comprising: the first reactor, imports and have described helium in this first reactor, the second reactor, imports in this second reactor and has the helium flowing out from described the first reactor, hydrogen concentration setting device, this hydrogen concentration setting device is set as the value of 2 times higher than oxygen volumetric molar concentration by adding hydrogen by the hydrogen volumetric molar concentration in the described helium importing in described the second reactor, water extracter, this water extracter reduces the moisture containing ratio of the described helium flowing out from described the second reactor by carrying out dehydration operation, the 3rd reactor, imports and has the described helium that has reduced moisture containing ratio by described water extracter in the 3rd reactor, adsorption unit, this adsorption unit is connected with described the 3rd reactor, in described the first reactor, be filled with catalyzer, make the oxygen in described helium in described the first reactor, hydrogen and carbon monoxide react, thereby generate water and carbonic acid gas, in described the second reactor, be filled with catalyzer, make oxygen and H-H reaction in described helium in described the second reactor, thereby generate water to remain the state of hydrogen, in described the 3rd reactor, be filled with metal oxide, make the hydrogen in described helium in described the 3rd reactor oxidation occur and generate water, described adsorption unit has PSA unit and TSA unit, this PSA unit is by being used the pressure swing adsorption process of zeolites sorbent material at least to adsorb the nitrogen in the impurity the described helium flowing out from described the 3rd reactor, carbonic acid gas and water, this TSA unit at least adsorbs the nitrogen in the impurity in described helium by the Temp .-change adsorptive process of-10 ℃～-50 ℃.
If adopt device of the present invention, can implement method of the present invention.
Utilize the present invention, can in the situation that effectively reduce and at least sneak into hydrogen, carbon monoxide, derive from the nitrogen of air and oxygen as the impurity containing ratio in the helium of impurity without a large amount of purifying energy, thereby provide, can helium be purified to low cost to the method and apparatus of highly purified practicality.
Accompanying drawing explanation
Fig. 1 is the structure explanatory view of the helium purification devices of embodiments of the present invention.
Fig. 2 is the structure explanatory view of the pressure-swing absorption apparatus in the helium purification devices of embodiments of the present invention.
Fig. 3 is the structure explanatory view of the Temp .-changing adsorption device in the helium purification devices of embodiments of the present invention.
The explanation of symbol
α: purification devices, 2: well heater, 3: the first reactors, 4: the second reactors, 5: hydrogen concentration setting device, 6: water extracter, 7: the three reactors, 9: adsorption unit, 10:PSA unit, 20:TSA unit
Embodiment
Helium purification devices α shown in Fig. 1 comprises: as supply source 1, well heater 2, the first reactor 3, the second reactor 4, hydrogen concentration setting device 5, water extracter 6, the 3rd reactor 7, water cooler 8, the adsorption unit 9 of the helium of purifying object.
The helium as purifying object of supplying with from supply source 1, by the not shown dedustings such as strainer, imports well heater 2 via the gas transport unit such as gas blower (omitting diagram).Helium as purifying object is considered at least to contain hydrogen, carbon monoxide, derive from the nitrogen of air and oxygen as impurity, but also can contain other trace impurity.In the present invention, the hydrogen as impurity and carbon monoxide contained in the helium as purifying object are included in hydrogen and the carbon monoxide that in air, trace contains, but mainly not derive from air, but sneak in the environment for use of helium.For example, by in the situation that be distributed to the helium recovery in atmosphere after using in the wire-drawing process of light, the nitrogen and oxygen that derive from air of sneaking into when containing the hydrogen of sneaking into and carbon monoxide and reclaim in wire-drawing process in helium, also contain the trace impurity of negligible degree such as deriving from the carbonic acid gas of this air and hydrocarbon.In helium as purifying object, sneak in the situation of air and can contain argon, but because the content of airborne argon is lower than oxygen and nitrogen, and the purposes of purified helium has been utilized as replacing with argon gas in the situation of the characteristic of rare gas element, so can not ignore it using argon as impurity.The concentration of the impurity in the helium being purified is not particularly limited, for example, be 1 % by mole～60 % by mole left and right.For the reaction in each reactor 3,4,7 is carried out completely, the temperature heating with 2 pairs of helium of well heater is preferably more than 250 ℃, and from preventing the angle of the lost of life of catalyzer, described temperature is preferably below 400 ℃.
The helium of heater via 2 heating is imported into the first reactor 3.In the first reactor 3, be filled with the catalyzer that makes oxygen and hydrogen and reaction of carbon monoxide.By this, oxygen, hydrogen and carbon monoxide contained in the helium in the first reactor 3 react, thereby generate water and carbonic acid gas with the state of residual aerobic.As long as the catalyzer being filled in the first reactor 3 makes oxygen and hydrogen and reaction of carbon monoxide, be not particularly limited, can use such as the precious metals such as platinum, platinum alloy, palladium being carried on to aluminum oxide etc. catalyzer.In addition, the helium of recovery contains the hydrocarbon as combustible component, and this hydrocarbon is oxidized carbonic acid gas and the water of resolving in the first reactor 3, but because its volumetric molar concentration is few, only for number molar ppm left and right, so can impact hardly residual oxygen amount.
The helium flowing out from the first reactor 3 is imported into the second reactor 4.The effect of hydrogen concentration setting device 5 is, by adding hydrogen, the hydrogen volumetric molar concentration in the helium importing in the second reactor 4 is set as to the value of 2 times higher than oxygen volumetric molar concentration.The hydrogen concentration setting device 5 of present embodiment has density measuring device 5a, hydrogen supply source 5b, hydrogen amount regulator 5c, controller 5d.Density measuring device 5a measures the oxygen volumetric molar concentration in the helium that imports the second reactor 4, and its measured signal is sent to controller 5d.Controller 5d by with hydrogen volumetric molar concentration in helium is reached higher than control signal corresponding to the required hydrogen amount of the value of 2 times of measured oxygen volumetric molar concentration be sent to hydrogen amount regulator 5.Hydrogen amount regulator 5c carries out aperture adjustment to the stream from hydrogen supply source 5b to the second reactor 4, thereby supplies with the hydrogen of the amount corresponding with control signal.By this, the hydrogen volumetric molar concentration as in the helium of purifying object in the second reactor 4 reaches the value of 2 times higher than oxygen volumetric molar concentration.Better by utilizing hydrogen concentration setting device 5 to add hydrogen in helium, make hydrogen volumetric molar concentration in helium reach the value of 2.05 times～2.10 times of oxygen volumetric molar concentration, by this value is reached more than 2.05 times, can reduce reliably oxygen, by this value is reached below 2.10 times, the hydrogen concentration in helium can be not too high.
In the second reactor 4, be filled with the catalyzer that makes oxygen and H-H reaction.By this, oxygen and H-H reaction in the helium in the second reactor 4, generate water to remain the state of hydrogen.As long as the catalyzer being filled in the second reactor 4 makes oxygen and H-H reaction, be not particularly limited, can use such as the precious metals such as platinum, platinum alloy, palladium being carried on to aluminum oxide etc. catalyzer.
Water extracter 6 reduces the moisture containing ratio of the helium flowing out from the second reactor 4 by carrying out dehydration operation.As water extracter 6, such as can with to helium pressurization and by sorbent material remove the adding pressure type dewatering unit that under reduced pressure makes adsorbent reactivation after moisture, by helium pressurize the cooling freezing type dewatering unit of removing the moisture of condensation, by dewatering agent, remove after moisture contained in helium thermal regeneration formula dewatering unit that to dewatering agent heating makes its regeneration etc.From the viewpoint of effectively reducing moisture containing ratio, preferred thermal regeneration formula dewatering unit, as long as can remove moisture contained in helium approximately 99% left and right.
The helium that has reduced moisture containing ratio by water extracter 6 is imported into the 3rd reactor 7.In the 3rd reactor 7, be filled with metal oxide, make the hydrogen in the interior described helium of the 3rd reactor 7 oxidation occur and generate water.By this, the hydrogen in the helium in the 3rd reactor 7 and reactive metal oxide and generate water.As long as the metal oxide being filled in the 3rd reactor 7 can generate with H-H reaction water, preferably be carried on the commercially available product of aluminum oxide etc., for example can use cupric oxide and zinc oxide are carried on to aluminum oxide and metal oxide or nickel oxide is carried on to aluminum oxide and metal oxide.Temperature of reaction in the 3rd reactor 7 is 200～300 ℃ of left and right preferably.
The 3rd reactor 7 is situated between and is connected with adsorption unit 9 with water cooler 8.The helium flowing out from the 3rd reactor 7 device 8 that is cooled is imported into adsorption unit 9 cooling.Adsorption unit 9 has 10HeTSA unit, PSA unit 20.PSA unit 10 at least adsorbs nitrogen, carbonic acid gas and the water in the impurity in helium by the pressure swing adsorption process under the normal temperature of use zeolites sorbent material.TSA unit 20 at least adsorbs the nitrogen in the impurity in helium by the Temp .-change adsorptive process of-10 ℃～-50 ℃.
PSA unit 10 can be used known unit.Example PSA unit 10 is as shown in Figure 2 four-tower, has compressor 12 and the four first～the 4th adsorption tower 13 that the argon gas to flowing out from the 3rd reactor 7 compresses, in each adsorption tower 13, is filled with zeolites sorbent material.As this zeolites sorbent material, the zeolite molecular sieve of preferred nitrogen advantages of good adsorption effect.
Compressor 12 is situated between and is connected with the entrance 13a of each adsorption tower 13 with transforming valve 13b.
The entrance 13a of adsorption tower 13 is situated between respectively and is connected in atmosphere with transforming valve 13e and sourdine 13f.
The outlet 13k of adsorption tower 13 is situated between respectively and is connected with outflow pipeline 13m with transforming valve 13l, Jie is connected with the pipeline 13o that boosts with transforming valve 13n, Jie cleans out side pipe road 13q and is connected with all pressing with transforming valve 13p, is situated between and cleans into side pipe road 13s and be connected with equal pressures with transforming valve 13r.
Flow out pipeline 13m and be situated between and be connected with TSA unit 20 with pressure regulator valve 13t, make to import the constant pressure of the helium of TSA unit 20.
The pipeline 13o that boosts is situated between and is connected with outflow pipeline 13m with flowrate control valve 13u, flow indication accommodometer 13v, and the flow boosting in pipeline 13o is adjusted to constant, thereby prevents from importing the fluctuations in discharge of the helium of TSA unit 20.
All press to clean out side pipe road 13q and all press to clean into side pipe road 13s to be situated between and to interconnect with a pair of connecting tube 13w, each connecting tube 13w is provided with transforming valve 13x.
In first of PSA unit 10～four adsorption tower 13, carry out successively respectively absorption process, decompression I operation (purge gas goes out operation), decompression II operation (body of all calming the anger goes out operation), desorption step, matting (purge gas enters operation), the I operation of boosting (body of all calming the anger enters operation), the II operation of boosting.
That is, in the first adsorption tower 13, only transforming valve 13b and transforming valve 13l open, and the helium of supplying with from the 3rd reactor 7 imports the first adsorption tower 13 from compressor 12 through transforming valve 13b.By this, in the helium importing in the first adsorption tower 13, at least nitrogen, carbonic acid gas, moisture are adsorbed on sorbent material, thereby carry out absorption process, and the helium after impurity containing ratio reduces is delivered to TSA unit 20 from the first adsorption tower 13 through flowing out pipeline 13m.At this moment, a part that is sent to the helium that flows out pipeline 13m is delivered to other adsorption tower (being the second adsorption tower 13 in present embodiment), the II operation of boosting in the second adsorption tower 13 through the pipeline 13o that boosts, flowrate control valve 13u.
Then, close transforming valve 13b, the 13l of the first adsorption tower 13, open transforming valve 13p, open the transforming valve 13r of other adsorption tower (being the 4th adsorption tower 13 in present embodiment), open 1 in transforming valve 13x.By this, the less helium of the impurity containing ratio on the first adsorption tower 13 tops is delivered to the 4th adsorption tower 13 through all pressing to clean into side pipe road 13s, and I operation reduces pressure in the first adsorption tower 13.At this moment, in the 4th adsorption tower 13, transforming valve 13e opens, and carries out matting.
Then, opening under the state of the transforming valve 13p of the first adsorption tower 13 and the transforming valve 13r of the 4th adsorption tower 13, close the transforming valve 13e of the 4th adsorption tower 13, thereby carry out gas recovery to the four adsorption towers 13 until the mutual homogeneous of internal pressure or the decompression II operation of homogeneous roughly between the first adsorption tower 13 and the 4th adsorption tower 13.At this moment, transforming valve 13x can according to circumstances open 2.
Then, open the transforming valve 13e of the first adsorption tower 13, close transforming valve 13p, thereby carry out the desorption step from sorbent material desorb by impurity, impurity is released in atmosphere through sourdine 13f together with gas.
Then, open the transforming valve 13r of the first adsorption tower 13, close transforming valve 13b, the 13l of the second adsorption tower 13 of the state after absorption process finishes, open transforming valve 13p.By this, the less helium of the impurity containing ratio on the second adsorption tower 13 tops is delivered to the first adsorption tower 13 through all pressing to clean into side pipe road 13s, in the first adsorption tower 13, carries out matting.Matting gas used in the first adsorption tower 13 is released in atmosphere through transforming valve 13e, sourdine 13f.At this moment, the I operation that reduces pressure in the second adsorption tower 13.Then, under the state of opening the transforming valve 13p of the second adsorption tower 13 and the transforming valve 13r of the first adsorption tower 13, close the transforming valve 13e of the first adsorption tower, thereby boost I operation.At this moment, transforming valve 13x can according to circumstances open 2.
Then, close the transforming valve 13r of the first adsorption tower 13, temporary transient in the holding state without operation.The II operation of boosting that this holding state continues to the 4th adsorption tower 13 finishes.The end of boosting of the 4th adsorption tower 13, absorption process is from the 3rd adsorption tower 13 switches to the 4th adsorption tower 13, open the transforming valve 13n of the first adsorption tower, from the other adsorption tower in absorption process (being the 4th adsorption tower 13 present embodiment), deliver to a part for the helium that flows out pipeline 13m and through the pipeline 13o that boosts, flowrate control valve 13u, deliver to the first adsorption tower 13, the II operation of boosting in the first adsorption tower 13.
By repeatedly carry out successively respectively each above-mentioned operation in the first～four adsorption tower 13, the helium after impurity containing ratio reduces is delivered to TSA unit 20 continuously.
Also have, PSA unit 10 is not limited to the unit shown in Fig. 2, and for example tower number can be the number beyond 4, and for example 2 or 3.
TSA unit 20 can be used known unit.TSA unit 20 as shown in Figure 3 of example is two tower, there is heat exchange type pre-cooler 21 that helium to sending here from PSA unit 10 carries out precooling, to further carrying out cooling heat exchange type water cooler 22, the first and second adsorption towers 23 through the cooling helium of pre-cooler 21, cover the heat exchange department 24 of each adsorption tower 23.Heat exchange department 24 by the cooling sorbent material of cooling agent, passes through the agent of thermophore heating adsorption when absorption process when desorption step.Each adsorption tower 23 has many inner tubes that are filled with sorbent material.As this sorbent material, use is applicable to the sorbent material of the absorption of nitrogen, preferably using exchange ion is the cationic X-type zeolite of divalent or y-type zeolite, for example can use the zeolites sorbent material that carries out ion-exchange with calcium (Ca) or lithium (Li), this divalent positively charged ion is more preferably selected from least one in magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba).
Water cooler 22 is situated between and is connected with the entrance 23a of each adsorption tower 23 with transforming valve 23b.
The entrance 23a of adsorption tower 23 is situated between respectively and is communicated in atmosphere with transforming valve 23c.
The outlet 23e of adsorption tower 23 is situated between respectively and is connected with outflow pipeline 23g with transforming valve 23f, is situated between and with pipeline 23i, is connected with cooling boosting with transforming valve 23h, is situated between and is connected with cleaning tube road 23k with transforming valve 23j.
A part that flows out pipeline 23g formation pre-cooler 21, the helium of sending here from PSA unit 10 is by the purified helium gas cooling flowing out from flowing out pipeline 23g.Purified helium flows out through transforming valve 23l from flowing out pipeline 23g.
Cooling boosting is situated between and is connected with under meter 23m, flowrate control valve 23o, transforming valve 23n and outflow pipeline 23g with pipeline 23i, cleaning tube road 23k.
Heat exchanger 24 adopts multitube, has outer tube 24a, the cooling agent supply source 24b, cooling agent radiator 24c, thermophore supply source 24d, the thermophore radiator 24e that surround many inner tubes that form adsorption tower 23.In addition, be provided with a plurality of transforming valve 24f, the state circulating with radiator 24c by outer tube 24a, cooling agent for the cooling agent making to supply with from cooling agent supply source 24b and the thermophore of supplying with from thermophore supply source 24d are by changing between outer tube 24a, the state of thermophore with radiator 24e circulation.In addition, by form a part for water cooler 22 with the pipeline of radiator 24c branch from cooling agent, helium is cooling by the cooling agent of supplying with from cooling agent supply source 24b at water cooler 22, and this cooling agent is back to tank 24g.
In first, second adsorption tower 23 of TSA unit 20, carry out successively respectively absorption process, desorption step, matting, refrigerating work procedure, the operation of boosting.
That is,, in TSA unit 20, after the helium of supplying with is cooled pre-cooler 21, water cooler 22, through transforming valve 23b, import the first adsorption tower 23 from PSA unit 10.At this moment, the first adsorption tower 23 is in being cooled to the state of-10 ℃～-50 ℃ by circulating cooling agent in heat exchanger 24, and transforming valve 23c, 23h, 23j close, and transforming valve 23f opens, and at least in helium, contained nitrogen is adsorbed on sorbent material.By this, in the first adsorption tower 23, carry out absorption process, the purifying helium after impurity containing ratio reduces flows out through transforming valve 23l from adsorption tower 23.
During carrying out absorption process in the first adsorption tower 23, in the second adsorption tower 23, carry out desorption step, matting, refrigerating work procedure, the operation of boosting.
That is, in the second adsorption tower 23, after absorption process finishes, in order to implement desorption step, close transforming valve 23b, 23f, open transforming valve 23c.By this, in the second adsorption tower 23, impure helium is released in atmosphere, and pressure drop is to normal atmosphere left and right.In this desorption step, the transforming valve 24f that has the heat exchange department 24 of refrigerant cycle in the second adsorption tower 23 when the absorption process is switched to closing condition and stop the circulation of cooling agent, will cooling agent be discharged and the transforming valve 24f that gets back to cooling agent supply source 24b switches to open mode from heat exchange department 24.
Then, in order to implement matting in the second adsorption tower 23, the transforming valve 23n of transforming valve 23c, the 23j of the second adsorption tower 23 and cleaning tube road 23k is set as open mode, and by the heat exchange in heat exchange type pre-cooler 21, a part for heated purifying helium imports the second adsorption tower 23 through cleaning tube road 23k.By this, in the second adsorption tower 23, implement the desorb of impurity and the cleaning of employing purifying helium of self-absorbent, this cleans helium used and is released into atmosphere together with impurity from transforming valve 23c.In this matting, by the second adsorption tower 23 for making the transforming valve 24f of the heat exchange department 24 of thermophore circulation switch to open mode.
Then, in order to implement refrigerating work procedure in the second adsorption tower 23, the transforming valve 23n of the transforming valve 23j of the second adsorption tower 23 and cleaning tube road 23k is set as closing condition, the transforming valve 23h of the second adsorption tower 23 and cooling boosting are set as open mode with the transforming valve 23n of pipeline 23i, and a part for the purifying helium flowing out from the first adsorption tower 23 imports the second adsorption tower 23 through cooling boosting with pipeline 23i.By this, cooling purifying helium having been carried out in the second adsorption tower 23 inside is released in atmosphere through transforming valve 23c.In this refrigerating work procedure, will stop for making the transforming valve 24f of thermophore circulation switch to closing condition the circulation of thermophore, the transforming valve 24f that makes thermophore get back to thermophore supply source 24d from heat exchange department 24 discharges will be switched to open mode.After thermophore is discharged and to be finished, by the second adsorption tower 23 for making the transforming valve 24f of the heat exchange department 24 of refrigerant cycle switch to open mode, make it be refrigerant cycle state.This refrigerant cycle state continuance to the operation of boosting of following, absorption process thereafter finishes.
Then, in order to implement to boost operation in the second adsorption tower 23, close the transforming valve 23c of the second adsorption tower 23, import a part for the purifying helium flowing out from the first adsorption tower 23, thereby boosted in the inside of the second adsorption tower 23.This operation of boosting continues to the interior pressure of the second adsorption tower 23 and the interior pressure of the first adsorption tower 23 about equally.After the operation of boosting finishes, close transforming valve 23h and cooling the boosting with the transforming valve 23n of pipeline 23i of the second adsorption tower 23, form by this state that all transforming valve 23b, 23c, 23f, 23h, the 23j of the second adsorption tower 23 close, the second adsorption tower 23 keeps holding states to the absorption process of following.
The absorption process of the absorption process of the second adsorption tower 23 and the first adsorption tower 23 is similarly implemented.During carrying out absorption process in the second adsorption tower 23, in the first adsorption tower 23, similarly carry out desorption step, matting, refrigerating work procedure, the operation of boosting with the second adsorption tower 23.
Also have, TSA unit 20 is not limited to the unit shown in Fig. 3, and for example tower number can be more than 2 number, and for example 3 or 4.
Utilize above-mentioned purification devices α, first in the first reactor 3, utilize catalyzer make helium in the contained oxygen as impurity, hydrogen and reaction of carbon monoxide, with the state of residual aerobic, generate carbonic acid gas and water.By this, the hydrogen in helium and carbon monoxide react with oxygen, thereby are removed.Then, in the second reactor 4, make oxygen and the H-H reaction of adding in helium, thereby generate water to remain the state of hydrogen.The addition of this hydrogen can be set as making the hydrogen amount by residual with reacting of oxygen few.Then, by dehydration operation, reduce the moisture containing ratio of helium.By this, the water in helium is removed, and can reduce the water adsorption load of adsorption unit 9.Then, make hydrogen and the reactive metal oxide in helium in the 3rd reactor 7, thereby generate water, this hydrogen had been implemented dehydration operation with reacting of metal oxide before reacting, and therefore can prevent that reaction from being suppressed by moisture.By this, the hydrogen in helium is removed, and can tackle the situation that requires to reduce hydrogen.In addition, the major impurity of helium is nitrogen, a small amount of carbonic acid gas and a small amount of water.Therefore, can be easily by adopting the pressure swing adsorption process of PSA unit 10 to reduce gas concentration lwevel and moisture containing ratio.Can, by improve the adsorption effect of nitrogen with zeolites sorbent material in this pressure swing adsorption process, can reduce the nitrogen absorption load in follow-up Temp .-change adsorptive process.And, because can be without adopting Temp .-change adsorptive process to carry out adsorb oxygen, so the temperature in the time of can the adsorption temp of impurity being increased to higher than adsorb oxygen.Therefore, can be in the situation that the cooling energy while not increasing adsorption treatment improves the rate of recovery and the purity of helium.
Embodiment 1
Use above-mentioned purification devices α to carry out the purifying of helium.In recovery helium used, the nitrogen that contains 23.43 % by mole, the oxygen, the hydrogen of 4500 molar ppm, the carbonic acid gas of the carbon monoxide of 300 molar ppm, 300 molar ppm, the moisture of 20 molar ppm of 6.28 % by mole are as impurity.In the helium reclaiming, contain argon, but ignored, other trace ingredients is also ignored.
The flow that this helium is counted to 3.75L/min with standard state imports the first reactor 3.In the first reactor 3, fill 45mL and be carried on the platina catalyzer of aluminum oxide, reaction conditions is 280 ℃ of temperature, normal atmosphere, space velocity 5000/h.
The remaining oxygen amount of the helium that mensuration flows out from the first reactor 3, imports the second reactor 4 by the hydrogen that makes an addition to helium with the flow of 0.456L/min.The catalyzer that is filled in the second reactor 4 is identical with the first reactor 3 with the temperature of reaction in the second reactor 4, and catalytic amount is 50.6ml, and space velocity is 5000/h.
Use thermal regeneration formula dewatering unit as water extracter 6, carry out dewatered dehydration operation in the helium from being flowed out by the second reactor 4, the moisture containing ratio of helium is reduced to 90 molar ppm.
The helium flowing out from water extracter 6 is imported to the 3rd reactor 7.In the 3rd reactor 7, fill 210mL and be carried on cupric oxide and the zinc oxide (southern chemical catalyst Co., Ltd. (ズ mono-De ケ ミ mono-catalyst) system) of aluminum oxide.Temperature of reaction is 250 ℃, and space velocity is 1000/h.
The helium flowing out from the 3rd reactor 7 is cooling with water cooler 8, with adsorption unit 9, reduce the containing ratio of impurity.
PSA unit 10 is four-tower, is filled with 1.25L as the zeolite molecular sieve (CaA of UOP system) of sorbent material in each tower.Adsorptive pressure is 0.9MPa, and desorption pressures is 0.1MPa.Be 100 seconds cycling time.
Helium through PSA unit 10 purifying is imported to TSA unit 20.TSA unit 20 is two tower, is filled with 1.5L as the CaX type zeolite of sorbent material in each tower, and adsorptive pressure is 0.8MPa, and adsorption temp is-35 ℃, and desorption pressures is 0.1MPa, and desorption temperature is 40 ℃.
From TSA unit, the composition of the 20 purified helium that flow out is shown in following table 1.Because argon contained in the helium as purifying object is ignored, so the helium purity in table 1 is to have removed argon and the purity of trying to achieve.
The oxygen concn of purified helium is used Tai Li dyne technology company (Teledyne Technologies, Inc.) micro amount of oxygen densitometer model 311 processed to measure.Methane concentration is used the GC-FID processed of Shimadzu Scisakusho Ltd (SHIMADZU Corporation) to measure; The concentration of carbon monoxide and carbonic acid gas is used the GC-FID processed of Shimadzu Scisakusho Ltd to measure via methanator equally.Hydrogen concentration is used GL scientific company (GL Science, Inc.) GC-PDD processed to measure; Nitrogen concentration is measured with the GC-PDD processed of Shimadzu Scisakusho Ltd.Moisture is measured with the dew point instrument MST-5 that detects scientific & technical corporation (GE Sensing & Inspection Technologies, Inc.) system by GE sensing.
Impurity in the helium in the exit of PSA unit 10 consist of oxygen lower than 1ppm, nitrogen 380ppm, hydrogen lower than 1ppm, carbon monoxide lower than 1ppm, carbonic acid gas lower than 1ppm, methane lower than 1ppm, moisture lower than 1ppm.
Embodiment 2
Except being changed into, the metal oxide that is filled in the 3rd reactor 7 is carried on the cupric oxide (Sigma aldrich Co., Ltd. (シ グ マ ァ Le De リ ッ チ) system) of aluminum oxide, similarly to Example 1 purifying helium.The composition of the helium that this is purified is shown in following table 1.
Embodiment 3
Except the sorbent material using in TSA unit 20 being changed into LiX type zeolite, purifying helium similarly to Example 1.The composition of the helium that this is purified is shown in following table 1.
Embodiment 4
Except the adsorption temp in TSA unit 20 being changed into-50 ℃, purifying helium similarly to Example 1.The composition of the helium that this is purified is shown in following table 1.
Embodiment 5
Except the catalyzer that is filled in the first reactor 3 and the second reactor 4 being changed into the palladium that is carried on aluminum oxide, purifying helium similarly to Example 1.The composition of the helium that this is purified is shown in following table 1.
Comparative example 1
Except not using for the 3rd reactor 7 except dehydrogenation, purifying helium similarly to Example 1.The composition of the helium that this is purified is shown in following table 1.
Comparative example 2
Except not adopting the dehydration operation of thermal regeneration water extracter, purifying helium similarly to Example 1.The composition of the helium that this is purified is shown in following table 1.
[table 1]
By above-mentioned table 1, can be confirmed, in each embodiment, helium purity is higher than each comparative example, and hydrogen concentration is lower than comparative example 1,2.
The present invention is not limited to the above-described embodiment and examples.For example, the helium that carries out purifying by the present invention is not limited to be distributed to the helium that the helium recovery in atmosphere obtains in the wire-drawing process of optical fiber after using, to being distributed to helium recovery in atmosphere after using in the cooling purposes of the pressure in the manufacturing process of semiconductor wafer helium etc. while carrying out purifying, also can apply the present invention, so long as at least contain hydrogen, carbon monoxide, derive from the nitrogen of air and oxygen as the helium of impurity.
Claims (2)
1. a purification process for helium, is characterized in that,
To at least containing hydrogen, carbon monoxide, when deriving from the nitrogen of air and oxygen and carrying out purifying as the helium of impurity,
Utilize catalyzer to make oxygen, hydrogen and the reaction of carbon monoxide in described helium, thereby generate carbonic acid gas and water with the state of residual aerobic,
Then add hydrogen, make the hydrogen volumetric molar concentration in described helium reach the value of 2 times higher than oxygen volumetric molar concentration,
Then utilize catalyzer to make oxygen and the H-H reaction in described helium, thereby generate water to remain the state of hydrogen,
Then by dehydration operation, reduce the moisture containing ratio of described helium,
Then make hydrogen and reactive metal oxide in described helium, thereby generate water,
Then, by using the pressure swing adsorption process of zeolites sorbent material at least to adsorb nitrogen, carbonic acid gas and the water in the impurity in described helium,
Then the Temp .-change adsorptive process by-10 ℃～-50 ℃ at least adsorbs the nitrogen in the impurity in described helium.
2. a purification devices for helium, this device be at least containing hydrogen, carbon monoxide, the nitrogen and the oxygen that derive from air carries out the device of purifying as the helium of impurity, it is characterized in that, comprising:
The first reactor, imports and has described helium in this first reactor;
The second reactor, imports in this second reactor and has the helium flowing out from described the first reactor;
Hydrogen concentration setting device, this hydrogen concentration setting device is set as the value of 2 times higher than oxygen volumetric molar concentration by adding hydrogen by the hydrogen volumetric molar concentration in the described helium importing in described the second reactor;
Water extracter, this water extracter reduces the moisture containing ratio of the described helium flowing out from described the second reactor by carrying out dehydration operation;
The 3rd reactor, imports and has the described helium that has reduced moisture containing ratio by described water extracter in the 3rd reactor;
Adsorption unit, this adsorption unit is connected with described the 3rd reactor;
In described the first reactor, be filled with catalyzer, oxygen, hydrogen and the carbon monoxide in described helium in described the first reactor reacted, thereby generate water and carbonic acid gas,
In described the second reactor, be filled with catalyzer, make oxygen and H-H reaction in described helium in described the second reactor, thereby generate water to remain the state of hydrogen,
In described the 3rd reactor, be filled with metal oxide, make the hydrogen in described helium in described the 3rd reactor oxidation occur and generation water,
Described adsorption unit has PSA unit and TSA unit, this PSA unit is by being used the pressure swing adsorption process of zeolites sorbent material at least to adsorb nitrogen, carbonic acid gas and the water in the impurity the described helium flowing out from described the 3rd reactor, and this TSA unit at least adsorbs the nitrogen in the impurity in described helium by the Temp .-change adsorptive process of-10 ℃～-50 ℃.
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| JP5846641B2 (en) * | 2012-07-02 | 2016-01-20 | 住友精化株式会社 | Helium gas purification method and purification apparatus |
| TWI625297B (en) * | 2014-03-28 | 2018-06-01 | 住友精化股份有限公司 | Purification method and purification system for helium gas |
| CN114229810B (en) * | 2021-12-15 | 2023-11-03 | 华能核能技术研究院有限公司 | Helium purification system and method for thermal aging test of high-temperature gas cooled reactor internals |
| JP7148748B1 (en) * | 2022-03-11 | 2022-10-05 | 大陽日酸株式会社 | gas purifier |
| CN118373390B (en) * | 2024-06-21 | 2024-10-22 | 宏芯气体(上海)有限公司 | Ultra-high purity helium purification system and purification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN85102708A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Inert gas engaging hydrogen, oxygen scavenging agent |
| CN1237124A (en) * | 1997-09-04 | 1999-12-01 | 液化空气日本有限公司 | Method and apparatus for purification of argon |
| CN1260231A (en) * | 1998-12-04 | 2000-07-19 | 气体产品与化学公司 | Purification for gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102708A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Inert gas engaging hydrogen, oxygen scavenging agent |
| CN1237124A (en) * | 1997-09-04 | 1999-12-01 | 液化空气日本有限公司 | Method and apparatus for purification of argon |
| CN1260231A (en) * | 1998-12-04 | 2000-07-19 | 气体产品与化学公司 | Purification for gas |
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