CN102730653A - Purification method for argon and purification device thereof - Google Patents
Purification method for argon and purification device thereof Download PDFInfo
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- CN102730653A CN102730653A CN2012101157487A CN201210115748A CN102730653A CN 102730653 A CN102730653 A CN 102730653A CN 2012101157487 A CN2012101157487 A CN 2012101157487A CN 201210115748 A CN201210115748 A CN 201210115748A CN 102730653 A CN102730653 A CN 102730653A
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- argon
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 485
- 229910052786 argon Inorganic materials 0.000 title claims abstract description 248
- 238000000034 method Methods 0.000 title claims abstract description 72
- 238000000746 purification Methods 0.000 title claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 191
- 239000001301 oxygen Substances 0.000 claims abstract description 125
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 125
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 123
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 120
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 77
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 76
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 76
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 59
- 239000001257 hydrogen Substances 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000012535 impurity Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910001868 water Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 239
- 238000010521 absorption reaction Methods 0.000 claims description 51
- 235000011089 carbon dioxide Nutrition 0.000 claims description 43
- 239000002594 sorbent Substances 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 39
- 150000002431 hydrogen Chemical class 0.000 claims description 30
- 230000008676 import Effects 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 239000010457 zeolite Substances 0.000 claims description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 description 94
- 239000003921 oil Substances 0.000 description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 238000003795 desorption Methods 0.000 description 15
- 239000002826 coolant Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 150000001485 argon Chemical class 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 102100022818 Disintegrin and metalloproteinase domain-containing protein 23 Human genes 0.000 description 2
- 101710121148 Disintegrin and metalloproteinase domain-containing protein 23 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000001914 calming effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- -1 argon hydrogen Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention provides a method and device for reducing percentage of impurity in argon, reducing energy consumption required by purification, purifying the argon with high purity during the preprocessing stage for adsorption and processing. when the argon with impurity containing at least oxygen, hydrogen, carbon monoxide, hydrocarbon and nitrogen is purified, oxygen is added to make the oxygen quantity surpass the set quantity if the oxygen quantity in the argon is less than the preset quantity for the oxygen required by reaction of all the hydrogen, carbon monoxide, hydrocarbon,the catalyst is used to make least oxygen, hydrogen, carbon monoxide, hydrocarbon in the argon react with the oxygen so as to generate carbon dioxide and water with residual oxygen,the oxygen in the argon is reacted with the metal to generate metal oxide,the carbon dioxide and water generated from the argon through the pressure swing adsorption method are adsorbed to the adsorbent together with the argon.
Description
Technical field
The present invention relates to the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity is at least carried out the method and apparatus of purifying.
Background technology
For example silicon single crystal lifting furnace, ceramic post sintering stove, steel-making are with in the equipment such as vacuum deaerator plant, silicon for solar cell plasma body fusing device, polysilicon foundry furnace, and argon gas is used as furnace atmosphere gas etc.Descend because of sneaking into purity such as hydrogen, carbon monoxide, air from the argon gas that such equipment reclaims in order to utilize again.So the purity of the argon gas that reclaims in order to improve adopts to make the impurity absorption of sneaking in the method for sorbent material.In addition, in order to carry out such impurity absorption efficiently, proposed that pre-treatment as adsorption treatment makes oxygen and the combustiblecomponents reaction in the impurity and the technical scheme (with reference to patent documentation 1,2) that is modified as carbonic acid gas and water.
In the method that patent documentation 1 is disclosed; Oxygen amount in the argon gas is adjusted to than is made the required a little less slightly degree of stoichiometry amount of combustiblecomponents perfect combustion such as hydrogen, carbon monoxide; So that having precedence over the palladium or the gold of the reaction of carbon monoxide and oxygen, the reaction of hydrogen and oxygen is catalyzer then; Make reactions such as oxygen and carbon monoxide in the argon gas, hydrogen, have the state of carbon monoxide to generate carbonic acid gas and water with residual by this.Then, make contained carbonic acid gas of argon gas and water be adsorbed in sorbent material at normal temperatures, under-10 ℃～-50 ℃ temperature, make contained carbon monoxide of argon gas and nitrogen be adsorbed in sorbent material again.
In the method that patent documentation 2 is disclosed; Making the oxygen amount in the argon gas is the amount that is enough to make combustiblecomponents perfect combustions such as hydrogen, carbon monoxide; Then use palladium class catalyzer to make reactions such as oxygen and carbon monoxide in the argon gas, hydrogen, the state with residual aerobic generates carbonic acid gas and water by this.Then, make contained carbonic acid gas of argon gas and water be adsorbed in sorbent material at normal temperatures, under the temperature about-170 ℃, make contained oxygen of argon gas and nitrogen be adsorbed in sorbent material again.
In addition; Following technical scheme has been proposed: when from the argon gas of discharges such as single crystal fabrication furnace, containing oil content; Oil removing tube, oil removal filter that gac etc. is equipped with in use are removed this oil content; Oxygen reaction in the hydrogen that then makes interpolation and the argon gas that imports the catalyzer tube and be converted into water will import water and carbonic acid gas in the argon gas of absorbing cylinder again and adsorb and remove, and carry out purifying (with reference to patent documentation 3) through distillation operation then.
The prior art document
Patent documentation
Patent documentation 1: No. 3496079 communique of Japanese Patent Laid
Patent documentation 2: No. 3737900 communique of Japanese Patent Laid
Patent documentation 3: Japanese Patent Laid is opened the 2000-88455 communique
Summary of the invention
Invent technical problem to be solved
In the method for patent documentation 1 record, the reacted adsorption treatment stage of oxygen in the impurity in making argon gas and combustiblecomponents, make carbonic acid gas and water be adsorbed in sorbent material at normal temperatures after, under-10 ℃～-50 ℃, make carbon monoxide and nitrogen be adsorbed in sorbent material.In the time of will under such low temperature, having adsorbed the adsorbent reactivation of carbon monoxide and nitrogen,, therefore be unfavorable for industrial production because carbon monoxide is compared from the sorbent material disengaging with nitrogen and needed more energy.
In the method for patent documentation 2 record, making in the argon gas as the contained oxygen amount of impurity at pretreatment stage is the amount that is enough to make perfect combustions such as hydrogen, carbon monoxide, thereby generates carbonic acid gas and water with the state of residual aerobic.But for adsorb oxygen, the temperature in the time of must making absorption drops to about-170 ℃.That is since in the pre-treatment of adsorption treatment residual oxygen, so the power consumption of the cooling during adsorption treatment increases the problem that exists purification load to increase.
In the method for patent documentation 3 records,, removes oil content contained in the argon gas through being adsorbed in gac.But, when reclaiming argon gas, for example use as adopt under the situation of machines such as oil sealed rotary vacuum pump of oil in order to keep resistance to air loss etc., even there is oil removing to use oil mist separator, the oil content that passes oil mist separator also can reach for example 5～20mg/m
3So the hydrocarbon that derives from oil content contained in the argon gas is very many, methane reaches hundreds of ppm, and (C2～C5) hydrocarbon (C1) conversion with carbon number 1 reaches thousands of ppm to the hydrocarbon of carbon number 2～5.Because methane can not be by charcoal absorption, the hydrocarbon of carbon number 2～5 also can be adsorbed on gac hardly and pass through the catalyzer tube, the shortcoming of the rectifying load increase after therefore existing.
The object of the present invention is to provide the purification process and the purification devices of the argon gas that can solve aforesaid prior art problems.
The technical scheme that the technical solution problem is adopted
Method of the present invention is for carrying out the method for purifying to the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity at least; It is characterized in that, the oxygen amount in the above-mentioned argon gas judged whether surpass with above-mentioned argon gas in the set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction; Oxygen amount in the above-mentioned argon gas is added oxygen and is made the oxygen amount surpass above-mentioned set amount when above-mentioned set amount is following; Then, use catalyzer to make carbon monoxide, hydrogen and hydrocarbon and oxygen reaction in the above-mentioned argon gas, thereby generate carbonic acid gas and water with the state of residual aerobic; Then, make above-mentioned argon gas and metallic contact, thereby make oxygen and the above-mentioned metal reaction in the above-mentioned argon gas and generate MOX; Then, utilize pressure swing adsorption process to make carbonic acid gas, water and nitrogen in the above-mentioned argon gas be adsorbed in sorbent material.According to the present invention, in the argon gas as the contained hydrogen of impurity, carbon monoxide and hydrocarbon through with argon gas in oxygen reaction generate carbonic acid gas and water is removed.In addition, the oxygen that remains in the argon gas through this reaction is removed through being used for the oxidized metal.By this, the pretreatment stage in adsorption treatment can prevent residual oxygen in the argon gas, hydrogen, carbon monoxide, hydrocarbon.Therefore, when adsorbent reactivation, need not to make carbon monoxide to break away from, so can reduce the regeneration power consumption.
Among the present invention, as above-mentioned metal, the preferred metal that uses beyond the metal that forms metal carbonyl.The metal that preferably uses among the present invention is copper, zinc or their mixture.The metal of iron, molybdenum, nickel, chromium, manganese, cobalt and so on can form deleterious metal carbonyl with contained reaction of carbon monoxide in the argon gas, so this metalloid is not suitable for using in the present invention.
In the method for the present invention; Better be that above-mentioned argon gas is when containing the oil content as impurity; Before the reaction of using above-mentioned catalyzer; Make a part and the oil content of the hydrocarbon in the above-mentioned argon gas be adsorbed in gac, carry out then oxygen amount in the above-mentioned argon gas whether surpass with said argon gas in the said judgement of set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction.
By this, when argon gas contains oil content, utilize gac can adsorb this oil content, and a part of utilizing gac can adsorb the hydrocarbon that derives from oil content, particularly utilizing gac can more effectively adsorb carbon number is the hydrocarbon beyond 1～5.Therefore, through reducing the hydrocarbon amount in the argon gas, can reduce by hydrocarbon and oxygen and react and the water and the carbonic acid gas of generation, the absorption burden after alleviating.
In the method for the present invention, preferably said utilize the absorption of pressure swing adsorption process after, make the nitrogen that residues in above-mentioned argon gas be adsorbed in sorbent material through the alternating temperature absorption method under-10 ℃～-50 ℃.By this, can further reduce the nitrogen content in the above-mentioned argon gas.In addition, owing to need not utilize alternating temperature absorption method adsorb oxygen, the cooling power consumption in the time of therefore can reducing adsorption treatment.
In the method for the present invention, when carrying out the above-mentioned absorption that utilizes pressure swing adsorption process,, preferably use zeolite and activated alumina as above-mentioned sorbent material.Activated alumina is adsorption moisture not only, goes back absorbing carbon dioxide, therefore can improve the nitrogen adsorption effect of zeolite.
Device of the present invention is for carrying out the device of purifying to the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity at least; It is characterized in that; Possess first reactor drum that supply to import above-mentioned argon gas, supply to import second reactor drum of the argon gas that flows out from above-mentioned first reactor drum and supply to import the adsorption unit of the argon gas that flows out from above-mentioned second reactor drum; In above-mentioned first reactor drum, take in carbon monoxide, hydrogen and the hydrocarbon and the oxygen catalyst for reaction that make in the above-mentioned argon gas; In above-mentioned second reactor drum, take in through with above-mentioned argon gas in oxygen reaction generate the metal of MOX, above-mentioned adsorption unit has the PSA unit that adsorbs carbonic acid gas, water and nitrogen in the above-mentioned argon gas through pressure swing adsorption process.
According to device of the present invention, when the oxygen amount in the argon gas surpass with this argon gas in during the required set amount of whole hydrogen, carbon monoxide and hydrocarbon reaction, can be according to this argon gas of method direct purification of the present invention.In addition, when the oxygen amount in the argon gas with this argon gas in the required set amount of whole hydrogen, carbon monoxide and hydrocarbon reaction when following, can utilize device of the present invention and add oxygen and make the argon gas after the oxygen amount surpasses this set amount according to method direct purification of the present invention.
In the device of the present invention, above-mentioned adsorption unit preferably has the TSA unit, and said TSA unit is used for adsorbing from the nitrogen of the effusive above-mentioned argon gas in above-mentioned PSA unit through the alternating temperature absorption method under-10 ℃～-50 ℃.By this, can further reduce the nitrogen content in the above-mentioned argon gas.
In the device of the present invention, preferably possesses the oxygen supply device that is used for adding oxygen to the argon gas that imports above-mentioned first reactor drum.By this, when the oxygen amount in the argon gas with this argon gas in the required set amount of whole hydrogen, carbon monoxide and hydrocarbon reaction when following, utilize device of the present invention to add oxygen and make the oxygen amount surpass this set amount.
Device of the present invention preferably possesses the adsorption tower that supply to import above-mentioned argon gas, in above-mentioned adsorption tower, takes in the part that is useful on the hydrocarbon in the above-mentioned argon gas of absorption and the gac of oil content, is imported into above-mentioned first reactor drum from the effusive above-mentioned argon gas of above-mentioned adsorption tower.By this, can tackle argon gas and contain situation as the oil content of impurity.
The effect of invention
According to the present invention; Can provide through reduce the impurity containing ratio of argon gas at the pretreatment stage of adsorption treatment; Can reduce the burden of adsorption treatment; Reduce the required power consumption of purifying and with the argon purification that reclaims to high purity, and the method and apparatus of the practicality that when argon gas contains hydrocarbon and oil content, also can tackle effectively.
The simple declaration of accompanying drawing
Fig. 1 is the structure explanatory view of the argon purification device of embodiment of the present invention.
Fig. 2 is the unitary structure explanatory view of two tower PSA in the argon purification device of embodiment of the present invention.
Fig. 3 is the unitary structure explanatory view of TSA in the argon purification device of embodiment of the present invention.
Fig. 4 is the unitary structure explanatory view of the four-tower PSA of variation of the present invention.
The explanation of symbol
α ... Purification devices, 3 ... Activated carbon adsorber, 5a ... First reactor drum, 5b ... Second reactor drum, 7 ... Adsorption unit, 8 ... The oxygen supply device, 10,10 ' ... The PSA unit, 20 ... The TSA unit.
The mode that carries out an invention
Argon purification device α shown in Figure 1 makes its device that can utilize again for reclaiming the argon gas after the use of supplying with from for example argon gas feed source such as silicon single crystal, polysilicon foundry furnace 1 and carrying out purifying, possesses strainer 2, charcoal trap 3, well heater 4, the reaction unit 5 that comprises the first reactor drum 5a and the second reactor drum 5b, water cooler 6 and adsorption unit 7.
Be considered to aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen at least as the contained trace impurity of the argon gas of purifying object, but can contain other impurity such as oil content, carbonic acid gas, water, be assumed to be the argon gas of oily sub in this embodiment.To not having special qualification, for example be about 5 molar ppm～80000 molar ppm as the concentration of the impurity in the argon gas of purifying object.
The argon gas of supplying with from supply source 1 with strainer 2 (for example CKD Corp. (CKD society) makes AF1000P) dedusting after, at first be imported into activated carbon adsorber 3.In activated carbon adsorber 3, take in the part that is useful on the hydrocarbon of absorption in the argon gas and the gac of oil content.Before the reaction of the use catalyzer in the first reactor drum 5a, a part and the oil content of the hydrocarbon in activated carbon adsorber 3 argon gas are adsorbed on gac.
Then, a part of judging hydrocarbon and oil content be adsorbed in the argon gas behind the gac the oxygen amount whether above with this argon gas in the set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction.This set amount in this embodiment be with this argon gas in the stoichiometry amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction.
Because make the required oxygen amount of hydrocarbon perfect combustion according to the kind of hydrocarbon contained in the argon gas and difference, therefore above-mentioned judgement better is to carry out afterwards in composition and the concentration of obtaining impurity contained in the argon gas through experiment in advance.For example, when the hydrocarbon that contains in the argon gas was methane, argon hydrogen, carbon monoxide and methane and the reaction formula of oxygen water generation reaction and carbonic acid gas wherein was as follows.
H
2+1/2O
2→H
2O
CO+1/2O
2→CO
2
CH
4+2O
2→CO
2+2H
2O
Under this situation, whether surpass and hydrogen volumetric molar concentration, carbon monoxide volumetric molar concentration and the value methane volumetric molar concentration and that equate, judge whether the oxygen amount in the argon gas gets final product above above-mentioned stoichiometry amount according to the oxygen volumetric molar concentration in the argon gas.Certainly, hydrocarbon contained in the argon gas is not limited to methane, also can contain the hydrocarbon more than 2 kinds.
Above-mentioned set amount needs not to be above-mentioned stoichiometry amount; Can be more than above-mentioned stoichiometry amount; For example preferably be made as 1.05～1.1 times value of above-mentioned stoichiometry amount,, can make oxygen and whole hydrogen, carbon monoxide and hydrocarbon reactions in the argon gas reliably through being made as more than 1.05 times; Through being made as below 1.1 times, can prevent that oxygen concn is up to more than the desired concn.
Oxygen amount in the argon gas is above-mentioned set amount when following, in argon gas, adds oxygen and makes the oxygen amount surpass above-mentioned set amount.When the oxygen amount in the argon gas surpasses above-mentioned set amount, needn't carry out the interpolation of oxygen.The purification devices α of this embodiment does not possess the structure that is used for carrying out adding to argon gas oxygen; Therefore when the oxygen amount in the argon gas surpasses above-mentioned set amount; This argon gas of direct purification; And in this oxygen amount when above-mentioned set amount is following, the argon gas that the oxygen amount is surpassed behind this set amount carries out purifying.In addition, shown in dotted line among Fig. 1, through being provided in the argon gas that imports the first reactor drum 5a, adding the oxygen supply device 8 of oxygen, when the oxygen amount in the argon gas when above-mentioned set amount is following, also can in argon gas, add oxygen and make the oxygen amount above above-mentioned set amount.Oxygen supply device 8 can be made up of with the structure of adding oxygen with the corresponding flow of the importing flow of the argon gas that imports the first reactor drum 5a the hyperbaric oxygen container that for example has flowrate control valve etc.In addition, you can set from a carbon adsorption tower 3 and the oxygen supply device 8 out of argon gas between the sampling line (sampling? Line), the oxygen supply before extraction and import of argon oxygen analyzer (sensor companies such as GE (GE Center for Shin bag Agency) made DE-150ε), carbon monoxide analyzer (such as Fuji Electric Systems Co., Ltd. (Fuji Electric cis Te Rousseau Season Club) system ZRE), hydrogen concentration analyzer (eg GL Science Co., Ltd. (GL thermal イ Oh nn su club) made GC-PDD) and total hydrocarbon analyzer (e.g. Horiba Ltd. (Horiba Co.) made FIA-510), the first reactor may be a second reactor 5a and 5b between the sample line, the first reactor. 5a After the reaction, argon and oxygen is introduced analyzer out through continuous monitoring of impurities in the argon gas, thus more reliably adding a slight excess of oxygen.
Be imported into the first reactor drum 5a from activated carbon adsorber 3 effusive argon gas heater vias 4.For the reaction among the first reactor drum 5a is carried out fully, the temperature that heats with 4 pairs of argon gas of well heater is preferably more than 200 ℃, and from the angle that prevents that life of catalyst from shortening, said temperature is preferably below 400 ℃.
Taken in catalyzer among the first reaction vessel 5a, made in the first reactor drum 5a, to make carbon monoxide, hydrogen and hydrocarbon and the oxygen reaction in the argon gas, thereby generate carbonic acid gas and water with the state of residual aerobic.Be accommodated in the catalyzer of the first reaction vessel 5a so long as make oxygen and the catalyzer of carbon monoxide, hydrogen and hydrocarbon reaction gets final product; There is not special the qualification; Can use the catalyzer that for example on aluminum oxide, carries platinum, platinum alloy, palladium, ruthenium or their mixture etc.; When argon gas contains lower hydrocarbon such as a large amount of methane, preferably on aluminum oxide, carry the catalyzer of palladium.
Be imported into the second reactor drum 5b from the effusive argon gas of the first reactor drum 5a.In the second reactor drum 5b, take in the metal that contacts with argon gas, generate MOX through the reaction of the residual oxygen in this metal and the argon gas.As this metal, be preferably formed the metal beyond the metal of metal carbonyl, for example copper, zinc or their mixture preferably are carried on the metal of oxide compounds such as aluminum oxide, silicon-dioxide.
By water cooler 6 coolings moisture is reduced the back from the effusive argon gas of the second reactor drum 5b and arrive adsorption unit 7.Adsorption unit 7 has PSA unit 10 and TSA unit 20.PSA unit 10 is for to utilize the pressure swing adsorption process under the normal temperature that carbonic acid gas at least, water and nitrogen in the argon gas are adsorbed in sorbent material.Be imported into PSA unit 10 through water cooler 6 cooled argon gas.The part of the nitrogen that carbonic acid gas that in the first reactor drum 5a, generates by this, and water contain in argon gas from the beginning is adsorbed on sorbent material in PSA unit 10.
Among Fig. 2, the inlet 13a of adsorption tower 13 is situated between respectively and is connected with raw material pipeline 13f with transforming valve 13b, is situated between to be connected in the atmosphere with transforming valve 13c and sourdine 13e, and being situated between is connected to each other with transforming valve 13d and bottom pressure-equalizing passageway 13g.Flow out and arrival raw material pipeline 13f after water cooler 6 refrigerative argon gas are compressed machine 12 compressions from the second reactor drum 5b.
The outlet 13k of adsorption tower 13 is situated between respectively and is connected with outflow pipeline 13o with transforming valve 13l, and being situated between is connected with pipe blow-through 13p with transforming valve 13m, and being situated between is connected to each other with transforming valve 13n and top pressure-equalizing passageway 13q.
Flowing out pipeline 13o Jie is connected with the inlet of balancing slit 14 with transforming valve 13s with the vacuum breaker 13r that is set up in parallel.The pressure regulator valve 14a that the outlet of balancing slit 14 is situated between with the adsorptive pressure that is used for controlling adsorption tower 13 is connected with the inlet of retention basin 15.The outlet of retention basin 15 is situated between and is connected with TSA unit 20 with outlet conduit 15a.In addition; Flow out pipeline 13o and be connected with pipe blow-through 13p with flowrate control valve 13u, flow indication accommodometer 13v, deliver to adsorption tower 13 again after the argon gas after can will reducing from adsorption tower 13 effusive impurity concentrations via pipe blow-through 13p be adjusted to certain flow with balancing slit 14 Jie.
Carry out absorption process, pressure process, desorption step, matting, pressure process, the operation of boosting in first, second adsorption tower 13 of PSA unit 10 shown in Figure 2 respectively successively.
That is, only open transforming valve 13b and transforming valve 13l in first adsorption tower 13, thereby will import first adsorption tower 13 by the argon gas after compressor 12 compressions via transforming valve 13b.Through the carbonic acid gas at least in the argon gas that will import, nitrogen, water adsorption in sorbent material, thereby carry out absorption process on first absorption tower 13.Argon gas via flowing out after pipeline 13o reduces impurity containing ratio in first adsorption tower 13 is delivered to balancing slit 14.At this moment; Only open transforming valve 13m, 13c in second adsorption tower 13; Thereby a part that is sent to the argon gas that flows out pipeline 13o from first adsorption tower 13 is sent to second adsorption tower 13 via pipe blow-through 13p, flowrate control valve 13u, carries out matting at second adsorption tower 13.
Then; Close transforming valve 13b, 13l in first adsorption tower 13; Close transforming valve 13m, 13c in second adsorption tower 13, open transforming valve 13n, 13d, thereby in first adsorption tower 13 and second adsorption tower 13, carry out the pressure process that purpose is to realize the internal pressure homogenization.
Then, close transforming valve 13n, 13d, in first adsorption tower 13, open transforming valve 13c, thereby carry out the desorption step of impurity from the sorbent material desorb discharged into the atmosphere via sourdine 13e with gas through the impurity of desorb at first adsorption tower 13.At this moment; In second adsorption tower 13, open transforming valve 13b, 13l, transforming valve 13s; Thereby argon gas Jie via compressor 12 compressions is imported into transforming valve 13b; Argon gas after impurity containing ratio in the balancing slit 14 reduces is imported into via transforming valve 13s and transforming valve 13l, the operation of in second adsorption tower 13, boosting, and beginning absorption process.
Then; In first adsorption tower 13, open transforming valve 13m; Close transforming valve 13s; To deliver to first adsorption tower 13 via pipe blow-through 13p, flowrate control valve 13u from the part that second adsorption tower 13 that just carries out absorption process is delivered to the argon gas that flows out pipeline 13o by this, carry out matting at first adsorption tower 13.Gas used in the matting is discharged into the atmosphere via transforming valve 13c, sourdine 13e.
Then; Close transforming valve 13c, 13m in first adsorption tower 13; Close transforming valve 13b, 13l in second adsorption tower 13, open transforming valve 13n, 13d, thereby in first adsorption tower 13 and second adsorption tower 13, carry out the pressure process that purpose is to realize the internal pressure homogenization.
Then; Close transforming valve 13n, 13d; In first adsorption tower 13, open transforming valve 13b, 13l, transforming valve 13s; Thereby be imported into the operation of in first adsorption tower 13, boosting, and beginning absorption process through the argon gas of compressor 12 compressions and the argon gas after the reduction of the impurity containing ratio in the balancing slit 14.At this moment, in second adsorption tower 13, open transforming valve 13c, thereby carry out the desorption step of impurity from the sorbent material desorb at second adsorption tower 13, impurity is discharged into the atmosphere via sourdine 13e with gas.
Through in first, second adsorption tower 13, carrying out each above-mentioned operation respectively successively repeatedly, the argon gas after the impurity containing ratio reduces is sent to TSA unit 20 via balancing slit 14, pressure regulator valve 14a, retention basin 15, outlet conduit 15a.
Also have, PSA unit 10 is not limited to unit shown in Figure 2, and for example the tower number can be the number beyond 2, and for example 3 or 4.
The argon gas that contains the nitrogen that is not adsorbed agent absorption in the PSA unit 10 is imported into TSA unit 20.TSA unit 20 is adsorbed in sorbent material through the nitrogen in alternating temperature absorption method to major general's argon gas of-10 ℃～-50 ℃.
Among Fig. 3, water cooler 22 is situated between and is connected with the inlet 23a of each adsorption tower 23 with transforming valve 23b.
The inlet 23a of adsorption tower 23 is situated between respectively and is communicated in the atmosphere with transforming valve 23c.
The outlet 23e of adsorption tower 23 be situated between respectively with transforming valve 23f with flow out pipeline 23g and be connected, be situated between with transforming valve 23h with cooling, boosting is connected with pipeline 23i, Jie is connected with cleaning tube road 23k with transforming valve 23j.
Flow out the part of pipeline 23g formation pre-cooler 21, the argon gas of sending here from PSA unit 10 is cooled off from flowing out the effusive purified argon gas of pipeline 23g.Purified argon gas flows out via transforming valve 23l from flowing out pipeline 23g.
Cooling is boosted 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 Jie.
Carry out absorption process, desorption step, matting, refrigerating work procedure, the operation of boosting in first, second adsorption tower 23 of TSA unit 20 shown in Figure 3 respectively successively.
That is, in the TSA unit 20, after the argon gas of supplying with from PSA unit 10 is cooled, import first adsorption tower 23 pre-cooler 21, water cooler 22 via transforming valve 23b.At this moment, first adsorption tower 23 is in to circulate in heat exchanger 24 through cooling agent and is cooled to-10 ℃～-50 ℃ state, and transforming valve 23c, 23h, 23j close, and transforming valve 23f opens, and contained nitrogen is adsorbed on sorbent material in the argon gas at least.By this, in first adsorption tower 23, carry out absorption process, the purifying argon gas after the impurity containing ratio reduces flows out via transforming valve 23l from adsorption tower 23, is sent to product jar (omitting diagram).
Carry out during the absorption process in first adsorption tower 23, carry out desorption step, matting, refrigerating work procedure, the operation of boosting in second adsorption tower 23.
That is, in second adsorption tower 23, absorption process in order to implement desorption step, is closed transforming valve 23b, 23f after finishing, and opens transforming valve 23c.By this, in second adsorption tower 23, impure argon gas is released in the atmosphere, and pressure drops to about normal atmosphere.In this desorption step; The transforming valve 24f that the heat exchange department 24 of refrigerant cycle is arranged when the absorption process in second adsorption tower 23 is switched to closing condition and stops the circulation of cooling agent, with cooling agent is 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 in second adsorption tower 23, to implement matting; The transforming valve 23n of the transforming valve 23c of second adsorption tower 23,23j and cleaning tube road 23k is set as open mode, and the part of heated purifying argon gas imports second adsorption tower 23 via cleaning tube road 23k through the heat exchange in the heat exchange type pre-cooler 21.By this, in second adsorption tower 23, implement the desorb and the cleaning of adopting the purifying argon gas of the impurity of self-absorbent, the used argon gas of this cleaning is released into the atmosphere with impurity from transforming valve 23c.In this matting, make the transforming valve 24f of perolene round-robin heat exchange department 24 switch to open mode with being used in second adsorption tower 23.
Then; In order in second adsorption tower 23, to implement refrigerating work procedure; The transforming valve 23n of the transforming valve 23j of second adsorption tower 23 and cleaning tube road 23k is set as closing condition; The transforming valve 23h of second adsorption tower 23 and the transforming valve 23n that cooling is boosted with pipeline 23i are set as open mode, and boosting via cooling from the part of first adsorption tower, 23 effusive purifying argon gas imports second adsorption tower 23 with pipeline 23i.By this, refrigerative purifying argon gas having been carried out in second adsorption tower, 23 inside is released in the atmosphere via transforming valve 23c.In this refrigerating work procedure, will be used to make perolene round-robin transforming valve 24f switch to closing condition and the circulation that stops perolene, with perolene is discharged and the transforming valve 24f that gets back to perolene supply source 24d switches to open mode from heat exchange department 24.After perolene discharge to finish, the transforming valve 24f of the heat exchange department 24 that is used to make refrigerant cycle in second adsorption tower 23 is switched to open mode, make it be the refrigerant cycle state.This refrigerant cycle state continuance to the operation of following of boosting, absorption process thereafter finish.
Then,, close the transforming valve 23c of second adsorption tower 23, import a part, thereby boosted in the inside of second adsorption tower 23 from first adsorption tower, 23 effusive purifying argon gas in order in second adsorption tower 23, to implement to boost operation.This operation of boosting continue to second adsorption tower 23 interior pressure and first adsorption tower 23 interior pressure about equally.After the operation of boosting finishes; The transforming valve 23h that closes second adsorption tower 23 boosts with the transforming valve 23n of pipeline 23i with cooling; Form all transforming valve 23b, 23c, 23f, 23h, the 23j closing state of second adsorption tower 23 by this, second adsorption tower 23 keeps holding state to the absorption process of following.
The absorption process of the absorption process of second adsorption tower 23 and first adsorption tower 23 is likewise implemented.Carry out during the absorption process in second adsorption tower 23, likewise carry out desorption step, matting, refrigerating work procedure, the operation of boosting with second adsorption tower 23 in first adsorption tower 23.
Also have, TSA unit 20 is not limited to unit shown in Figure 3, and for example the tower number can be the number more than 2, and for example 3 or 4.
According to above-mentioned purification devices α; At least the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity is being reclaimed and during purifying; The oxygen amount in the argon gas judged whether surpass with argon gas in the set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction; When this oxygen amount when above-mentioned set amount is following; Add oxygen and make the oxygen amount surpass set amount, then use catalyzer to make carbon monoxide, hydrogen and hydrocarbon and oxygen reaction in the argon gas, thereby generate carbonic acid gas and water with the state of residual aerobic.By this, the major impurity in the argon gas becomes carbonic acid gas, water, oxygen and nitrogen.Then, through making argon gas and metallic contact, make oxygen and this metal reaction in the argon gas and generate MOX.By this, residue in oxygen in the argon gas and be used to the oxidized metal and remove, the major impurity in the argon gas becomes water, carbonic acid gas and nitrogen.Then, make carbonic acid gas, water and nitrogen in the argon gas be adsorbed in sorbent material, make the nitrogen in the argon gas be adsorbed in sorbent material through the alternating temperature absorption method under-10 ℃～-50 ℃ then through pressure swing adsorption process.That is, the pretreatment stage in adsorption treatment can prevent residual oxygen in the argon gas, hydrogen, carbon monoxide, hydrocarbon.Therefore, when adsorbent reactivation, need not to make carbon monoxide to break away from, therefore can reduce the regeneration power consumption, and owing to need not utilize alternating temperature absorption method adsorb oxygen, the cooling power consumption in the time of therefore can reducing adsorption treatment.In addition,, can improve the adsorption effect of nitrogen, therefore can reduce the nitrogen absorption load in the TSA unit 20 through using zeolite as the sorbent material in the PSA unit 10, with the argon purification that reclaims to high purity.Also have,, can further improve the adsorption effect of nitrogen, therefore can further reduce the nitrogen absorption load in the TSA unit 20 through using activated alumina and zeolite as the sorbent material in the PSA unit 10.
Also have,, pass through activated carbon adsorber 3, in the first reactor drum 5a, use the reaction of catalyzer before a part and the oil content of the hydrocarbon in the argon gas to be adsorbed in gac through making argon gas according to above-mentioned purification devices α.By this, when argon gas contains oil content, utilize gac can adsorb this oil content, and a part of utilizing gac can adsorb the hydrocarbon that derives from oil content, particularly utilizing gac can more effectively adsorb carbon number is the hydrocarbon beyond 1～5.Therefore, through reducing the hydrocarbon amount in the argon gas, can reduce by hydrocarbon and oxygen and react and the water and the carbonic acid gas of generation, the absorption burden in the adsorption unit 9 after alleviating.
As variation, can remove TSA unit 20 from purification devices α.At this moment, utilize the absorption of pressure swing adsorption process, but do not utilize the absorption of alternating temperature absorption method.Do not use TSA unit 20 as stated and when the argon gas that reclaims carried out purifying, in order to improve the nitrogen adsorption effect that utilizes pressure swing adsorption process, the sorbent material that uses when preferably using activated alumina and zeolite as the absorption that utilizes pressure swing adsorption process.Also have,, preferably use two tower PSA unit 10 shown in Figure 2, four-tower PSA unit 10 shown in Figure 4 ' replace in order to improve the nitrogen adsorption effect that utilizes pressure swing adsorption process.
Four-tower PSA unit 10 shown in Figure 4 ' have to carry out from the effusive argon gas of the second reactor drum 5b compressor for compressing 12 ' with four adsorption towers, promptly first～the 4th adsorption tower 13 '.The used identical sorbent material of weighting agent in each adsorption tower 13 ' middle filling and the two tower PSA unit 10.
Among Fig. 4, compressor 12 ' Jie with transforming valve 13b ' and each adsorption tower 13 ' inlet 13a ' be connected.
Adsorption tower 13 ' inlet 13a ' be situated between respectively and be connected in the atmosphere with transforming valve 13e ' and sourdine 13f '.
Adsorption tower 13 ' outlet 13k ' be situated between respectively with transforming valve 13l ' with flow out pipeline 13m ' and be connected; Jie is connected with the pipeline 13o ' that boosts with transforming valve 13n '; Jie cleans out duct 13q ' and is connected with all pressing with transforming valve 13p ', is situated between to go into duct 13s ' with transforming valve 13r ' with equal pressure cleanings and be connected.
Flowing out pipeline 13m ' Jie is connected with the goods jar with pressure regulator valve 13t '.
Pipeline 13o ' Jie of boosting is connected with outflow pipeline 13m ' with flowrate control valve 13u ', flow indication accommodometer 13v ', and the flow among the pipeline 13o ' that boosts is adjusted to constant, thereby prevents to import the fluctuations in discharge of the argon gas of goods jar.
All press to clean out duct 13q ' and all press cleaning to go into duct 13s ' Jie to interconnect with a pair of connecting tube 13w ', each connecting tube 13w ' is provided with transforming valve 13x '.
That is, first adsorption tower 13 ' in only open transforming valve 13b ' and transforming valve 13l ', the argon gas of supplying with from the second reactor drum 5b from compressor 12 ' via transforming valve 13b ' importing first adsorption tower 13 '.By this; First adsorption tower 13 ' in nitrogen, carbon monoxide, carbonic acid gas and moisture are adsorbed on sorbent material at least in the argon gas that imported; Thereby carry out absorption process, the argon gas after the impurity containing ratio reduces is from first adsorption tower 13 ' deliver to the goods jar via flowing out pipeline 13m '.At this moment, a part that is sent to the argon gas that flows out pipeline 13m ' is delivered to other adsorption tower (in this embodiment be second adsorption tower 13 ') via the pipeline 13o ' that boosts, flowrate control valve 13u ', second adsorption tower 13 ' in the II operation of boosting.
Then, close first adsorption tower 13 ' transforming valve 13b ', 13l ', open transforming valve 13p ', open the transforming valve 13r ' of other adsorption tower (in this embodiment be the 4th adsorption tower 13 '), open 1 among the transforming valve 13x '.By this, the less argon gas of the impurity containing ratio on first adsorption tower, 13 ' top via all press clean duct 13s ' deliver to the 4th adsorption tower 13 ', first adsorption tower 13 ' in the I operation that reduces pressure.At this moment, the 4th adsorption tower 13 ' middle transforming valve 13e ' opens, and carries out matting.
Then, open first adsorption tower 13 ' transforming valve 13p ' and the 4th adsorption tower 13 ' the state of transforming valve 13r ' under, close the 4th adsorption tower 13 ' transforming valve 13e '.By this, the 4th adsorption tower 13 ' in be used to implement the decompression II operation of gas recovery, until first adsorption tower 13 ' with the 4th adsorption tower 13 ' the internal pressure homogeneous or reach roughly homogeneous.At this moment, transforming valve 13x ' can according to circumstances all open 2.
Then, open first adsorption tower 13 ' transforming valve 13e ', close transforming valve 13p ', thereby carry out the desorption step of impurity from the sorbent material desorb, impurity is released in the atmosphere via sourdine 13f ' with gas.
Then, open first adsorption tower 13 ' transforming valve 13r ', close second adsorption tower 13 of the state after absorption process finishes ' transforming valve 13b ', 13l ', open transforming valve 13p '.By this, the less argon gas of the impurity containing ratio on second adsorption tower, 13 ' top through all press clean duct 13s ' deliver to first adsorption tower 13 ', first adsorption tower 13 ' in carry out matting.First adsorption tower 13 ' in the used gas of matting be released in the atmosphere via transforming valve 13e ', sourdine 13f '.At this moment, second adsorption tower 13 ' in the I operation that reduces pressure.
Then, open second adsorption tower 13 ' transforming valve 13p ' and first adsorption tower 13 ' the state of transforming valve 13r ' under close first adsorption tower 13 ' transforming valve 13e ', thereby boost the I operation.At this moment, transforming valve 13x ' can according to circumstances all open 2.
Then, close first adsorption tower 13 ' transforming valve 13r '.By this, temporarily be in the holding state of no operation.This holding state continue to the 4th adsorption tower 13 ' the II operation of boosting finish.The 4th adsorption tower 13 ' the end of boosting, absorption process is opened the transforming valve 13n ' of first adsorption tower from 13 ' time of the 3rd adsorption tower 13 ' be converted to the 4th adsorption tower.By this; A part of delivering to the argon gas that flows out pipeline 13m ' from another adsorption tower of being in absorption process (this embodiment be the 4th adsorption tower 13 ') via the pipeline 13o ' that boosts, flowrate control valve 13u ' be sent to first adsorption tower 13 ', thereby in the first adsorption tower 13 ' II operation of boosting.
Through first～the 4th adsorption tower 13 ' in carry out each above-mentioned operation respectively successively repeatedly, the argon gas after the impurity containing ratio reduces is delivered to the goods jar continuously.
[embodiment 1]
Use above-mentioned purification devices α to carry out the purifying of argon gas.
Contain 2000 molar ppm oxygen, 1000 molar ppm hydrogen, 900 molar ppm carbon monoxide, 1000 molar ppm nitrogen, 100 molar ppm carbonic acid gas, 20 molar ppm moisture respectively, be scaled hydrocarbon, the 10g/m of the C2～C5 of 600 molar ppm as 70 molar ppm methane of hydrocarbon with the hydrocarbon of C1 as impurity in the argon gas
3Oil content.
This argon gas is counted 4.2L/ minute flow with standard state import activated carbon adsorber 3.Activated carbon adsorber 2 is the tubulose of nominal diameter 32A, fills the system GX6/8 of 1.0L Japan Enviro Chemicals Ltd. (Japanese エ Application バ イ ロ ケ ミ カ Le ズ) forming charcoal.
Import the first reactor drum 5a from activated carbon adsorber 3 effusive argon gas.In the first reactor drum 5a, fill 50mL and be carried on the palladium catalyst (the system DASH-220D of NE chemical catalyst Co., Ltd. (NE ケ system キ ヤ Star ト)) of aluminum oxide, reaction conditions is 300 ℃ of temperature, normal atmosphere, space velocity 5000/ hour.
To import the second reactor drum 5b from the effusive argon gas of the first reactor drum 5a.In the second reactor drum 5b, fill 50ml and be carried on the copper and zinc oxide (5% hydrogen with argon-dilution is made the catalyzer after MDC-3 reduces in 250 ℃ to generation Dehua chemical catalyst company (ズ one De ケ ミ one)) of aluminum oxide, reaction conditions is 250 ℃ of temperature, normal atmosphere, space velocity 5000/ hour.
To cooling off, reduce its impurity containing ratio with adsorption unit 7 from the effusive argon gas of the second reactor drum 5b.
In the gangway of the outlet of activated carbon adsorber 3, PSA unit 10 and the impurity of the argon gas in the exit of TSA unit 20 form as follows.
The activated carbon adsorber outlet
Oxygen: 2000 molar ppm, hydrogen: 1000 molar ppm, carbon monoxide: 900 molar ppm, nitrogen: 100 molar ppm, carbonic acid gas: 100 molar ppm, moisture: 20 molar ppm, methane: 70 molar ppm, C2～C5 hydrocarbon: C1 hydrocarbon convert 430 molar ppm, oil content: do not detect.
PSA unit inlet
Hydrogen: 0.5 molar ppm, oxygen: 0.4 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: 1500 molar ppm, nitrogen: 1000 molar ppm, moisture: 1500 molar ppm, hydrocarbon and oil content: do not detect.
The outlet of PSA unit
Hydrogen: 0.5 molar ppm, oxygen: 0.3 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: 110 molar ppm, moisture: be lower than 1 molar ppm.
The outlet of TSA unit
Hydrogen: 0.5 molar ppm, oxygen: 0.2 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: be lower than 1 molar ppm, moisture: be lower than 1 molar ppm.
In addition, the purified argon concentration of oxygen in a Delta F Corporation (Delta? F Co.) Built trace oxygen concentration meter DF-150E type measured, carbon monoxide, and carbon dioxide concentrations using Shimadzu (Shimadzu) system GC -FID by the methanation unit (methanizer) were measured.Use the system GC-PID of GL science Co., Ltd. (GL science society) to measure for nitrogen concentration; Use the system GC-FID of Shimadzu Seisakusho Ltd. to measure for hydrocarbon; Measure according to the calculating of the increasing amount of the filtration yield of the filter made device VFA1000 of CKD Corp. for oil content, use dew point instrument to measure for moisture.
[embodiment 2]
Except the argon flow amount that will import the first reactor drum 5a changes space velocity 2500/ hour into, with embodiment 1 purifying argon gas likewise.This purified argon gas is formed as follows at the impurity in the exit of TSA unit 20.
Hydrogen: 0.2 molar ppm, oxygen: 0.1 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: be lower than 1 molar ppm, moisture: be lower than 1 molar ppm.
[embodiment 3]
As containing 20 molar ppm oxygen, 1000 molar ppm hydrogen, 900 molar ppm carbon monoxide, 100 molar ppm nitrogen, 100 molar ppm carbonic acid gas, 20 molar ppm moisture respectively, be scaled hydrocarbon, the 10g/m of the C2～C5 of 600 molar ppm as 70 molar ppm methane of hydrocarbon with the hydrocarbon of C1 as impurity in the argon gas of purifying object
3Oil content.Before importing the first reactor drum 5a, in argon gas, add 2000 molar ppm oxygen.In addition, with embodiment 1 purifying argon gas likewise.This purified argon gas is formed as follows at the impurity in the exit of TSA unit 20.
Hydrogen: 0.3 molar ppm, oxygen: 0.2 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: be lower than 1 molar ppm, moisture: be lower than 1 molar ppm.
[embodiment 4]
Use above-mentioned purification devices α to carry out the purifying of argon gas.
Contain 2000 molar ppm oxygen, 1000 molar ppm hydrogen, 900 molar ppm carbon monoxide, 1000 molar ppm nitrogen, 100 molar ppm carbonic acid gas, 20 molar ppm moisture respectively, be scaled hydrocarbon, the 10g/m of the C2～C5 of 600 molar ppm as 70 molar ppm methane of hydrocarbon with the hydrocarbon of C1 as impurity in the argon gas
3Oil content.
This argon gas is counted 4.2L/ minute flow with standard state import activated carbon adsorber 3.Activated carbon adsorber 2 is the tubulose of nominal diameter 32A, fills the system GX6/8 of 1.0L Japan Enviro Chemicals Ltd. forming charcoal.
Import the first reactor drum 5a from activated carbon adsorber 3 effusive argon gas.In the first reactor drum 5a, fill 50mL and be carried on the palladium catalyst (the system DASH-220D of NE chemical catalyst Co., Ltd.) of aluminum oxide, reaction conditions is 300 ℃ of temperature, normal atmosphere, space velocity 5000/ hour.
To import the second reactor drum 5b from the effusive argon gas of the first reactor drum 5a.In the second reactor drum 5b, fill copper that 50ml is carried on aluminum oxide and zinc oxide (with 5% hydrogen of argon-dilution in 250 ℃ of catalyzer after generation Dehua chemical catalyst corporate system MDC-3 reduced), reaction conditions is 250 ℃ of temperature, normal atmosphere, space velocity 5000/ hour.
To cooling off, reduce its impurity containing ratio with adsorption unit 7 from the effusive argon gas of the second reactor drum 5b.
In the gangway of PSA unit 10 and the impurity of the argon gas in the exit of TSA unit 20 form as follows.
PSA unit inlet
Hydrogen: 0.5 molar ppm, oxygen: 0.4 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: 1500 molar ppm, nitrogen: 1000 molar ppm, moisture: 1500 molar ppm, hydrocarbon and oil content: do not detect.
The outlet of PSA unit
Hydrogen: 0.5 molar ppm, oxygen: 0.3 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: 1.4 molar ppm, moisture: be lower than 1 molar ppm.
The outlet of TSA unit
Hydrogen: 0.5 molar ppm, oxygen: 0.3 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: be lower than 1 molar ppm, moisture: be lower than 1 molar ppm.
[embodiment 5]
PSA unit 10 ' be four-tower, each tower is the tubulose of nominal diameter 32A.Fill the LiX type zeolite of 1.0L, the activated alumina of 0.05L as sorbent material in each tower.In each tower, make LiX type zeolite and activated alumina range upon range of, activated alumina is filled in inlet side, LiX type zeolite is filled in outlet side.PSA unit 10 ' operational condition be adsorptive pressure 0.8MPaG, desorption pressures 10kPaG, cycling time 100 seconds/tower, implement to clean 10 seconds, all pressed 5 seconds.In addition, do not use TSA unit 20.Likewise operate with embodiment 4 in addition.
The impurity of the argon gas of locating in the gangway of PSA unit 10 is formed as follows.
PSA unit inlet
Hydrogen: 0.5 molar ppm, oxygen: 0.4 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: 1500 molar ppm, nitrogen: 1000 molar ppm, moisture: 1500 molar ppm, hydrocarbon and oil content: do not detect.
The outlet of PSA unit
Hydrogen: 0.5 molar ppm, oxygen: 0.3 molar ppm, carbon monoxide: be lower than 1 molar ppm, carbonic acid gas: be lower than 1 molar ppm, nitrogen: 1.2 molar ppm, moisture: be lower than 1 molar ppm.
According to above-mentioned each embodiment, can confirm can be with the argon purification that reclaims to high purity.
The present invention is not limited to the above-described embodiment and examples.For example, be used for machine that argon gas reclaims and be not limited to the machine that oil sealed rotary vacuum pump etc. uses oil, also can use oilless vacuum pump etc. not use the pump of oil.Under this situation; Can remove the activated carbon adsorber 3 among the purification devices α, under a part that does not make the hydrocarbon in the argon gas and oil content are adsorbed in the state of gac, judge whether surpass as the oxygen amount in the argon gas of purifying object with this argon gas in the set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction.
Claims (10)
1. the purification process of an argon gas, it is characterized in that for the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity at least being carried out the method for purifying,
The oxygen amount in the said argon gas judged whether surpass with said argon gas in the set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction;
Oxygen amount in the said argon gas is added oxygen and is made the oxygen amount surpass said set amount when said set amount is following;
Then, use catalyzer to make carbon monoxide, hydrogen and hydrocarbon and oxygen reaction in the said argon gas, thereby generate carbonic acid gas and water with the state of residual aerobic;
Then, make said argon gas and metallic contact, thereby make oxygen and the said metal reaction in the said argon gas and generate MOX;
Then, make carbonic acid gas, water and nitrogen in the said argon gas be adsorbed in sorbent material through pressure swing adsorption process.
2. the purification process of argon gas as claimed in claim 1; It is characterized in that; When said argon gas contains as the oil content of impurity; Before the reaction of carrying out said use catalyzer, make the part of the hydrocarbon in the said argon gas and oil content be adsorbed in gac, carry out then oxygen amount in the said argon gas whether surpass with said argon gas in the said judgement of set amount of the required oxygen of whole hydrogen, carbon monoxide and hydrocarbon reaction.
3. according to claim 1 or claim 2 the purification process of argon gas is characterized in that, as said metal, uses the metal beyond the metal that forms metal carbonyl.
4. the purification process of argon gas as claimed in claim 3 is characterized in that, said metal is copper, zinc or their mixture.
5. according to claim 1 or claim 2 the purification process of argon gas is characterized in that, said utilize the absorption of pressure swing adsorption process after, make the nitrogen that residues in said argon gas be adsorbed in sorbent material through the alternating temperature absorption method under-10 ℃～-50 ℃.
6. according to claim 1 or claim 2 the purification process of argon gas is characterized in that, when carrying out the said absorption that utilizes pressure swing adsorption process, uses zeolite and activated alumina as said sorbent material.
7. the purification devices of an argon gas, it is characterized in that for the argon gas that contains aerobic, hydrogen, carbon monoxide, hydrocarbon and nitrogen as impurity at least being carried out the device of purifying,
Possess first reactor drum that supply to import said argon gas, supply to import second reactor drum of the argon gas that flows out from said first reactor drum and supply to import the adsorption unit of the argon gas that flows out from said second reactor drum,
In said first reactor drum, take in carbon monoxide, hydrogen and the hydrocarbon and the oxygen catalyst for reaction that make in the said argon gas,
In said second reactor drum, take in through with said argon gas in oxygen reaction generate the metal of MOX,
Said adsorption unit has the PSA unit that adsorbs carbonic acid gas, water and nitrogen in the said argon gas through pressure swing adsorption process.
8. the purification devices of argon gas as claimed in claim 7 is characterized in that, possesses the oxygen supply device that is used for adding to the argon gas that imports said first reactor drum oxygen.
9. like the purification devices of claim 7 or 8 described argon gas; It is characterized in that; Possesses the adsorption tower that supplies to import said argon gas; In said adsorption tower, take in the part that is useful on the hydrocarbon of absorption in the said argon gas and the gac of oil content, be imported into said first reactor drum from the effusive said argon gas of said adsorption tower.
10. like the purification devices of claim 7 or 8 described argon gas, it is characterized in that said adsorption unit has the TSA unit, said TSA unit is used for adsorbing from the nitrogen of the effusive said argon gas in said PSA unit through the alternating temperature absorption method under-10 ℃～-50 ℃.
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| JP2011-088055 | 2011-04-12 | ||
| JP2011088055 | 2011-04-12 | ||
| JP2012-043316 | 2012-02-29 | ||
| JP2012043316A JP5791113B2 (en) | 2011-04-12 | 2012-02-29 | Argon gas purification method and purification apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111491711A (en) * | 2018-03-29 | 2020-08-04 | 爱沃特株式会社 | Apparatus for producing purified gas and method for producing purified gas |
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| CN101690864A (en) * | 2007-10-23 | 2010-04-07 | 气体产品与化学公司 | Purification of noble gases using online regeneration of getter beds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5134588B2 (en) * | 2009-06-12 | 2013-01-30 | 住友精化株式会社 | Argon purification method, argon purification apparatus, target gas purification method, and target gas purification apparatus |
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2012
- 2012-04-09 CN CN2012101157487A patent/CN102730653A/en active Pending
- 2012-04-09 KR KR1020120036689A patent/KR101800031B1/en not_active Application Discontinuation
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| CN1102138A (en) * | 1993-09-30 | 1995-05-03 | 美国Boc氧气集团有限公司 | Purification of fluids by adsorption |
| US5601634A (en) * | 1993-09-30 | 1997-02-11 | The Boc Group, Inc. | Purification of fluids by adsorption |
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| CN111491711A (en) * | 2018-03-29 | 2020-08-04 | 爱沃特株式会社 | Apparatus for producing purified gas and method for producing purified gas |
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| KR101800031B1 (en) | 2017-11-21 |
| KR20120116339A (en) | 2012-10-22 |
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