CN103523822B - The purification process of helium and purification devices - Google Patents
The purification process of helium and purification devices Download PDFInfo
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- CN103523822B CN103523822B CN201310167349.XA CN201310167349A CN103523822B CN 103523822 B CN103523822 B CN 103523822B CN 201310167349 A CN201310167349 A CN 201310167349A CN 103523822 B CN103523822 B CN 103523822B
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention utilizes low cost and compact equipment, it is not necessary to very big purifying energy just can effectively and efficiently reduce the impurity containing ratio in helium. Helium at least contains hydrogen, carbon monoxide, nitrogen and oxygen as impurity, and the oxygen amount contained at first is more than with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide. Utilize hydrogen and carbon monoxide that catalyzer makes to contain at first and the oxygen reaction contained at first. Add hydrogen, this hydrogen amount less than with thus remain in helium whole oxygen reaction needed for stoichiometric quantity. Then, catalyzer is utilized to make the H-H reaction of oxygen and the interpolation remaining in helium. Then, the moisture containing ratio of helium is reduced by dehydration operation. Then, made by pressure swing adsorption process to remain in helium is at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material.
Description
Technical field
The present invention relates to the method and device that are suitable for purifying helium, described helium, as the helium reclaimed after using in the manufacturing process of such as optical fiber, at least contains hydrogen, carbon monoxide, nitrogen and oxygen as impurity.
Background technology
For the helium used in the wire-drawing process of such as optical fiber, be distributed in air after a procedure, sometimes by its recycling. This recovery helium contain be mixed in the wire-drawing process of optical fiber hydrogen, carbon monoxide and because be distributed to after a procedure air is mixed into the nitrogen deriving from air, oxygen etc. as impurity, it is thus desirable to carry out purifying to improve purity.
So, it is known that by the cryogenic operations using liquid nitrogen as cold source, the impurity liquefaction contained in the helium before purifying is removed, the method (with reference to patent documentation 1) the trace impurity absorption of remnants removed with sorbent material. in addition, it is also known that helium before purification adds hydrogen, make this hydrogen and the oxygen reaction of the air composition as impurity and generate moisture, after removing this moisture, remove the method (with reference to patent documentation 2) of the impurity of residual with membrane separation plant. also the known impurity by containing in the rare gas such as the helium before making purifying contacts the method (with reference to patent documentation 3) removed by this impurity with alloy degasser. also known following method: add hydrogen in helium before purification, then by the first water generation reaction of the oxygen in helium and hydrogen, then the moisture containing ratio of helium is reduced by dehydration operation, then oxygen is added as required, thus the oxygen volumetric molar concentration in helium is set as the value of 1/2 higher than carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, then by making the 2nd reaction of the oxygen in helium and carbon monoxide and H-H reaction generate carbonic acid gas and water, then absorption process is carried out, in this absorption process, the oxygen in helium is made by pressure swing adsorption process and change temperature absorption method, nitrogen, carbonic acid gas and water are adsorbed in sorbent material (with reference to patent documentation 4).
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 10-311674 publication
Patent documentation 2: Japanese Patent Laid-Open 2003-246611 publication
Patent documentation 3: Japanese Patent Laid-Open 4-209710 publication
Patent documentation 4: Japanese Patent Laid-Open 2012-31049 publication
Summary of the invention
Invent technical problem to be solved
In the method that patent documentation 1 is recorded, because needing to carry out cryogenic operations with liquid nitrogen, so cooling energy increases, the recovery income of helium reduces.
In the method that patent documentation 2 is recorded, because needing membrane sepn module, so equipment cost height, therefore the recovery income of helium reduces. In addition, in the method that patent documentation 2 is recorded, remove deoxidation by adding hydrogen in the helium of purifying object, but do not consider the abundant removing of hydrogen, it is possible to the material of deterioration that occurs under the effect of hydrogen of optical fiber starting material and so on can be caused detrimentally affect.
In the method that patent documentation 3 is recorded, because the ability of alloy degasser is little, so the helium of the low-purity that can only be used for making impurity concentration be ppm level reaches the situation of ultra-high purity, the situation mixing a large amount of impurity cannot be directly used in.
In the method that patent documentation 4 is recorded, if adding the oxygen amount in the helium after hydrogen and comparing very few with the stoichiometric quantity needed for whole H-H reactions, then a large amount of carbon monoxide can not react with oxygen, but remains in helium. Now, because carbon monoxide is poisonous, so the operational difficulty of helium, until carbon monoxide is combined with oxygen by the 2nd reaction. On the other hand, if the oxygen amount in helium after interpolation hydrogen with compare too much with the stoichiometric quantity needed for whole hydrogen and reaction of carbon monoxide, then after the 2nd reaction, in helium, the oxygen amount of residual is also a lot, and the absorption load of the follow-up oxygen in absorption process increases. Therefore, in order to the hydrogen addition before reacting first and the oxygen addition before the 2nd reaction reach suitable value, it is necessary to carrying out the analysis of helium before two reactions respectively, then add oxygen and hydrogen, purification process becomes loaded down with trivial details.
In addition, in the method that patent documentation 4 is recorded, between the first reaction and the 2nd reaction, dehydration operation is carried out. So, each reaction carries out usually under about 250 DEG C, and on the other hand, dehydration operation carries out usually after by helium gas cooling to room temperature. It is therefore necessary to temporarily cool when the first reaction through the helium heated in order to dehydration operation, then again heating in order to the 2nd reaction, energy consumption increases. In addition, in order to supply continuously and process the helium as purifying object, must be provided separately there is the reaction vessel of the conversion zone for implementing the first reaction and there is the reaction vessel for implementing the conversion zone that the 2nd reacts, between two reaction vessels, dewatering unit is set, equipment enlarging, cost increases.
It is an object of the invention to provide the purification process of the helium of a kind of problem that can solve above-mentioned prior art and purification devices.
The technical scheme that technical solution problem adopts
The inventive method is characterised in that, purifying at least containing hydrogen, carbon monoxide, nitrogen and oxygen as impurity, the oxygen amount that contains at first than during with the helium that the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide is many, comprise: the first reaction process, in this operation, utilize the oxygen reaction that catalyzer makes the hydrogen contained at first in described helium and carbon monoxide and contains at first; Hydrogen add operation, in this operation, in described helium, add hydrogen, this hydrogen amount less than with remain in described helium by implementing described first reaction process whole oxygen reaction needed for stoichiometric quantity; 2nd reaction process, in this operation, utilizes catalyzer to make the H-H reaction remaining in the oxygen in described helium by implementing described first reaction process and adding in described hydrogen interpolation operation; Dehydration procedure, in this operation, reduces the moisture containing ratio of the described helium after implementing described 2nd reaction process by dehydration operation; Transformation absorption process, in this operation, remaining in after making described dehydration operation by pressure swing adsorption process in described helium is at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material.
In the helium being purified by the present invention, the oxygen amount contained at first is more than with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide.Therefore, the hydrogen contained at first in helium and carbon monoxide and the part of oxygen contained at first can become water and carbonic acid gas by the first reaction process. Remain in the oxygen in helium and hydrogen to add in operation the hydrogen added can become water by the 2nd reaction process by implementing the first reaction process. The hydrogen amount of this interpolation less than with the stoichiometric quantity needed for the whole oxygen reaction remaining in helium by implementing the first reaction process, be therefore possible to prevent to implement helium to remain hydrogen after the 2nd reaction process. By this, the analysis and the gas that do not carry out the impurity concentration of helium before the first reaction process add, and before the 2nd reaction process, only carry out analysis and the gas interpolation of the impurity concentration of helium, a large amount of carbon monoxide is remained after just preventing the first reaction process, and before absorption process can be prevented, remain a large amount of oxygen, therefore can simplify purification process. In addition, it is possible to before absorption process, from helium, remove the hydrogen being difficult to be separated from helium by absorption method. Removed the water generated by the 2nd reaction process from helium by dehydration operation, thus the moisture containing ratio of helium reduces, and therefore can alleviate the absorption load of the moisture in follow-up absorption process.
It is better with the stoichiometric quantity needed for the whole oxygen reaction remaining in described helium by implementing described first reaction process more than 95% and less than 100% that described hydrogen adds in operation the hydrogen amount added. By this, make the most of oxygen in helium by the 2nd reaction process and H-H reaction, in absorption process, if the oxygen of the minute quantity remained in absorption helium.
Described dehydration procedure is better by being implemented by described helium gas cooling after implementing described 2nd reaction process. According to the present invention, dehydration operation carries out after the 2nd reaction process, therefore so, it is not necessary to again heated by the helium temporarily cooled in order to dehydration operation, it is possible to reduce energy consumption.
It is better use activated alumina, zeolite class sorbent material and carbonaceous molecular sieve as described sorbent material, after making carbonic acid gas be adsorbed in activated alumina, makes N2 adsorption in zeolite class sorbent material. By activated alumina absorbing carbon dioxide, zeolite class sorbent material thus can be prevented the decline of the adsorption effect of nitrogen, it is possible to effectively remove nitrogen from helium.
It is better comprise becoming temperature absorption process after described transformation absorption process, in this operation, makes the nitrogen remained in described helium and oxygen desorption in sorbent material by the change temperature absorption method at-10 DEG C��-50 DEG C. By this, the containing ratio of the nitrogen in helium and oxygen can be reduced further.
Apparatus of the present invention be purifying at least containing hydrogen, carbon monoxide, nitrogen and oxygen as impurity, the oxygen amount that contains at first than the device of the helium many with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide, it is characterized in that, comprise: well heater, helium described in this heater heats; Reaction unit, this reaction unit has the connecting zone of the first conversion zone, second reaction zone and described first conversion zone and described second reaction zone, described first conversion zone is filled with for making hydrogen and the catalyzer of carbon monoxide and oxygen reaction, and described second reaction zone is filled with for making hydrogen and the catalyzer of oxygen reaction; Hydrogen adding set, this hydrogen adding set comprises hydrogen supply source, analyzer and hydrogen amount regulator, and described analyzer obtains the oxygen concn of helium, and described hydrogen amount regulator adjusts the hydrogen amount from the supply of described hydrogen supply source according to the oxygen concn tried to achieve;Dewatering unit; Adsorption unit, this adsorption unit is connected with described dewatering unit. The hydrogen that described reaction unit is provided with gas outlet port that the gas flow outlet that the gas introduction port being connected with described well heater is connected is connected with described analyzer with described dewatering unit, be connected with described hydrogen supply source via described hydrogen amount regulator adds mouth. Configure described gas introduction port, described first conversion zone, described connecting zone, described second reaction zone and described gas flow outlet so that the described helium importing described reaction unit from described gas introduction port is successively by flowing out from described gas flow outlet after described first conversion zone, described connecting zone, described second reaction zone. Described gas outlet port is configured in the position that can be extracted out by the helium in described connecting zone, and described hydrogen interpolation mouth is configured in can to by being imported into, after described first conversion zone, the position adding hydrogen in the helium of described second reaction zone. Oxygen concn according to the described helium in the described connecting zone tried to achieve by described analyzer, adjust the hydrogen amount from the supply of described hydrogen supply source by described hydrogen amount regulator so that from described hydrogen add the mouth hydrogen amount that is added into described helium less than with the stoichiometric quantity needed for the whole oxygen reaction remaining in described helium by the reaction in described first conversion zone. Described dewatering unit is connected with described gas flow outlet so that the moisture containing ratio of the described helium flowed out from described gas flow outlet is reduced by dehydration operation. Described adsorption unit has psa unit, and this psa unit makes in described helium to be at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material by pressure swing adsorption process.
Utilize apparatus of the present invention can implement the inventive method.
In apparatus of the present invention, it is better that described reaction unit has a reaction vessel, in described reaction vessel, it is provided with described first conversion zone, connecting zone and second reaction zone. By this, it is possible in a reaction vessel, carry out the first reaction process and the 2nd reaction process, facility compact can be made, reduce costs.
The effect of invention
By the present invention, the impurity containing ratio that can provide and utilize low cost and compact equipment, just can effectively and efficiently reduce in helium without the need to very big purifying energy, can high purity ground purifying helium, the method that possesses practicality and device.
Accompanying drawing explanation
Fig. 1 is the formation explanation figure of the purification devices of the helium of embodiments of the present invention.
Fig. 2 is the formation explanation figure of the psa unit in the purification devices of the helium of embodiments of the present invention.
Fig. 3 is the formation explanation figure of the change temperature absorbing unit in the purification devices of the helium of embodiments of the present invention.
Fig. 4 is the figure of the variation of the reaction unit in the purification devices of the helium representing embodiments of the present invention.
The explanation of symbol
�� ... purification devices, 2 ... well heater, 3 ... reaction unit, 3A ... first conversion zone, 3B ... second reaction zone, 3C ... connecting zone, 3a ... reaction vessel, 3b ... gas introduction port, 3c ... gas flow outlet, 3d ... gas outlet port, 3e ... hydrogen adds mouth, 4 ... hydrogen adding set, 4a ... hydrogen supply source, 4b ... analyzer, 4c ... hydrogen amount regulator, 5 ... dewatering unit, 9 ... adsorption unit, 10 ... psa unit
Embodiment
The purification devices �� of the helium shown in Fig. 1, using the helium that supplies from supply source 1 as purifying object, comprises well heater 2, reaction unit 3, hydrogen adding set 4, dewatering unit 5 and adsorption unit 9.
The helium as purifying object supplied continuously from supply source 1, by dedustings such as the strainers figure, imports well heater 2 via the gas transportation facilitieses such as gas blower 6. In helium as purifying object, except helium (He), at least containing hydrogen (H2), carbon monoxide (CO), nitrogen (N2) and oxygen (O2) as impurity, it is also possible to containing the impurity beyond these impurity of trace. The concentration of the impurity contained at first in the helium as purifying object is 1 volume %��50 volume % preferably.
When being the helium helium recovery being distributed in air after using in the wire-drawing process of such as optical fiber obtain as the helium of purifying object, contain the impurity deriving from air than other impurity more, i.e. oxygen and nitrogen. Now, it is 10��50 moles of % as the air concentration in the helium of purifying object, it is generally 20��40 moles of %, about hydrogen concentration and carbon monoxide concentration are respectively tens of molar ppm. Therefore, the oxygen amount contained at first in helium as purifying object is more than with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide. That is, the volumetric molar concentration of the oxygen contained at first is higher than the 1/2 of the volumetric molar concentration of the hydrogen contained at first and the volumetric molar concentration sum of carbon monoxide. Hydrogen and carbon monoxide as containing as impurity in the helium of purifying object comprise in air the hydrogen and carbon monoxide that contain with trace, but mainly do not derive from air, but be mixed in the environment for use of helium. Such as, by in the wire-drawing process of optical fiber use after be distributed in air helium recovery time, except the nitrogen deriving from air being mixed into except the hydrogen that is mixed in wire-drawing process and carbon monoxide and when reclaiming and oxygen, as the helium of purifying object also containing the trace impurity deriving from the degree that the carbonic acid gas of this air and hydrocarbon etc. can not be ignored. When helium as purifying object has been mixed into air, although containing argon (Ar), but because the containing ratio of the argon in air is lower than oxygen and nitrogen, and the purposes of the helium after purifying utilizes to replace with argon as when the purposes of the characteristic of rare gas element, so argon can not regard as impurity and ignore.
After being heated by well heater 2 as the helium of purifying object, import reaction unit 3. About well heater 2 to the Heating temperature of helium, when reaction unit 3 using ruthenium (Ru) as catalyzer, in order to make reaction complete, the temperature of reaction of reaction unit 3 is better be set as more than 150 DEG C, on the other hand, from the viewpoint preventing the life-span of catalyzer from shortening, temperature of reaction is better be set as less than 250 DEG C, from the viewpoint reducing energy consumption, temperature of reaction is more preferably and is set as less than 200 DEG C. When reaction unit 3 uses containing palladium (Pd) catalyzer, it is better the Heating temperature of setting helium so that the temperature of reaction of reaction unit 3 reaches 200 DEG C��300 DEG C.
The reaction unit 3 of present embodiment has a tower-like reaction vessel 3a, is provided with the first conversion zone 3A, second reaction zone 3B and connecting zone 3C in the inside of reaction vessel 3a. It is filled with in first conversion zone 3A for making hydrogen and the catalyzer of carbon monoxide and oxygen reaction. It is filled with in second reaction zone 3B for making hydrogen and the catalyzer of oxygen reaction. The catalyzer filled in two reaction zones territory 3A, 3B can also be different catalyzer, but what fill in the present embodiment is identical catalyzer. Such as, in two reaction zones territory 3A, 3B, fill the noble metal catalysts such as ruthenium, palladium, platinum, particularly preferably fill the ruthenium catalyst that can react at low temperature.Catalyzer uses the catalyzer being carried on aluminum oxide etc. Is connecting zone 3C between the first conversion zone 3A and second reaction zone 3B. In connecting zone 3C can not also catalyst filling, but in the present embodiment, in connecting zone 3C, be filled with the catalyzer identical with the catalyzer filled in two reaction zones territory 3A, 3B.
Reaction vessel 3a is provided with gas introduction port 3b, gas flow outlet 3c, gas outlet port 3d and hydrogen and adds mouth 3e. Being connected with well heater 2 on gas introduction port 3b, the helium as purifying object through heating imports reaction unit 3 from gas introduction port 3b. One end of autoreaction container 3a is risen and is configured with gas introduction port 3b, the first conversion zone 3A, connecting zone 3C, second reaction zone 3B and gas flow outlet 3c successively, and gas flow outlet 3c is positioned at the other end of reaction vessel 3a. Such as, connecting zone 3C is configured near the central authorities of gas introduction port 3b and gas flow outlet 3c. By this, from the helium of gas introduction port 3b importing reaction unit 3 successively by, after the first conversion zone 3A, connecting zone 3C, second reaction zone 3B, flowing out from gas flow outlet 3c. Gas outlet port 3d is configured in the position that can be extracted out by the helium in connecting zone 3C, in the present embodiment, is configured to be connected with connecting zone 3C. Hydrogen adds mouth 3e and is configured in and can, to the position adding hydrogen by being imported in the helium of second reaction zone 3B after the first conversion zone 3A, in the present embodiment, be configured to be connected with near second reaction zone 3B and the border of connecting zone 3C.
The helium heated by well heater 2 arrives the first conversion zone 3A from gas introduction port 3b. By this, implement the first reaction process, in this operation, utilize hydrogen and carbon monoxide that catalyzer makes to contain at first in helium and the oxygen reaction contained at first. Now, it is not necessary to add the impurity beyond the impurity contained at first to arriving in the helium of the first conversion zone 3A. By the first reaction process, the hydrogen contained at first in helium and carbon monoxide and the part of oxygen contained at first become water and carbonic acid gas. Even if by implement the first reaction process, in helium also can residual oxygen, therefore by implement the first reaction process, the main impurity contained in helium becomes nitrogen, oxygen, carbonic acid gas, water.
Hydrogen adding set 4 adds mouth 3e via gas outlet port 3d and hydrogen and is connected with reaction unit 3. That is, hydrogen adding set 4 such as comprises: hydrogen supply source 4a, and this hydrogen supply source 4a is made up of High Pressure Hydrogen steel cylinder; Analyzer 4b, this analyzer 4b obtains the oxygen concn of helium; Hydrogen amount regulator 4c, this hydrogen amount regulator 4c adjust the hydrogen amount supplied from hydrogen supply source 4a according to the oxygen concn tried to achieve by analyzer 4b. Analyzer 4b is connected with gas outlet port 3d, obtains the oxygen concn from the helium in the connecting zone 3C of gas outlet port 3d extraction. Hydrogen supply source 4a adds mouth 3e via hydrogen amount regulator 4c with hydrogen and is connected. Hydrogen amount regulator 4c adjusts the aperture joining pipe such as connecting hydrogen supply source 4a and hydrogen interpolation mouth 3e by flowrate control valve etc., adjusts the hydrogen amount supplied from hydrogen supply source 4a by this according to the oxygen concn tried to achieve by analyzer 4b. By this adjustment, from hydrogen add the mouth 3e hydrogen amount that is added into helium less than with the stoichiometric quantity needed for the whole oxygen reaction remaining in helium by the reaction in the first conversion zone 3A. By this, implement hydrogen add operation, in this operation, in helium, add hydrogen by hydrogen adding set 4, this hydrogen amount less than with remain in helium by implementing the first reaction process whole oxygen reaction needed for stoichiometric quantity.In present embodiment, it is with the stoichiometric quantity needed for the whole oxygen reaction remaining in helium by implementing the first reaction process more than 95% and less than 100% that hydrogen adds in operation the hydrogen amount being added in helium. That is, being added by this hydrogen, the hydrogen volumetric molar concentration in helium is more than 1.9 times of oxygen volumetric molar concentration and less than 2 times.
In second reaction zone 3B, implementing the 2nd reaction process, in this operation, utilize oxygen that catalyzer makes to remain in helium by implementing the first reaction process and hydrogen to add the H-H reaction of interpolation in operation, this reacted oxygen and hydrogen become water. By implementing the 2nd reaction process, what the main impurity contained in helium was same with after enforcement the first reaction process is nitrogen, oxygen, carbonic acid gas, water, but oxygen level reduces. The size of the first conversion zone 3A can be determined by experiment, so that hydrogen and carbon monoxide and oxygen can be made fully to react by the first reaction process. The size of second reaction zone 3B can be determined by experiment, so that hydrogen and oxygen from hydrogen interpolation mouth 3e interpolation can be made fully to react by the 2nd reaction process. The size of connecting zone 3C can be determined by experiment, is used for analyzing so that can be extracted out by the helium after implementing the first reaction process, and make to add, from hydrogen, the hydrogen that mouth 3e adds and can not arrive the first conversion zone 3A.
As dewatering unit 5, the 2nd dewatering unit 5b that present embodiment comprises the first dewatering unit 5a and is connected with the first dewatering unit 5a. First dewatering unit 5a is connected with the gas flow outlet 3c of reaction unit 3. Implement dehydration procedure by the first dewatering unit 5a, in this operation, reduce the moisture containing ratio from the helium after enforcement the 2nd reaction process of gas flow outlet 3c outflow by dehydration operation. First dewatering unit 5a of present embodiment is by implementing dehydration procedure by the 2nd reacted helium gas cooling. That is, the temperature of helium flowed out from gas flow outlet 3c is generally 200 DEG C��350 DEG C, therefore with cooler etc. be cooled to room temperature, such as 0 DEG C��40 DEG C, with air water separator etc., the water of cohesion is expelled to outside system. A part for the carbonic acid gas contained in helium is dissolved in the water of cohesion, therefore can be removed from helium by dehydration operation.
By the first dewatering unit 5a, it is possible to the saturated steam amount moisture amount in helium being reduced at the temperature after cooling. The saturated steam amount that moisture amount in helium is reduced by least at this temperature by the 2nd dewatering unit 5b, such as, can be made up of thermal regeneration formula water trap, adding pressure type water trap, freezing type water trap. By the 2nd dewatering unit 5b, it is possible to the moisture containing ratio of helium is reduced to lower than hundreds of ppm. As long as dewatering unit 5 can reduce the moisture containing ratio of helium, form unrestricted, such as can only have either one in the first dewatering unit 5a, the 2nd dewatering unit 5b, but because follow-up transformation absorption process is implemented usually at normal temperatures, so it is better dewatered by cooling helium. In addition, because the sorbent material Preferential adsorption moisture such as the activated alumina used in transformation absorption process, so being better the moisture containing ratio being reduced helium by dewatering unit 5 as much as possible, prevent the carbonic acid gas absorption property of the sorbent materials such as activated alumina from reducing, therefore it is better comprise the first dewatering unit 5a, the 2nd dewatering unit 5b.
Adsorption unit 9 is connected with dewatering unit 5, comprises the PSA unit (psa unit) 10 being connected with the 2nd dewatering unit 5b and the TSA unit (becoming temperature absorbing unit) 20 being connected with PSA unit 10.Implementing transformation absorption process by PSA unit 10, in this operation, remaining in after making to carry out dehydration operation by dewatering unit 5 by pressure swing adsorption process in helium is at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material. In addition, PSA unit 10 also adsorb carry out dehydration operation by dewatering unit 5 after remain in helium moisture. By PSA unit 10, it is possible to the containing ratio of the carbonic acid gas in helium and water is reduced to such as lower than 1 molar ppm, about nitrogen containing ratio and oxygen containing ratio are reduced to such as 1 molar ppm. After transformation absorption process, implemented by TSA unit 20 to become temperature absorption process, in this operation, make the N2 adsorption of residual in helium in sorbent material by the change temperature absorption method at-10 DEG C��-50 DEG C. In addition, TSA unit 20 also remains in the oxygen in helium after pressure swing adsorption operation. By TSA unit 20, it is possible to the nitrogen containing ratio in helium, oxygen containing ratio are reduced to respectively such as lower than 1 molar ppm.
PSA unit 10 can use known unit. The such as PSA unit 10 shown in Fig. 2 is 4 tower, comprises the compressor 12 of helium compression that flows out from dewatering unit 5 and the 4 first��the 4th adsorption tower 13, is filled with sorbent material in each adsorption tower 13. Such as, as this sorbent material, it may also be useful to be suitable for the sorbent material of the absorption of carbonic acid gas, nitrogen and oxygen, activated alumina, zeolite class sorbent material and carbonaceous molecular sieve be laminated in adsorption tower with predetermined order and fill. As zeolite class sorbent material, it it is better X type zeolite. The lamination order of these sorbent materials is better be followed successively by activated alumina, zeolite class sorbent material, carbonaceous molecular sieve from the introduction side of helium, or activated alumina, carbonaceous molecular sieve, zeolite class sorbent material. When nitrogen contained in helium is more, it is better use zeolite class sorbent material more, when oxygen is more, it is better use carbonaceous molecular sieve more. Activated alumina, at the introduction side primary attachment carbonic acid gas of helium, by this, can prevent zeolite class sorbent material subsequently to the decline of the adsorption effect of nitrogen. The volume ratio of the loading level of these sorbent materials is such as: activated alumina: X type zeolite: carbonaceous molecular sieve is 2��3:7��4:1��3. By making most of oxygen and the H-H reaction of residual in helium in the 2nd reaction process, the oxygen desorption load of PSA unit 10 can be alleviated, make adsorption tower 13 miniaturization.
Compressor 12 is connected via the entrance 13a of switching valve 13b with each adsorption tower 13.
The entrance 13a of adsorption tower 13 is respectively via switching valve 13e and sourdine 13f and bonding in air.
The outlet 13k of adsorption tower 13 joins pipe 13m via switching valve 13l with outflow respectively and is connected, via switching valve 13n, press fit pipe 13o is connected with rising, wash out side line 13q via switching valve 13p with all compressing and washing to be connected, wash with all compressing and washing via switching valve 13r and be connected into side line 13s.
Outflow is joined pipe 13m and is connected with TSA unit 20 via pressure regulator valve 13t, imports the maintain constant pressure of the helium of TSA unit 20.
Rise press fit pipe 13o to join pipe 13m with outflow be connected via flowrate control valve 13u, flow instruction accommodometer 13v, it is constant by the Flow-rate adjustment that will rise in press fit pipe 13o, thus prevents the flow variation importing the helium of TSA unit 20.
All compress and wash to wash out side line 13q and all compress and wash to wash and it is interconnected via one couple of connecting pipings 13w into side line 13s, each connecting pipings 13w is provided with switching valve 13x.
In the first��four adsorption tower 13 of PSA unit 10, carry out absorption process, decompression I operation (washing gas goes out operation), decompression II operation (body of all calming the anger goes out operation), desorption step, washing procedure (washing gas enters operation), boosting I operation (body of all calming the anger enters operation), boosting II operation respectively successively.Each operation is described taking the first adsorption tower 13 as benchmark.
That is, in the first adsorption tower 13, only opening switching valve 13b and switching valve 13l, the helium supplied from dewatering unit 5 is imported into the first adsorption tower 13 from compressor 12 via switching valve 13b. By this, in the first adsorption tower 13, in the helium of importing be at least carbonic acid gas, nitrogen and oxygen by adsorbent, thus carry out absorption process, the helium that impurity containing ratio decreases is joined pipe 13m from the first adsorption tower 13 via outflow and is sent to TSA unit 20. Now, deliver to the part flowing out the helium joining pipe 13m via rising press fit pipe 13o, flowrate control valve 13u is sent to other adsorption tower (being the 2nd adsorption tower 13 in present embodiment), carries out boosting II operation in the 2nd adsorption tower 13.
Then, close switching valve 13b, 13l of the first adsorption tower 13, open switching valve 13p, open the switching valve 13r of other adsorption tower (being the 4th adsorption tower 13 in present embodiment), open in switching valve 13x. By this, the less helium of the impurity containing ratio on the first adsorption tower 13 top is washed via all compressing and washing and is sent to the 4th adsorption tower 13 into side line 13s, carries out decompression I operation in the first adsorption tower 13. Now, in the 4th adsorption tower 13, open switching valve 13e, carry out washing procedure.
Then, when opening the switching valve 13r of the switching valve 13p of the first adsorption tower 13 and the 4th adsorption tower 13, the switching valve 13e of the 4th adsorption tower 13 is closed. By this, carry out implementing the decompression II operation of gas recovery in the 4th adsorption tower 13, until the internal pressure of the first adsorption tower 13 and the 4th adsorption tower 13 reaches equal one or roughly equal one. Now, according to circumstances two switching valve 13x can also be opened.
Then, opening the switching valve 13e of the first adsorption tower 13, close switching valve 13p, thus carry out the desorption step that makes impurity from desorb sorbent material, impurity is released in air via sourdine 13f together with gas.
Then, open the switching valve 13r of the first adsorption tower 13, close absorption process terminate after switching valve 13b, 13l of the 2nd adsorption tower 13 of state, open switching valve 13p. By this, the less helium of the impurity containing ratio on the 2nd adsorption tower 13 top is washed via all compressing and washing and is sent to the first adsorption tower 13 into side line 13s, carries out washing procedure in the first adsorption tower 13. The gas used in washing procedure in first adsorption tower 13 is released in air via switching valve 13e, sourdine 13f. Now, in the 2nd adsorption tower 13, carry out decompression I operation.
Then, when opening the switching valve 13r of the switching valve 13p of the 2nd adsorption tower 13 and the first adsorption tower 13, close the switching valve 13e of the first adsorption tower 13, thus carry out boosting I operation. Now, according to circumstances two switching valve 13x can also be opened.
Then, close the switching valve 13r of the first adsorption tower 13. By this, the standby state not having operation temporarily it is in. Till this state lasts till that the boosting II operation of the 4th adsorption tower 13 terminates. After the boosting of the 4th adsorption tower 13 terminates, absorption process switches to the 4th adsorption tower 13 from the 3rd adsorption tower 13, open the switching valve 13n of the first adsorption tower. By this, be sent to from other adsorption tower (being the 4th adsorption tower 13 present embodiment) being in absorption process the part flowing out the helium joining pipe 13m via rising press fit pipe 13o, flowrate control valve 13u is sent to the first adsorption tower 13, thus carries out boosting II operation in the first adsorption tower 13.
By repeatedly carrying out above-mentioned each operation in the first��four adsorption tower 13 respectively successively, thus TSA unit 20 delivered to continuously by the helium decreased by impurity containing ratio.
PSA unit 10 is not limited to the PSA unit shown in Fig. 2, and such as tower number is except 4, such as, can also be 2 or 3.
TSA unit 20 can use known unit. The such as TSA unit 20 shown in Fig. 3 is 2 tower, comprising: the heat exchange type pre-cooler 21 of helium precooling will sent here from PSA unit 10; The heat exchange type water cooler 22 that the helium cooled through pre-cooler 21 is cooled further; First, second adsorption tower 23; Cover the heat exchange department 24 of each adsorption tower 23. Heat exchange department 24 utilizes refrigerant to be cooled by sorbent material when absorption process, utilizes hot matchmaker to be heated by sorbent material when desorption step. Each adsorption tower 23 has the interior pipe that many are filled with sorbent material. As this sorbent material, it may also be useful to be suitable for the sorbent material of the absorption of nitrogen and oxygen. As the sorbent material of N2 adsorption, it it is better such as the zeolite class sorbent material using and having carried out ion-exchange with calcium (Ca) or lithium (Li), in addition, particularly preferably ion exchange ratio is more than 70%, and particularly preferably specific surface area is more than 600m2. As the sorbent material of oxygen desorption, it is better use carbonaceous molecular sieve, it is filled in adsorption tower 23 with layered laminate together with the zeolite class sorbent material of N2 adsorption.
Water cooler 22 in TSA unit 20 is connected via the entrance 23a of switching valve 23b with each adsorption tower 23.
The entrance 23a of adsorption tower 23 is connected with air via switching valve 23c respectively.
The outlet 23e of adsorption tower 23 joins pipe 23g via switching valve 23f with outflow respectively and is connected, and is connected with joining pipe 23i with cooling boosting via switching valve 23h, is connected with joining pipe 23k with the 2nd washing via switching valve 23j.
Flow out and join the part that pipe 23g forms pre-cooler 21, utilize the helium after the purifying joining pipe 23g outflow from outflow to cool the helium sent here from PSA unit 10. Join pipe 23g through the helium of purifying from outflow to flow out via a wall pressure control valve 23l.
Cooling boosting with joining pipe 23i, washing joins pipe 23g via under meter 23m, flowrate control valve 23o, switching valve 23n with outflow be connected with joining pipe 23k.
Heat exchange department 24 is multitube, is made up of with scatterer 24e the outer tube 24a surrounded by many that form adsorption tower 23 interior pipes, refrigerant supply source 24b, refrigerant scatterer 24c, hot matchmaker supply source 24d, hot matchmaker. Refrigerant supply source 24b comprises the refrigerator that refrigerant is cooled to-10 DEG C��-50 DEG C, and hot matchmaker supply source 24d comprises heating medium for heating to the well heater of room temperature, refrigerator and well heater see it is better use commercially available Industrial products originally from becoming. In addition, also being provided with multiple switching valve 24f, these switching valves 24f is used for switching between the state making the refrigerant supplied from refrigerant supply source 24b circulate and the state making the hot matchmaker supplied from hot matchmaker supply source 24d circulate with scatterer 24e via outer tube 24a, hot matchmaker via outer tube 24a, refrigerant scatterer 24c. In addition, joining, from what refrigerant scatterer 24c separated, the part that pipe forms water cooler 22, utilize the refrigerant supplied from refrigerant supply source 24b to cool helium water cooler 22, this refrigerant is back to tank 24g.
In first, second adsorption tower 23 of TSA unit 20, carry out absorption process, desorption step, washing procedure, cooling operation, boosting operation respectively successively.
That is, in TSA unit 20, after the helium of PSA unit 10 supply is cooled pre-cooler 21, water cooler 22, the first adsorption tower 23 is imported via switching valve 23b.Now, by the circulation of refrigerant in heat exchange department 24, the first adsorption tower 23 is in the state being cooled to-10 DEG C��-50 DEG C, closes switching valve 23c, 23h, 23j, opens switching valve 23f, and what contain in helium is at least that nitrogen and oxygen are by adsorbent. By this, carrying out absorption process in the first adsorption tower 23, the purifying helium that impurity containing ratio decreases flows out from the first adsorption tower 23 via a wall pressure control valve 23l, such as, be sent to products pot (omitting diagram).
First adsorption tower 23 carries out in the process of absorption process, the 2nd adsorption tower 23 carries out desorption step, washing procedure, cooling operation, boosting operation.
That is, in the 2nd adsorption tower 23, after absorption process terminates, in order to implement desorption step, close switching valve 23b, 23f, open switching valve 23c. By this, in the 2nd adsorption tower 23, the helium containing impurity is released in air, and pressure is down near normal atmosphere. In this desorption step, the switching valve 24f of the heat exchange department 24 making refrigerant circulate in the 2nd adsorption tower 23 when absorption process is switched to closing condition, the circulation of refrigerant is stopped, and the switching valve 24f that will take out refrigerant from heat exchange department 24 and refrigerant is back to refrigerant supply source 24b switches to the state of opening.
Then, in order to implement washing procedure in the 2nd adsorption tower 23, making switching valve 23c, 23j and the washing switching valve 23n joining pipe 23k of the 2nd adsorption tower 23 be in the state of opening, a part for the purifying helium heated by the heat exchange in heat exchange type pre-cooler 21 is imported into the 2nd adsorption tower 23 via washing with joining pipe 23k. By this, in the 2nd adsorption tower 23, implementing to come the desorb of the impurity of self-absorbent and use the washing of purifying helium, the helium used in this washing is released into air together with impurity from switching valve 23c. In this washing procedure, the switching valve 24f of the heat exchange department 24 being used for hot matchmaker is circulated in the 2nd adsorption tower 23 is switched to the state of opening.
Then, in order to implement cooling operation in the 2nd adsorption tower 23, switching valve 23j and the washing of the 2nd adsorption tower 23 is made to be in closing condition with the switching valve 23n joining pipe 23k, make switching valve 23h and the cooling boosting of the 2nd adsorption tower 23 be in, with the switching valve 23n joining pipe 23i, the state of opening, it is imported into two adsorption tower 23 via cooling boosting with joining pipe 23i from a part for the purifying helium of the first adsorption tower 23 outflow. By this, the purifying helium cooled in the 2nd adsorption tower 23 is released in air via switching valve 23c. In this cooling operation, the switching valve 24f being used for hot matchmaker is circulated being switched to closing condition, hot matchmaker is circulated stopping, the switching valve 24f that will take out hot matchmaker from heat exchange department 24 and hot matchmaker is back to hot matchmaker supply source 24d switches to the state of opening. After the taking-up of hot matchmaker terminates, the switching valve 24f of the heat exchange department 24 being used for refrigerant is circulated in the 2nd adsorption tower 23 is switched to the state of opening, it is achieved refrigerant circulation state. Till this refrigerant circulation state lasts till the end of follow-up boosting operation and absorption process subsequently.
Then, in order to implement boosting operation in the 2nd adsorption tower 23, close the switching valve 23c of the 2nd adsorption tower 23, a part for the purifying helium flowed out from the first adsorption tower 23 is imported, thus boost in the inside making the 2nd adsorption tower 23. Till this boosting operation lasts till that the interior pressure of the 2nd adsorption tower 23 is roughly equal with the interior pressure of the first adsorption tower 23.After boosting operation terminates, close the switching valve 23h and the cooling boosting switching valve 23n joining pipe 23i of the 2nd adsorption tower 23, all switching valve 23b, 23c, 23f, 23h, 23j of the 2nd adsorption tower 23 are made to be in closing condition by this, 2nd adsorption tower 23 is in standby state, until follow-up absorption process.
The absorption process of the 2nd adsorption tower 23 is implemented samely with the absorption process of the first adsorption tower 23. 2nd adsorption tower 23 carries out in the process of absorption process, in the first adsorption tower 23, carry out desorption step, washing procedure, cooling operation, boosting operation samely with the 2nd adsorption tower 23.
TSA unit 20 is not limited to the TSA unit shown in Fig. 3, and such as tower number is more than 2, such as, can also be 3 or 4.
Adopting in the helium of purifying object of above-mentioned purification devices ��, the oxygen amount contained at first is more than with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide. By this, the helium as purifying object that heated by well heater 2 is imported the first conversion zone 3A of reaction unit 3, such that it is able to make the hydrogen contained at first and carbon monoxide and the part of oxygen that contains at first be become water and carbonic acid gas by the first reaction process. The oxygen in helium is remained in and the hydrogen that is added in helium by hydrogen adding set 4 can become water by the 2nd reaction process in second reaction zone 3B by implementing the first reaction process. The hydrogen amount added by hydrogen adding set 4 less than with the stoichiometric quantity needed for the whole oxygen reaction remaining in helium by implementing the first reaction process, be therefore possible to prevent to implement helium to remain hydrogen after the 2nd reaction process. By this, the analysis and the gas that do not carry out the impurity concentration of helium before the first reaction process add, and before the 2nd reaction process, only carry out analysis and the gas interpolation of the impurity concentration of helium, a large amount of carbon monoxide is remained after just preventing the first reaction process, and before absorption process can be prevented, remain a large amount of oxygen, therefore can simplify purification process. In above-mentioned enforcement mode, the hydrogen amount added by hydrogen adding set 4 be with remain in helium whole oxygen reaction needed for stoichiometric quantity more than 95% and less than 100%, therefore the most of oxygen in helium can be made by the 2nd reaction process and H-H reaction, in absorption process, if the oxygen of the minute quantity remained in absorption helium. In addition, it is possible to before absorption process, from helium, remove the hydrogen being difficult to be separated from helium by absorption method. In addition, it is possible in a reaction vessel 3a, carry out the first reaction process and the 2nd reaction process, facility compact can be made, reduce costs. The water generated by the 2nd reaction is removed from helium by the dehydration operation of dewatering unit 5. By this, the moisture containing ratio of helium reduces, and therefore can alleviate the absorption load of the moisture of the adsorption unit 9 in follow-up absorption process. In addition, after implementing the 2nd reaction process, dehydration procedure is implemented by cooling helium, therefore without the need to again being heated by the helium temporarily cooled in order to dehydration operation, it is possible to reduce energy consumption. In addition, after transformation absorption process, make the nitrogen remained in helium and oxygen desorption in sorbent material by becoming temperature absorption method, thus the containing ratio of the nitrogen in helium and oxygen can be reduced further.
Fig. 4 represents the variation of reaction unit 3. Be with the difference of above-mentioned enforcement mode, reaction unit 3 comprise the first reaction vessel 3a', the 2nd reaction vessel 3b' and connect the first reaction vessel 3a' and the 2nd reaction vessel 3b' join pipe 3c'.Being the first conversion zone 3A in first reaction vessel 3a', be second reaction zone 3B in the 2nd reaction vessel 3b', joining is connecting zone 3C in pipe 3c', non-catalyst filling in connecting zone 3C. Hydrogen adds mouth 3e and is configured to be connected with connecting zone 3C. Other is identical with above-mentioned enforcement mode.
[embodiment 1]
Above-mentioned purification devices �� is used to carry out the purifying of helium. In the present embodiment, do not use TSA unit 20. Reaction unit 3 uses the reaction unit recorded in variation.
Helium as purifying object uses the helium helium recovery being distributed in air after use in the wire-drawing process of optical fiber obtained, as impurity, respectively containing nitrogen 23.43 moles of %, oxygen 6.28 moles of %, hydrogen 50 molar ppm, carbon monoxide 30 molar ppm, carbonic acid gas 50 molar ppm, methane 2 molar ppm, moisture 20 molar ppm. Helium as purifying object comprises argon, but is ignored.
After this helium well heater 2 is heated, in normal conditions with the flow feeding reaction device 3 of 3.31L/min. Filling the ruthenium catalyst 45mL of supported on alumina in the first reaction vessel 3a', the reaction conditions in the first reaction vessel 3a' is temperature 190 DEG C, space velocity 5000/h.
Analyzing the oxygen concn of the helium flowed out from the first reaction vessel 3a', add hydrogen from hydrogen adding set 4 to helium, the amount of this hydrogen is reacted with whole oxygen and generates 98% of the stoichiometric quantity needed for water. Filling the catalyzer 150mL identical with the first reaction vessel 3a' in the 2nd reaction vessel 3b', the reaction conditions in the 2nd reaction vessel 3b' is identical with the first reaction vessel 3a'.
The helium flowed out from the 2nd reaction vessel 3b' is cooled to 25 DEG C by the first dewatering unit 5a, the water of liquefaction is removed from helium. By this, the moisture containing ratio of helium is reduced to 25 DEG C saturated (being about 3% when total pressure is set to normal atmosphere). Then, in the packed tower of the dehydration activated alumina used as the 2nd dewatering unit 5b, import helium, moisture amount is reduced to 95ppm. Activated alumina (Sumitomo chemistry KHD-24 processed) 250mL is filled in the packed tower of the 2nd dewatering unit 5b.
The impurity containing ratio of the helium flowed out from the 2nd dewatering unit 5b is reduced by desorption apparatus 9. PSA unit 10 is 4 tower, in each tower, from gas introduction side, it is sequentially laminated with activated alumina (Sumitomo chemistry KHD-24 processed), LiX type zeolite molecular sieve (east Cao (��) Inc. NSA-700), carbonaceous molecular sieve (laughable beautiful chemistry (Network �� �� �� �� �� Le) Inc. GN-UC-H) as sorbent material, fills 1.25L altogether. The volume ratio of these sorbent materials is activated alumina: zeolite molecular sieve: carbonaceous molecular sieve=25:65:10. The adsorptive pressure of PSA unit 10 is set as that 0.9MPa, desorption pressures are set as that 0.03MPa, cycling time are 250 seconds.
From PSA unit 10 flow out purifying after helium impurity composed as follows described in.
Oxygen 1.0 molar ppm, nitrogen 1.2 molar ppm, hydrogen less than 1 molar ppm, carbon monoxide less than 1 molar ppm, carbonic acid gas less than 1 molar ppm, methane less than 1 molar ppm, moisture less than 1 molar ppm. As purifying object helium contained by argon ignore.
Here, oxygen concn Te Lidan company (Teledyne society) the micro amount of oxygen densitometer model 311 processed of helium measures, methane concentration Shimadzu makes institute (institute is done in Tianjin) GC-FID processed and measures, and the concentration of carbon monoxide and carbonic acid gas makes made GC-FID by Shimadzu equally and measures via methanator.Hydrogen concentration GL scientific company (GLScience society) GC-PID processed measures. Nitrogen concentration Shimadzu makes made GC-PDD and measures. The dew point meter DEWMET-2 that moisture GE sensing Japanese firm (GE �� Application �� Application �� �� �� �� Application society) makes measures.
[embodiment 2]
The volume ratio of the sorbent material filled in each tower of PSA unit 10 is activated alumina: zeolite molecular sieve: carbonaceous molecular sieve=25:60:15. Other purifying helium similarly to Example 1.
From PSA unit 10 flow out purifying after helium impurity composed as follows described in.
Oxygen less than 1 molar ppm, nitrogen 1.3 molar ppm, hydrogen less than 1 molar ppm, carbon monoxide less than 1 molar ppm, carbonic acid gas less than 1 molar ppm, moisture less than 1 molar ppm.
[embodiment 3]
Helium TSA unit 20 after the purifying flowed out from PSA unit 10 is further purified. TSA unit 20 is 2 tower, in each adsorption tower, is filled with CaX type zeolite molecular sieve (Dong Cao Inc. SA-600A) 1.2L, carbonaceous molecular sieve 0.3L respectively as sorbent material. The adsorptive pressure of TSA unit 20 to be 0.8MPaG, desorption pressures be 0.03MPaG, adsorption temp are-35 DEG C, desorption temperature is 40 DEG C. From TSA unit 20 flow out purifying after helium impurity composed as follows described in.
Oxygen less than 1 molar ppm, nitrogen less than 1 molar ppm, hydrogen less than 1 molar ppm, carbon monoxide less than 1 molar ppm, carbonic acid gas less than 1 molar ppm, methane less than 1 molar ppm, moisture less than 1 molar ppm.
[embodiment 4]
The loading level of activated alumina in the packed tower of the dehydration activated alumina used as the 2nd dewatering unit 5b is 2 times of embodiment 1, as the sorbent material filled in each tower of PSA unit 10, do not use activated alumina, but fill zeolite molecular sieve 1.0L, carbonaceous molecular sieve 0.25L respectively. Other purifying helium similarly to Example 1.
From PSA unit 10 flow out purifying after helium impurity composed as follows described in.
Oxygen 1.2 molar ppm, nitrogen 1.4 molar ppm, hydrogen less than 1 molar ppm, carbon monoxide less than 1 molar ppm, carbonic acid gas less than 1 molar ppm, moisture less than 1 molar ppm.
[comparative example 1]
The purifying helium when the moisture not using dewatering unit to carry out helium reduces. Other is identical with embodiment 1.
From PSA unit 10 flow out purifying after helium impurity composed as follows described in.
Oxygen 1.9 molar ppm, nitrogen 200ppm, hydrogen less than 1ppm, carbon monoxide less than 1ppm, carbonic acid gas less than 1ppm, moisture less than 1ppm.
The present invention is not limited to above-mentioned enforcement mode, variation, embodiment. Such as, the helium being purified by the present invention is not limited to the helium that obtain by the helium recovery that is distributed in air after using in the wire-drawing process of optical fiber, as long as at least contain hydrogen, carbon monoxide, nitrogen and oxygen as impurity, the oxygen amount that contains at first than the helium many with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide. In addition, not necessarily, purification devices can not comprise TSA unit in the absorption adopting change temperature absorption method.
Claims (7)
1. the purification process of helium, it is characterised in that, purifying at least containing hydrogen, carbon monoxide, nitrogen and oxygen as impurity, the oxygen amount that contains at first than, during with the helium that the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide is many, comprising:
First reaction process, in this operation, utilizes the oxygen reaction that catalyzer makes the hydrogen contained at first in described helium and carbon monoxide and contains at first;
Hydrogen add operation, in this operation, in described helium, add hydrogen, this hydrogen amount less than with remain in described helium by implementing described first reaction process whole oxygen reaction needed for stoichiometric quantity;
2nd reaction process, in this operation, utilizes catalyzer to make the H-H reaction remaining in the oxygen in described helium by implementing described first reaction process and adding in described hydrogen interpolation operation;
Dehydration procedure, in this operation, reduces the moisture containing ratio of the described helium after implementing described 2nd reaction process by dehydration operation;
Transformation absorption process, in this operation, remaining in after making described dehydration operation by pressure swing adsorption process in described helium is at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material;
It is with the stoichiometric quantity needed for the whole oxygen reaction remaining in described helium by implementing described first reaction process more than 95% and less than 100% that described hydrogen adds in operation the hydrogen amount added.
2. the purification process of helium as claimed in claim 1, it is characterised in that, by described helium gas cooling being implemented described dehydration procedure after implementing described 2nd reaction process.
3. the purification process of helium as claimed in claim 1 or 2, it is characterised in that, it may also be useful to activated alumina, zeolite class sorbent material and carbonaceous molecular sieve, as described sorbent material, after making carbonic acid gas be adsorbed in activated alumina, make N2 adsorption in zeolite class sorbent material.
4. the purification process of helium as claimed in claim 1 or 2, it is characterized in that, comprise after described transformation absorption process and become temperature absorption process, in this operation, make the nitrogen remained in described helium and oxygen desorption in sorbent material by the change temperature absorption method at-10 DEG C��-50 DEG C.
5. the purification process of helium as claimed in claim 3, it is characterised in that, comprise after described transformation absorption process and become temperature absorption process, in this operation, make the nitrogen remained in described helium and oxygen desorption in sorbent material by the change temperature absorption method at-10 DEG C��-50 DEG C.
6. the purification devices of helium, its be purifying at least containing hydrogen, carbon monoxide, nitrogen and oxygen as impurity, the oxygen amount that contains at first than the device of the helium many with the stoichiometric quantity needed for the whole hydrogen contained at first and reaction of carbon monoxide, it is characterized in that, comprising:
Well heater, helium described in this heater heats;
Reaction unit, this reaction unit has the connecting zone of the first conversion zone, second reaction zone and described first conversion zone and described second reaction zone, described first conversion zone is filled with for making hydrogen and the catalyzer of carbon monoxide and oxygen reaction, and described second reaction zone is filled with for making hydrogen and the catalyzer of oxygen reaction;
Hydrogen adding set, this hydrogen adding set comprises hydrogen supply source, analyzer and hydrogen amount regulator, and described analyzer obtains the oxygen concn of helium, and described hydrogen amount regulator adjusts the hydrogen amount from the supply of described hydrogen supply source according to the oxygen concn tried to achieve;
Dewatering unit;
Adsorption unit, this adsorption unit is connected with described dewatering unit;
The hydrogen that described reaction unit is provided with gas outlet port that the gas flow outlet that the gas introduction port being connected with described well heater is connected is connected with described analyzer with described dewatering unit, be connected with described hydrogen supply source via described hydrogen amount regulator adds mouth;
Configure described gas introduction port, described first conversion zone, described connecting zone, described second reaction zone and described gas flow outlet so that the described helium importing described reaction unit from described gas introduction port is successively by flowing out from described gas flow outlet after described first conversion zone, described connecting zone, described second reaction zone;
Described gas outlet port is configured in the position that can be extracted out by the helium in described connecting zone, and described hydrogen interpolation mouth is configured in can to by being imported into, after described first conversion zone, the position adding hydrogen in the helium of described second reaction zone;
Oxygen concn according to the described helium in the described connecting zone tried to achieve by described analyzer, the hydrogen amount from the supply of described hydrogen supply source is adjusted so that adding the mouth hydrogen amount that is added into described helium from described hydrogen is with the stoichiometric quantity needed for the whole oxygen reaction remaining in described helium by the reaction in described first conversion zone more than 95% and less than 100% by described hydrogen amount regulator;
Described dewatering unit is connected with described gas flow outlet so that the moisture containing ratio of the described helium flowed out from described gas flow outlet is reduced by dehydration operation;
Described adsorption unit has psa unit, and this psa unit makes in described helium to be at least that carbonic acid gas, nitrogen and oxygen desorption are in sorbent material by pressure swing adsorption process.
7. the purification devices of helium as claimed in claim 6, it is characterised in that, described reaction unit has a reaction vessel, is provided with described first conversion zone, connecting zone and second reaction zone in described reaction vessel.
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