CN103159192B - The purification process of helium and purification devices - Google Patents
The purification process of helium and purification devices Download PDFInfo
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- CN103159192B CN103159192B CN201210488702.XA CN201210488702A CN103159192B CN 103159192 B CN103159192 B CN 103159192B CN 201210488702 A CN201210488702 A CN 201210488702A CN 103159192 B CN103159192 B CN 103159192B
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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]
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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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
There is provided and can will reclaim the method and apparatus that helium purifying is highly purified practicality with low cost.Dealkylation is removed from the oxygen amount contained as impurity than adsorbing the helium many with the amount required for the whole hydrogen contained as impurity, carbon monoxide, hydrocarbon reaction by gac.Then, with palladium or rhodium for catalyzer makes the oxygen in impurity and hydrogen, carbon monoxide, residual hydrocarbon reaction.Then, according to do not make the hydrogen volumetric molar concentration in helium be more than 2 times of the volumetric molar concentration of residual oxygen condition add hydrogen, with palladium, platinum or rhodium for after catalyzer makes it react, reduce moisture containing ratio by dewatering unit, add the carbon monoxide of the volumetric molar concentration of 2 times higher than residual oxygen volumetric molar concentration.Then, with ruthenium, palladium or rhodium for after catalyzer makes oxygen and reaction of carbon monoxide, the carbon monoxide in helium, carbonic acid gas, nitrogen, water is made to be adsorbed on activated alumina and zeolite by pressure swing adsorption process.
Description
Technical field
The present invention relates to be suitable for reclaim after such as using in the manufacturing process of optical fiber, at least containing hydrogen, carbon monoxide, hydrocarbon with derive from the nitrogen of air and oxygen to carry out purifying method and apparatus as the helium of impurity.
Background technology
For the helium be distributed to after such as use in the wire-drawing process of optical fiber, use in air, sometimes by its recycling.Described recovery helium contain such as be mixed in the wire-drawing process of optical fiber hydrogen, carbon monoxide, by being distributed to the nitrogen deriving from air that is mixed in air and oxygen etc. and deriving from recovery after using time use the hydrocarbon of oil seal rotary vacuum pump, oil content as impurity, therefore need to carry out purifying to improve purity.
So known following method: by impurity contained in the helium before purifying liquefaction being removed using liquid nitrogen as the cryogenic operations of refrigeration source, by sorbent material by the trace impurity of remnants absorption removing (with reference to patent documentation 1).Also known following method: add hydrogen in helium before purification, makes this hydrogen and reacts as the oxygen in the air composition of impurity and generate moisture, removes residual impurity (with reference to patent documentation 2) after removing this moisture by membrane separation unit.Also known following method: impurity contained in the rare gas such as the helium before purifying is contacted with alloy degasser, thus be removed (with reference to patent documentation 3).
Prior art document
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
Summary of the invention
In the method that patent documentation 1 is recorded, because need to carry out cryogenic operations with liquid nitrogen, so cooling energy increases; In the method that patent documentation 2 is recorded, because need membrane sepn module, equipment cost is high; The recovery income of the helium of any one method is all less.In addition, in the method that patent documentation 2 is recorded, remove deoxidation by adding hydrogen in the helium as purifying object, but and reckon without the abundant removing of hydrogen, detrimentally affect may be caused to the material that the meeting of optical fiber starting material and so on cause deterioration to aggravate because of hydrogen.In the method that patent documentation 3 is recorded, because the ability of alloy degasser is little, so can only be used for being the situation that the low-purity helium of ppm level is purified to ultra-high purity by impurity concentration, the situation being mixed into a large amount of impurity cannot be directly used in.In addition, by the air containing tens % and the content deriving from the hydrocarbon of the oil seal rotary vacuum pump used in recovery be not ppm level but the helium purifying of hundreds of ~ several thousand ppm for high purity and the method reclaimed also do not exist.
Method of the present invention is used for purifying helium, described helium is at least containing hydrogen, carbon monoxide, hydrocarbon with derive from the nitrogen of air and oxygen as impurity, the amount of its oxygen contained is than more with the amount required for the whole hydrogen, carbon monoxide and the hydrocarbon reaction that contain, and method of the present invention has following operation.
In the present invention, as the first operation, by the hydrocarbon in charcoal absorption removing helium.Thus, can remove on the activated carbon by making the many hydrocarbon of the carbon number in the helium of purifying object adsorb.
Such as, helium is delivered to the activated carbon tower being filled with gac.When helium contains oil content, it is desirable to by passing oil strainer thus passing activated carbon tower again after removing oil content.The hydrocarbon that carbon number is few is not tightly held by activated carbon.Therefore, from activated carbon tower helium out contain such as about about 30% air and carbon monoxide, carbonic acid gas, hydrogen and carbon number be that the hydrocarbon of 1 ~ 6 is as impurity.
As the second operation, the first anti-applications catalyst is used to make hydrogen in the oxygen in described helium and described helium, carbon monoxide and not by the hydrocarbon reaction of described charcoal absorption.
Thus, the hydrocarbon that residual in helium carbon number is few is transformed into water and carbonic acid gas by the reaction of the oxygen with the anti-applications catalyst of use first.Now, owing to not adding hydrogen in helium, can prevent the temperature of reaction caused by a large amount of generations of water from declining thus promoting reaction.
In order to make hydrocarbon and oxygen fully react, need to make temperature of reaction be 300 ~ 400 DEG C.Therefore, use the palladium of reactivity at high temperature, good endurance or rhodium as the first anti-applications catalyst.Temperature of reaction it is desirable to more than 350 DEG C.
Be filled with in the first reactor of palladium catalyst or rhodium catalyst by being delivered to by helium, hydrogen is transformed into water, carbon monoxide is converted into carbonic acid gas, hydrocarbon is converted into water and carbonic acid gas, and oxygen remains.
As the 3rd operation, be that the condition of more than 2 times of oxygen volumetric molar concentration adds hydrogen in described helium according to not making the hydrogen volumetric molar concentration in described helium.
Under such circumstances, it is desirable to the residual oxygen amount analyzed in helium and add hydrogen with make the mol ratio of hydrogen than whole oxygen residual in helium with the theoretical molar required for H-H reaction than less slightly.
Thus, after can preventing using the second catalysts below, hydrogen remains.
As the 4th operation, the second anti-applications catalyst is used to make oxygen in described helium and H-H reaction.Thus, make to generate water under the residual state of oxygen.
Thus, due to the residual oxygen amount in helium can be reduced, therefore can reduce thereafter in order to use the 3rd anti-applications catalyst to make residual oxygen react the carbon monoxide addition added.That is, the high and addition of the carbon monoxide that toxicity is higher of valency can be reduced.
Owing to using the temperature of reaction of the second anti-applications catalyst to be advisable with 100 ~ 300 DEG C, therefore use palladium, platinum or rhodium as the second anti-applications catalyst.
After this reaction, containing nitrogen, water, carbonic acid gas and residual oxygen in helium.
As the 5th operation, use dewatering unit reduces the moisture containing ratio in described helium.
Thus, can prevent carbon monoxide and water reaction in the 7th operation below from generating hydrogen.Because hydrogen has the behavior same with helium, be therefore all difficult to absorption removing by pressure swing adsorption process and thermal swing adsorbent method.Therefore, need to dewater between the 4th operation and the 7th operation.
As dewatering unit, such as, the tower that two are filled with dewatering agent activated alumina is set, uses the device be connected alternately with the stream of helium, during being dewatered by a tower, make the dewatering agent of another tower regenerate.
When oxygen level in the helium of purifying object is high, owing to generating a large amount of water in the 4th operation, it is therefore desirable that arrange multistage dewatering unit.Under such circumstances, the packed tower of the dewatering agent such as making helium ventilate can be used as prime dewatering unit, helium pressurization cooling is removed the freezing type dewatering unit of the moisture be condensed.
As the 6th operation, in described helium, add carbon monoxide higher than the condition of 2 times of oxygen volumetric molar concentration according to the carbon monoxide volumetric molar concentration made in described helium.
Under such circumstances, analyze the residual oxygen amount in helium, it is desirable to add carbon monoxide with make the mol ratio of carbon monoxide than with whole oxygen of remaining in helium with the theoretical molar required for H-H reaction than slightly many.
As the 7th operation, the 3rd anti-applications catalyst is used to make oxygen in described helium and reaction of carbon monoxide.Thus, make to generate carbonic acid gas under the residual state of carbon monoxide.
Now, though in order to have in helium trace water remaining also not with reaction of carbon monoxide, use ruthenium, palladium or rhodium as the 3rd anti-applications catalyst.Thus, the water gas shift reaction of carbon monoxide and water vapor can be prevented, prevent the generation of hydrogen.In addition, even if more preferably use the ruthenium or rhodium that also can carry out reacting below 150 DEG C as the 3rd anti-applications catalyst.
After this reaction, the water containing nitrogen, carbonic acid gas, trace in helium, the carbon monoxide of trace.Sometimes in helium containing the argon deriving from air, when the purposes of helium being the characteristic as utilizing it as rare gas element the wire-drawing process of optical fiber, because argon can replace helium, therefore also can not it can be used as impurity and ignore.
As the 8th operation, use sorbent material by least one carbonoxide, carbonic acid gas, nitrogen and the water in the described helium of pressure swing adsorption process absorption removing.
When being adsorbed by pressure swing adsorption process, do not need the absorption of hydrocarbon, oxygen, hydrogen, can reduce moisture containing ratio by dewatering unit yet, therefore, reduce the absorption load of sorbent material, the rate of recovery and the purity of helium can be improved.
By pressure swing adsorption process, it is desirable to the containing ratio of the carbon monoxide in helium, carbonic acid gas, moisture to be reduced to below molar ppm level, nitrogen content percentage can be reduced to below several molar ppm further.
Adopt the sorbent material used during the absorption of pressure swing adsorption process can use activated alumina, carbonaceous molecular sieve, zeolite etc., but in order to improve N2 adsorption effect, use activated alumina and zeolite.Particularly desirably stacked use activated alumina and X-type zeolite.
By implementing the first ~ eight operation of the invention described above, such as can use the rear helium reclaimed by purifying in the cooling of optical fiber, the foreign matter content in the helium after purifying can be made for such as counting below molar ppm, making oxygen, hydrogen, carbon monoxide, carbonic acid gas, hydrocarbon lower than 1 molar ppm.
When needing the further nitrogen concentration reduced in helium, after adopting described pressure swing adsorption process to adsorb, the thermal swing adsorbent method absorption that it is desirable to use sorbent material to pass through-10 DEG C ~-50 DEG C removes the nitrogen in the impurity of described helium.By adopting the absorption of thermal swing adsorbent method, the nitrogen content percentage in helium can be reduced to lower than 1 molar ppm.
In thermal swing adsorbent method, because the lower adsorptive power of adsorption temp is higher, if only consider the reduction of nitrogen concentration, it is desirable to adsorption temp low.But, need when owing to industrially using to consider to produce cold and hot cost, it is therefore desirable that use commercially available industrial refrigerator with the adsorption temp of-10 DEG C ~-50 DEG C.
Device of the present invention is the device of purifying helium, described helium is at least containing hydrogen, carbon monoxide, hydrocarbon and derive from the nitrogen of air and oxygen as impurity, the amount of its oxygen contained is than many with the amount required for the whole hydrogen, carbon monoxide and the hydrocarbon reaction that contain, and device of the present invention has following structure.
Import the activated carbon tower of described helium.Activated carbon tower can be made up of such as oil content strainer and the tower being filled with gac.
Import the first reactor of the described helium flowed out from described activated carbon tower.The the first anti-applications catalyst making oxygen and hydrogen, carbon monoxide and hydrocarbon reaction is loaded in the first reactor.Example is if be heated to the palladium catalyst of 300 ~ 400 DEG C or rhodium catalyst as the first anti-applications catalyst.
Import the second reactor of the helium flowed out from described first reactor.The the second anti-applications catalyst making oxygen and H-H reaction is loaded in the second reactor.Example if be heated to the palladium of 100 ~ 300 DEG C, platinum or rhodium be as the second anti-applications catalyst.
The condition being more than 2 times of the volumetric molar concentration of oxygen according to the volumetric molar concentration of the hydrogen in the described helium do not made in described second reactor of importing adds the hydrogen supplier of hydrogen in described helium.Hydrogen supplier such as can be formed by the analysis meter of the oxygen amount analyzed in helium with according to the feeder of its analytical results supply hydrogen.
Import the 3rd reactor of the described helium flowed out from described second reactor.The 3rd anti-applications catalyst making oxygen and reaction of carbon monoxide is loaded in the 3rd reactor.Example if be heated to the ruthenium of 50 ~ 300 DEG C, palladium or rhodium be as the 3rd anti-applications catalyst.
In described helium, add the carbon monoxide feedway of carbon monoxide higher than the condition of 2 times of the volumetric molar concentration of oxygen according to the volumetric molar concentration of the carbon monoxide in the described helium made in described 3rd reactor of importing.Carbon monoxide feedway such as can be formed by the analysis meter of the oxygen amount analyzed in helium with according to the feeder of its analytical results supply carbon monoxide.
The dewatering unit of the moisture containing ratio of the described helium of reduction between described second reactor and described 3rd reactor.Dewatering unit can be made up of the tower being such as filled with aluminum oxide.
The adsorption unit be connected with described 3rd reactor.Adsorption unit has the psa unit using sorbent material to be adsorbed at least one carbonoxide, carbonic acid gas, nitrogen and water in described helium by pressure swing adsorption process.Psa unit has multiple adsorption towers of the X-type zeolite being filled with such as aluminum oxide and Li-X type and so on.
Adsorption unit of the present invention it is desirable to have thermal swing adsorbent unit, described thermal swing adsorbent unit is after the described pressure swing adsorption process adsorbing contaminant of employing, uses sorbent material to pass through the thermal swing adsorbent method of-10 DEG C ~-50 DEG C by the thermal swing adsorbent unit of at least nitrogen adsorption in the impurity of described helium.Thermal swing adsorbent unit has multiple adsorption towers of the shell-cast being filled with such as Ca-X type zeolite, makes desorption temperature be 20 ~ 50 DEG C.
Adopt device of the present invention then can be to implement the method.
Utilize the present invention, the method and apparatus of the practicality of purification nitrogen can be provided, when purifying contains hydrogen, carbon monoxide, hydrocarbon and derive from the recovery helium of the nitrogen of air and oxygen, impurity containing ratio can be effectively reduced without the need to a large amount of purifying energy, with low cost, helium high purity can be purified to.
Accompanying drawing explanation
Fig. 1 is the structure explanatory view of the helium purification devices of embodiments of the present invention.
Fig. 2 is the structure explanatory view of the PSA unit in the helium purification devices of embodiments of the present invention.
Fig. 3 is the structure explanatory view of the TSA unit in the helium purification devices of embodiments of the present invention.
Embodiment
Helium purification devices α shown in Fig. 1 has: the supply source 1 of purifying object helium, strainer 2, activated carbon tower 3, first reactor 4, hydrogen supplier 5, second reactor 6, dewatering unit 7a, 7b, carbon monoxide feedway 8, the 3rd reactor 9, water cooler 10 and adsorption unit 11.
Purifying object helium is recovered from supply source 1 through oil seal rotary vacuum pump (diagram is omitted), removes oil content and after dedusting, import activated carbon tower 3 by strainer 2.There is no need to use special strainer as strainer 2, general strainer can be used, such as CKD Inc. AF1000P.
The purifying object helium that have passed strainer 2, except helium (He), at least contains hydrogen (H as impurity
2), carbon monoxide (CO), nitrogen (N from air
2) and oxygen (O
2), also containing the hydrocarbon deriving from oil seal rotary vacuum pump, in addition also containing the oil content that cannot be removed by strainer 2.Also can containing other trace impurity.
The hydrogen as impurity contained in purifying object helium and carbon monoxide comprise the hydrogen and carbon monoxide that trace in atmosphere contains, but mainly not derive from air, but are mixed in the environment for use of helium.Such as, by when being distributed in air after using in the wire-drawing process of optical fiber helium recovery, except containing except the nitrogen deriving from air be mixed into when the hydrogen be mixed in wire-drawing process and carbon monoxide, recovery and oxygen and the hydrocarbon deriving from described oil seal rotary vacuum pump and oil content in helium, also containing the carbonic acid gas etc. deriving from this air.Argon (Ar) can be contained when entrained air in purifying object helium, but because the containing ratio of the argon in air is lower than oxygen and nitrogen, and the purposes of purified helium can replace with argon gas when make use of the characteristic as rare gas element, so argon can not be ignored as impurity.
The amount of the oxygen contained in purifying object helium is than many with the amount required for the whole hydrogen, carbon monoxide and the hydrocarbon reaction that contain.Such as, when being recovered in the wire-drawing process of optical fiber the helium spilt into after use in air, oxygen level in purifying object helium is far more than hydrogen richness, carbon monoxide content and hydrocarbon content, air concentration is 10 ~ 50 % by mole, be generally 20 ~ 40 % by mole, hydrogen concentration and carbon monoxide concentration are respectively 10 ~ 90 molar ppm, and hydrocarbon concentration is about thousands of molar ppm.
In activated carbon tower 3, the hydrocarbon that in helium, carbon number is many is tightly held by activated carbon removing, and is not also tightly held by activated carbon removing in the lump by the oil content that strainer 2 removes.Do not need to use special gac as gac, forming charcoal, such as Japan environmental protection Co., Ltd. (Japanese エ Application バ イ ロ) the GX6/8 forming charcoal processed etc. easily obtained can be used.
From activated carbon tower 3 in helium out, as impurity at least containing hydrogen, carbon monoxide, the hydrocarbon of carbon number 1 ~ 6 be not tightly held by activated carbon and the air of such as about about 30 % by mole, therefore containing the nitrogen, oxygen, carbonic acid gas etc. that derive from air.The helium flowed out from this activated carbon tower 3 is imported into the first reactor 4.
In the first reactor 4, by the hydrocarbon reaction utilizing the first anti-applications catalyst to make the oxygen in described helium and hydrogen, carbon monoxide and be not tightly held by activated carbon, thus generate carbonic acid gas and water with the state of residual aerobic.Therefore, in the first reactor 4, load the first anti-applications catalyst making oxygen and hydrogen, carbon monoxide and hydrocarbon reaction.In the first reactor 4, in order to completely except dealkylation, need to make temperature of reaction be 300 ~ 400 DEG C.Therefore, palladium (Pd) catalyzer selecting in platinum class catalyzer reactivity at high temperature, weather resistance good or rhodium (Rh) catalyzer are as the first anti-applications catalyst.In the first reactor 4, the hydrogen in helium is converted into water, carbon monoxide is converted into carbonic acid gas, hydrocarbon is converted into water and carbonic acid gas.Under such circumstances, in the helium through reclaiming, containing q.s with the oxygen of hydrogen, carbon monoxide and hydrocarbon reaction, therefore, reclaiming helium and only ventilating to the first reactor, there is no need to add oxygen.
The helium flowed out from the first reactor 4 is imported into the second reactor 6.Import the hydrogen adjustment of hydrogen concentration by being added by hydrogen supplier 5 in the helium in this second reactor 6.Hydrogen supplier 5 adds hydrogen according to the condition that the hydrogen volumetric molar concentration in the helium do not made in described second reactor 6 of importing is more than 2 times of oxygen volumetric molar concentration in helium.It is desirable to by adding hydrogen in this helium, the hydrogen volumetric molar concentration in helium is made to be the value of 1.97 times ~ 1.99 times of oxygen volumetric molar concentration, by making this value be less than 1.99 times, in the second reactor 6, after reaction, in helium, hydrogen concentration can not remain more than 1 molar ppm.
The hydrogen supplier 5 of present embodiment has oxygen concentration determination device 5a, hydrogen supply source 5b, hydrogen amount regulator 5c and controller 5d.Oxygen concentration determination device 5a measures the oxygen volumetric molar concentration in the helium of importing second reactor 6, and its measured value is sent to controller 5d.According to this measured value, the control signal corresponding with the interpolation hydrogen flowrate making hydrogen volumetric molar concentration required for the value of 2 times lower than oxygen volumetric molar concentration is sent to hydrogen amount regulator 5c by controller 5d.Hydrogen amount regulator 5c carries out aperture adjustment to from hydrogen supply source 5b to the stream of the second reactor 6, thus supplies the hydrogen of the flow corresponding with control signal.Thus, the hydrogen volumetric molar concentration in the purifying object helium in the second reactor 6 reaches the value of 2 times lower than oxygen volumetric molar concentration.
Be filled with in second reactor 6 and make second of oxygen and H-H reaction the anti-applications catalyst.Thus, the oxygen in the helium making in the second reactor 6 by using the second anti-applications catalyst and H-H reaction, make to generate water under the residual state of oxygen.At this moment, temperature of reaction is 100 ~ 300 DEG C.As the second anti-applications catalyst, any catalyzer of the palladium of platinum class catalyzer, platinum (Pt) or rhodium can be used.
Dewatering unit 7a, 7b between the second reactor 6 and the 3rd reactor 9 is used to reduce the moisture containing ratio of the helium flowed out from the second reactor 6.Thus, when oxygen and carbon monoxide are reacted in the 3rd reactor 9, anti-sealing and reaction of carbon monoxide generate hydrogen.This is because the behavior of hydrogen is identical with helium during adsorption operations, be difficult to remove from helium in pressure swing adsorption process and thermal swing adsorbent method.
Dewatering unit 7a, 7b of present embodiment have front stage arrangement 7a and downstream component 7b, also can be the devices of further device or more than three grades.Dewatering unit 7a, 7b use refrigerator and are filled with the post etc. of dehumidizier, are reduced to the moisture containing ratio in helium lower than about 1000 molar ppm by dehydration operation.Such as under reduced pressure can make the adding pressure type dewatering unit of adsorbent reactivation to helium pressurization and by sorbent material removing moisture, helium pressurization cooling removed the freezing type dewatering unit of the moisture of condensation, combinationally use by heating to dewatering agent the thermal regeneration formula dewatering unit etc. making it regenerate after moisture contained in dewatering agent removing helium.In addition, by thermal regeneration formula dewatering unit 1 or multiple stage in parallel or be connected in series be used as the dewatering unit 7b of rear class effectively reduce in moisture containing ratio this point ideal, thus, the moisture removing more than about 99 % by mole that can contain in helium.
The helium flowed out from the second reactor 6 is imported in the 3rd reactor 9 after reducing moisture containing ratio by dewatering unit 7a, 7b.Carbon monoxide feedway 8 adds carbon monoxide higher than the condition of 2 times of oxygen volumetric molar concentration according to the carbon monoxide volumetric molar concentration in the helium made in importing the 3rd reactor 9 in helium.Carbon monoxide feedway 8 adds carbon monoxide higher than the condition of 2 times of the volumetric molar concentration of oxygen according to the volumetric molar concentration of the carbon monoxide in the helium made in importing the 3rd reactor 9 in helium.It is desirable to by adding carbon monoxide in this helium, making the carbon monoxide volumetric molar concentration in helium be the value of 2.02 times ~ 2.5 times of oxygen volumetric molar concentration, by making this value be more than 2.02 times, reliably can reduce oxygen, by making this value be less than 2.5 times, carbon monoxide concentration can not be too high.
The carbon monoxide feedway 8 of present embodiment has oxygen concentration determination device 8a, carbon monoxide supply source 8b, CO content regulator 8c and controller 8d.Oxygen concentration determination device 8a measures the oxygen volumetric molar concentration in the helium of importing the 3rd reactor 9, and its measured value is sent to controller 8d.Controller 8d sends to CO content regulator 8c by with making carbon monoxide volumetric molar concentration higher than the control signal that the interpolation carbon monoxide flow required for the value of 2 times of oxygen volumetric molar concentration is corresponding according to this measured value.CO content regulator 8c carries out aperture adjustment to from carbon monoxide supply source 8b to the stream of the 3rd reactor 9, thus supplies the carbon monoxide of the flow corresponding with its control signal.Thus, the carbon monoxide volumetric molar concentration in the purifying object helium in the 3rd reactor column 9 is made to be the value of 2 times higher than oxygen volumetric molar concentration.
The 3rd anti-applications catalyst making oxygen and reaction of carbon monoxide is filled with in 3rd reactor 9.Thus, the oxygen in the helium making in the 3rd reactor 9 by using the 3rd anti-applications catalyst and reaction of carbon monoxide, make to generate carbonic acid gas and water under the residual state of carbon monoxide.Ruthenium (Ru), rhodium or palladium is used as the 3rd anti-applications catalyst.In these catalyzer, ruthenium and rhodium can make reaction carry out below 150 DEG C, even if the moisture of residual minim also can not be affected in helium, therefore ideal.
The higher then carbon monoxide of temperature of reaction in 3rd reactor 9 and water react that to generate hydrogen easier, lower then because carbon monoxide hinders the poisoning of catalyst phenomenon of catalyst action thus hinder the reaction of oxygen and carbon monoxide.Therefore, the temperature of reaction of oxygen and carbon monoxide it is desirable to 50 ~ 130 DEG C.In addition, it is desirable to make the volumetric molar concentration of carbon monoxide to be 2.02 times ~ 2.4 times of oxygen volumetric molar concentration, or make it reach 3000 molar ppm, make oxygen volumetric molar concentration reach 1000 molar ppm.Thus, the oxygen concn be expected in helium is reduced to about 1 molar ppm, does not have newly-generated hydrogen, and hydrogen concentration is suppressed in lower than 1 molar ppm, and the residual quantity of carbon monoxide is some amounts, and carbon monoxide concentration is reduced to hundreds of molar ppm or following.
In order to the helium in importing first reactor 4 be preheating to the temperature that adapts to the reacting phase in the first reactor 4 and arrange well heater, water cooler helium out from the first reactor 4 being cooled to before importing the 3rd reactor 9 temperature adapted to the reacting phase in the 3rd reactor 9 also can be set.
3rd reactor 9 is connected with adsorption unit 11 through water cooler 10.Be cooled after device 10 cools from the helium of the 3rd reactor 9 outflow and be imported into adsorption unit 11.Adsorption unit 11 has PSA (pressure-variable adsorption) unit X1 and TSA (thermal swing adsorbent) unit X2.PSA unit X1 at least adsorbs by using the pressure swing adsorption process under the normal temperature of sorbent material and removes carbon monoxide, carbonic acid gas, water and the nitrogen in the impurity of helium.By PSA unit X1, can the containing ratio of the carbon monoxide in helium, carbonic acid gas and water be reduced to such as lower than 1 molar ppm, nitrogen content percentage is reduced to below several molar ppm.TSA unit X2 is after the described pressure swing adsorption process adsorbing contaminant of employing, and the thermal swing adsorbent method using sorbent material to pass through-10 DEG C ~-50 DEG C is by the nitrogen adsorption in the impurity of described helium and remove.Nitrogen content percentage in helium can be reduced to lower than 1 molar ppm by TSA unit X2.
PSA unit X1 can use known unit.PSA unit X1 such as shown in Fig. 2 is four-tower, having the compressor 12 that compresses of helium to flowing out from the 3rd reactor 9 and the four first ~ the 4th adsorption tower 13, being filled with sorbent material in each adsorption tower 13.
Sorbent material for pressure swing adsorption process can use the sorbent material being suitable for sorbing carbon monoxide, carbonic acid gas, moisture and nitrogen, such as, the zeolites sorbent material that dehydration uses aluminum oxide, primary attachment carbonic acid gas to use carbon class sorbent material, planar water and carbonic acid gas to use activated alumina, primary attachment carbon monoxide and nitrogen to use, they are stacked and fill.Zeolites sorbent material and other sorbent material both can be stacked two-layer, also can more than three layers alternately laminated.The high zeolite molecular sieve of the adsorption effect of carbon monoxide and nitrogen is it is desirable to, more preferably X-type zeolite as zeolites sorbent material.
In order to be adsorbed efficiently by pressure swing adsorption process and remove denitrification, it is desirable to stacked use activated alumina and X-type zeolite.Use the reason of activated alumina and X-type zeolite be based on: because can by activated alumina absorption and desorb moisture, carbonic acid gas, adopt X-type zeolite to the adsorption effect of carbon monoxide, nitrogen so can improve.That is, although carbonic acid gas is more difficult from the desorb of X-type zeolite, thus the adsorption effect of X-type zeolite being reduced, can suppress carbon dioxide adsorption on X-type zeolite by using activated alumina.If activated alumina diminishes relative to the weight ratio of X-type zeolite, then the absorption out-of-service time of nitrogen shortens, if this weight ratio becomes large, the absorption out-of-service time is elongated, and therefore, the stacked ratio of activated alumina and X-type zeolite is 5/95 ~ 30/70 better.
Compressor 12 is connected with the entrance 13a of each adsorption tower 13 through transforming valve 13b.
The entrance 13a of adsorption tower 13 is connected in air through transforming valve 13e and sourdine 13f respectively.
The outlet 13k of adsorption tower 13 is connected with outflow conduit 13m through transforming valve 13l respectively, is connected with boosting pipeline 13o through transforming valve 13n, cleans out side ducts 13q through transforming valve 13p and is connected with all pressing, and is connected with all pressing to clean through transforming valve 13r into side ducts 13s.
Outflow conduit 13m is connected with TSA unit X2 through inlet-side pressure variable valve 13t, makes the constant pressure of the helium of importing TSA unit 2.
Boosting pipeline 13o is connected with outflow conduit 13m through flowrate control valve 13u, flow instruction accommodometer 13v, and the flow in boosting pipeline 13o is adjusted to constant, thus prevents the fluctuations in discharge of the helium importing TSA unit X2.
All pressure is cleaned out side ducts 13q and is all pressed to clean and is interconnected through a pair connecting tube 13w into side ducts 13s, and each connecting tube 13w is provided with transforming valve 13x.
Absorption process, I operation that reduces pressure (purge gas goes out operation), II operation that reduces pressure (body of all calming the anger goes out operation), desorption step, matting (purge gas enters operation), I operation of boosting (body of all calming the anger enters operation), II operation of boosting is carried out respectively successively in first ~ four adsorption tower 13 of PSA unit X1.Each operation is illustrated as follows for benchmark with the first adsorption tower 13.
That is, in the first adsorption tower 13, only transforming valve 13b and transforming valve 13l opens, and the helium supplied from the 3rd reactor 9 imports the first adsorption tower 13 from compressor 12 through transforming valve 13b.Thus, in the helium imported in first adsorption tower 13, the major part of at least one carbonoxide, carbonic acid gas, moisture and nitrogen is adsorbed on sorbent material, thus carrying out absorption process, the helium after impurity containing ratio reduces is sent to TSA unit X2 from the first adsorption tower 13 through outflow conduit 13m.At this moment, the part being sent to the helium of outflow conduit 13m delivers to other adsorption tower (being the second adsorption tower 13 in present embodiment) through boosting pipeline 13o, flowrate control valve 13u, carries out boosting II operation in the second adsorption tower 13.
Then, close transforming valve 13b, 13l of the first adsorption tower 13, open transforming valve 13p, open the transforming valve 13r of other adsorption tower (being the 4th adsorption tower 13 in present embodiment), open 1 in transforming valve 13x.Thus, the helium that the impurity containing ratio on the first adsorption tower 13 top is less delivers to the 4th adsorption tower 13 through all pressing to clean into side ducts 13s, carries out decompression I operation in the first adsorption tower 13.At this moment, in the 4th adsorption tower 13, transforming valve 13e opens, and carries out matting.
Then, under the state of the transforming valve 13r of the transforming valve 13p and the 4th adsorption tower 13 that open the first adsorption tower 13, close the transforming valve 13e of the 4th adsorption tower 13, thus carry out gas recovery to the 4th adsorption tower 13 until decompression II operation that between the first adsorption tower 13 and the 4th adsorption tower 13, internal pressure is mutually homogeneous or roughly homogeneous.At this moment, transforming valve 13x can according to circumstances open 2.
Then, open the transforming valve 13e of the first adsorption tower 13, close transforming valve 13p, thus carry out the desorption step of impurity from sorbent material desorb, impurity is released in air through sourdine 13f together with gas.
Then, open the transforming valve 13r of the first adsorption tower 13, transforming valve 13b, 13l of the second adsorption tower 13 of the state after closedown absorption process terminates, open transforming valve 13p.Thus, the helium that the impurity containing ratio on the second adsorption tower 13 top is less delivers to the first adsorption tower 13 through all pressing to clean into side ducts 13s, in the first adsorption tower 13, carry out matting.Matting in first adsorption tower 13 gas used is released in air through transforming valve 13e, sourdine 13f.At this moment, in the second adsorption tower 13, decompression I operation is carried out.
Then, under the state of the transforming valve 13r of the transforming valve 13p and the first adsorption tower 13 that open the second adsorption tower 13, close the transforming valve 13e of the first adsorption tower, thus carry out boosting I operation.At this moment, according to circumstances transforming valve 13x can 2 all open.
Then, close the transforming valve 13r of the first adsorption tower 13, be temporarily in the holding state without operation.Boosting II operation that this holding state continues to the 4th adsorption tower 13 terminates.The boosting of the 4th adsorption tower 13 terminates, after absorption process switches to the 4th adsorption tower 13 from the 3rd adsorption tower 13, open the transforming valve 13n of the first adsorption tower, the part delivering to the helium of outflow conduit 13m from the other adsorption tower (being the 4th adsorption tower 13 present embodiment) being in absorption process delivers to the first adsorption tower 13 through boosting pipeline 13o, flowrate control valve 13u, carries out boosting II operation in the first adsorption tower 13.
By repeatedly carrying out above-mentioned each operation successively respectively in the first ~ four adsorption tower 13, the helium after impurity containing ratio reduces is delivered to TSA unit X2 continuously.
PSA unit X1 is not limited to the unit shown in Fig. 2, and such as tower number can be the number beyond 4, and such as 2 or 3.
TSA unit X2 can use known unit.Such as, TSA unit X2 shown in Fig. 3 is two tower, has and carries out the heat exchange type pre-cooler 21 of precooling, heat exchange type water cooler 22, first and second adsorption tower 23 cooled further the helium cooled through pre-cooler 21, the heat exchange department 24 that covers each adsorption tower 23 to the helium sent here from PSA unit 1.Heat exchange department 24 cools sorbent material when absorption process by cooling agent, when desorption step by the agent of thermophore heating adsorption.Each adsorption tower 23 has in many that are filled with sorbent material manages.As this sorbent material, the sorbent material being suitable for N2 adsorption can be used, it is desirable to use the zeolites sorbent material after such as using calcium (Ca) or lithium (Li) to carry out ion-exchange, and particularly desirably ion exchange ratio is the sorbent material of more than 70%, particularly desirably specific surface area is 600m
2the sorbent material of/more than g.
Water cooler 22 is connected with the entrance 23a of each adsorption tower 23 through transforming valve 23b.
The entrance 23a of adsorption tower 23 is communicated in air through transforming valve 23c respectively.
The outlet 23e of adsorption tower 23 is connected with outflow conduit 23g through transforming valve 23f respectively, is connected with cooling, boosting pipeline 23i through transforming valve 23h, is connected with cleaning tube road 23k through transforming valve 23j.
Outflow conduit 23g forms the part of pre-cooler 21, and the helium sent here from PSA unit 1 is by the purified helium gas cooling flowed out from outflow conduit 23g.Purified helium flows out from outflow conduit 23g through transforming valve 23l.
Cooling boosting pipeline 23i, cleaning tube road 23k are connected with outflow conduit 23g through under meter 23m, flowrate control valve 23o, transforming valve 23n.
Heat exchange department 24 adopts multitube, has the outer tube 24a, cooling agent supply source 24b, cooling agent radiator 24c, thermophore supply source 24d, the thermophore radiator 24e that surround the many interior pipes forming adsorption tower 23.In addition, be provided with multiple transforming valve 24f, change between the state circulated through outer tube 24a, thermophore radiator 24e for the state circulated through outer tube 24a, cooling agent radiator 24c at the cooling agent making to supply from cooling agent supply source 24b and the thermophore supplied from thermophore supply source 24d.In addition, be made up of a part for water cooler 22 pipeline from cooling agent radiator 24c branch, helium is cooled by the cooling agent supplied from cooling agent supply source 24b at water cooler 22, and this refrigerant return is to tank 24g.
Absorption process, desorption step, matting, refrigerating work procedure, boosting operation is carried out successively respectively in first, second adsorption tower 23 of TSA unit X2.
That is, in TSA unit X2, after the helium of PSA unit X1 supply is cooled pre-cooler 21, water cooler 22, the first adsorption tower 23 is imported through transforming valve 23b.At this moment, the first adsorption tower 23 is in and is circulated in heat exchanger 24 by cooling agent and be cooled to the state of-10 DEG C ~-50 DEG C, and transforming valve 23c, 23h, 23j close, and transforming valve 23f opens, and at least contained in helium nitrogen is adsorbed on sorbent material.Thus, in the first adsorption tower 23, carry out absorption process, the purifying helium after impurity containing ratio reduces flows out from adsorption tower 23 through transforming valve 23l.
During carrying out absorption process in first adsorption tower 23, in the second adsorption tower 23, carry out desorption step, matting, refrigerating work procedure, boosting operation.
That is, in the second adsorption tower 23, after absorption process terminates, in order to implement desorption step, closing transforming valve 23b, 23f, opening transforming valve 23c.Thus, in the second adsorption tower 23, impure helium is released in air, and pressure drop is to atm higher.In this desorption step, there is the transforming valve 24f of the heat exchange department 24 of refrigerant cycle to switch to closing condition by the second adsorption tower 23 and stop the circulation of cooling agent when absorption process, to discharge making cooling agent and the transforming valve 24f getting back to cooling agent supply source 24b switches to open mode from heat exchange department 24.
Then, in order to implement matting in the second adsorption tower 23, transforming valve 23c, 23j of second adsorption tower 23 and the transforming valve 23n of cleaning tube road 23k are set as open mode, are imported the second adsorption tower 23 by the heat exchange in heat exchange type pre-cooler 21 by a part for the purifying helium heated through cleaning tube road 23k.Thus, in the second adsorption tower 23, implement the desorb of the impurity of self-absorbent and adopt the cleaning of purifying helium, this cleaning helium used is released into air together with impurity from transforming valve 23c.In this matting, the transforming valve 24f of the heat exchange department 24 of heat transfer medium circuit is made to switch to open mode by being used in the second adsorption tower 23.
Then, in order to implement refrigerating work procedure in the second adsorption tower 23, the transforming valve 23j of the second adsorption tower 23 and transforming valve 23n of cleaning tube road 23k is set as closing condition, the transforming valve 23h of the second adsorption tower 23 and transforming valve 23n of cooling boosting pipeline 23i is set as open mode, imports the second adsorption tower 23 from a part for the purifying helium of the first adsorption tower 23 outflow through cooling boosting pipeline 23i.Thus, the purifying helium that the second adsorption tower 23 inside cools is released in air through transforming valve 23c.In this refrigerating work procedure, stopping the circulation of thermophore by being used for making the transforming valve 24f of heat transfer medium circuit to switch to closing condition, to discharge making thermophore and the transforming valve 24f getting back to thermophore supply source 24d switches to open mode from heat exchange department 24.Thermophore making the transforming valve 24f of the heat exchange department 24 of refrigerant cycle switch to open mode by being used in the second adsorption tower 23, making it be refrigerant cycle state after discharging and terminating.This refrigerant cycle state continuance terminates to boosting operation then, absorption process thereafter.
Then, in order to implement boosting operation in the second adsorption tower 23, closing the transforming valve 23c of the second adsorption tower 23, importing a part for the purifying helium flowed out from the first adsorption tower 23, thus being boosted in the inside of the second adsorption tower 23.Press in this boosting step lasts to the second adsorption tower 23 and press roughly equal in the first adsorption tower 23.After boosting operation terminates, close the transforming valve 23h of the second adsorption tower 23 and transforming valve 23n of cooling boosting pipeline 23i, the state that all transforming valve 23b, 23c, 23f, 23h, 23j of forming the second adsorption tower 23 thus close, the second adsorption tower 23 keeps holding state to absorption process then.
The absorption process of the second adsorption tower 23 is implemented in the same manner as the absorption process of the first adsorption tower 23.During carrying out absorption process in second adsorption tower 23, in the first adsorption tower 23, carry out desorption step, matting, refrigerating work procedure, boosting operation in the same manner as the second adsorption tower 23.
TSA unit X2 is not limited to the unit shown in Fig. 3, and such as tower number can be the number of more than 2, and such as 3 or 4.
By described purification devices α, by after the hydrocarbon in charcoal absorption removing helium in activated carbon tower 3, in the first reactor 4, by the hydrocarbon reaction utilizing the first anti-applications catalyst to make the oxygen in described helium and hydrogen, carbon monoxide and be not tightly held by activated carbon, thus generate carbonic acid gas and water with the state of residual aerobic.Then, be that the condition of more than 2 times of oxygen volumetric molar concentration adds hydrogen in described helium by hydrogen supplier 5 according to not making the hydrogen volumetric molar concentration in described helium.Then, the oxygen in the helium making in the second reactor 6 by using the second anti-applications catalyst and H-H reaction, make to generate water under the residual state of oxygen.Then, use the moisture containing ratio in dewatering unit 7a, 7b reduction helium, and in helium, add carbon monoxide higher than the condition of 2 times of oxygen volumetric molar concentration according to the carbon monoxide volumetric molar concentration made in helium by carbon monoxide feedway 8.Then, the oxygen in the helium making in the 3rd reactor 9 by using the 3rd anti-applications catalyst and reaction of carbon monoxide, make to generate carbonic acid gas under the residual state of carbon monoxide.Then, in PSA unit X1, use sorbent material by least one carbonoxide, carbonic acid gas, nitrogen and the water in pressure swing adsorption process absorption removing helium, in TSA unit X2, then use sorbent material to pass through at least nitrogen in the impurity of the thermal swing adsorbent method absorption helium of-10 DEG C ~-50 DEG C.
[embodiment 1]
Above-mentioned purification devices α is used to carry out the purifying of helium.Reclaim in helium as impurity respectively containing 30.0 % by mole nitrogen, 5.98 % by mole oxygen, the hydrogen of 80 molar ppm, the carbon monoxide of 80 molar ppm, the carbonic acid gas of 50 molar ppm, 20 molar ppm moisture, as 110 molar ppm of hydrocarbon methane and be scaled hydrocarbon, the 5g/m of C2 ~ C6 of 350 molar ppm with C1 carbon
3oil content.Containing argon in the helium reclaimed, but ignored.
Through oil strainer 2 (CKD strainer VFA1000), this helium was imported activated carbon tower 3 with the flow of 4.2L/ minute in normal conditions.Activated carbon tower 3 is the tubulose of nominal diameter 32A, fills 10L Japan Enviro Chemicals Ltd. (Japanese エ Application バ イ ロ ケ ミ カ Le ズ) GX6/8 forming charcoal processed.
Then, the helium that have passed activated carbon tower 3 is imported the first reactor 4.The palladium catalyst (NE Kai Jia Co., Ltd. (エ ヌ イ ー ケ system キ ャ ッ ト) DASH-220D processed) that 60mL aluminum oxide supports is filled in the first reactor 4.Reaction conditions as the first reactor 4 is temperature of reaction 350 DEG C, normal atmosphere, space velocity 4500/h.Importing in the helium of the first reactor 4 and contain the oxygen with the q.s of carbon monoxide, hydrogen and hydrocarbon reaction, therefore reacting without any need for being added in the first reactor 4.
Measuring from the oxygen concn the first reactor 4 helium out, is 5.9 % by mole, therefore, adds the hydrogen with 0.99 mole of the necessary amount of oxygen water generation reaction times, then imports the second reactor 6.Ruthenium catalyst (the generation Dehua chemical catalyst Co., Ltd. (ズ ー De ケ ミ ー) RUA3MM processed that 60mL aluminum oxide supports is filled) in the second reactor 6.Reaction conditions as the 3rd reactor 9 is temperature of reaction 150 DEG C, normal atmosphere, space velocity 4500/h.
Dewatering unit 7a, 7b is imported by from the second reactor 6 helium out.The device that dewatering unit 7a, 7b are connected in series by 2 towers being filled with activated alumina (Sumitomo Chemical KHD-24) 85L in the tubular vessel of nominal diameter 100A is formed.
Because the oxygen concn in helium out from dewatering unit 7a, 7b is 630 molar ppm, after therefore adding carbon monoxide 1320 molar ppm, import the 3rd reactor 9.
Ruthenium catalyst (the generation Dehua chemical catalyst Co., Ltd. (ズ ー De ケ ミ ー) RUA3MM processed that 60mL aluminum oxide supports is filled) in the 3rd reactor 9.Reaction conditions as the 3rd reactor 9 is temperature of reaction 110 DEG C, normal atmosphere, space velocity 4500/h.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2.
After the helium water cooler 10 flowed out from the 3rd reactor 9 is cooled to room temperature, reduce the containing ratio of impurity with adsorption unit 11.
PSA unit X1 is the tubulose four-tower of nominal diameter 80A, length 1m, fills activated alumina (Sumitomo Chemical KHD-24) and Li-X type zeolite (TOSOH Co., Ltd (East ソ ー) NSA-700 processed in each tower) 8L is as sorbent material.At this moment sorbent material is layered in each adsorption tower with the weight ratio of aluminum oxide/Li-X type zeolite=10/90.Adsorptive pressure is 0.8MPaG, and desorption pressures is 0.01MPaG.Be set as 110 seconds cycling time, all pressure is 15 seconds.
Be shown in following table 1 and following content from the composition of the purified helium of PSA unit X1 outflow.Because argon contained in the helium as purifying object is ignored, so the helium purity in table 1 is the purity eliminating argon and try to achieve.
Oxygen: lower than 1 molar ppm, nitrogen: 2.0 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, methane: lower than 1 molar ppm, moisture: lower than 1 molar ppm.
Oxygen concn in helium uses Te Leidai (Teledyne) Inc. micro amount of oxygen densitometer model 311 to measure, methane concentration uses Shimadzu Scisakusho Ltd (SHIMADZU Corporation) GC-FID processed to measure, and the concentration of carbon monoxide and carbonic acid gas uses Shimadzu Scisakusho Ltd GC-FID to measure through methanator equally.Hydrogen concentration uses GL scientific company (GL Science, Inc.) GC-PID processed to measure.Nitrogen concentration Shimadzu Scisakusho Ltd GC-PDD measures.The dew point instrument DEWMET-2 that moisture uses GE sensor Japanese firm (GE セ Application シ Application グ ジ ャ パ Application society) to make measures.
[embodiment 2]
The stacked ratio of the activated alumina of filling in PSA unit X1 and LiX is become 30/70 from 10/90, other similarly to Example 1, purifying helium.The composition of the purified helium in the exit of PSA unit X1 is shown in following table 1 and following content.
Oxygen: lower than 1 molar ppm, nitrogen: 1.5 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, methane: lower than 1 molar ppm, moisture: lower than 1 molar ppm.
[embodiment 3]
Determine the composition of the purified helium flowed out from PSA unit X1 in embodiment 1, in the present embodiment, determine the composition of the purified helium flowed out from TSA unit X2.TSA unit X2 is two tower, be filled with the CaX type zeolite (TOSOH Co., Ltd SA-600A) of 1.5L as sorbent material in each adsorption tower, adsorptive pressure is 0.8MPaG, and desorption pressures is 0.03MPaG, adsorption temp is-35 DEG C, and desorption temperature is 40 DEG C.Operate similarly to Example 1 in addition.The composition of the purified helium in the exit of TSA unit X2 is shown in following table 1 and following content.
Oxygen: lower than 1 molar ppm, nitrogen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, methane: lower than 1 molar ppm, moisture: lower than 1 molar ppm.
[comparative example 1]
Be only except Li-X type zeolite except the sorbent material of filling in PSA unit X1 is changed into, purifying helium similarly to Example 1.The composition of the purified helium in the exit of PSA unit X1 is shown in following table 1 and following content.
Oxygen: lower than 1 molar ppm, nitrogen: 160 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, methane: lower than 1 molar ppm, moisture: lower than 1 molar ppm.
[table 1]
[embodiment 4]
Rhodium catalyst (NE Kai Jia Co., Ltd. (エ ヌ イ ー ケ system キ ャ ッ ト) the makes 0.5% particle) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the first reactor 4.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the first reactor 4 exit is as follows.
Nitrogen: 30 % by mole, oxygen: 5.9 % by mole, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: 580 molar ppm, moisture: 700 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, TSA unit X2 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: lower than 1 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[embodiment 5]
Rhodium catalyst (the NE Kai Jia Co., Ltd. system 0.5% particle) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the second reactor 6.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the second reactor 6 exit is as follows.
Nitrogen: 28.4 % by mole, oxygen: 560 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: 570 molar ppm, moisture: 11.1 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 1.9 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[embodiment 6]
Platinum catalyst (the NE Kai Jia Co., Ltd. DASH-220) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the second reactor 6.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the second reactor 6 exit is as follows.
Nitrogen: 28.3 % by mole, oxygen: 550 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: 565 molar ppm, moisture: 11.2 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 1.8 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[embodiment 7]
Rhodium catalyst (the NE Kai Jia Co., Ltd. system 0.5% particle) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the 3rd reactor 9.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the 3rd reactor 9 exit is as follows.
Nitrogen: 31.8 % by mole, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: 60 molar ppm, carbonic acid gas: 1900 molar ppm, moisture: 0.1 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 2.2 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[embodiment 8]
Palladium catalyst (the NE Kai Jia Co., Ltd. DASH-220D) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the 3rd reactor 9.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the 3rd reactor 9 exit is as follows.
Nitrogen: 31.8 % by mole, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: 60 molar ppm, carbonic acid gas: 1890 molar ppm, moisture: 0.1 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, TSA unit X2 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: lower than 1 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[comparative example 2]
Platinum catalyst (the NE Kai Jia Co., Ltd. DASH-220) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the first reactor 4.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the first reactor 4 exit is as follows.
Nitrogen: 30 % by mole, oxygen: 5.9 % by mole, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: 560 molar ppm, moisture: 310 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: 20 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 1.9 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: 14 molar ppm.
Comparative example 3
Platinum catalyst (the NE Kai Jia Co., Ltd. DASH-220) 60mL that supports of aluminum oxide is filled, in addition purifying helium similarly to Example 1 in the 3rd reactor 9.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the 3rd reactor 9 exit is as follows.
Nitrogen: 31.8 % by mole, oxygen: 210 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: 480 molar ppm, carbonic acid gas: 1470 molar ppm, moisture: 0.1 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 1.8 molar ppm, oxygen: 220 molar ppm, hydrogen: lower than 1 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[comparative example 4]
In the 3rd reactor 9, fill platinum catalyst (the NE Kai Jia Co., Ltd. DASH-220) 60mL that aluminum oxide supports, reaction conditions is 250 DEG C for making temperature.In addition purifying helium similarly to Example 1.
Impurity concentration in the helium in the exit of each reactor 4,6,9 is as shown in table 2, and especially, the impurity concentration in the 3rd reactor 9 exit is as follows.
Nitrogen: 31.8 % by mole, oxygen: lower than 1 molar ppm, hydrogen: 40 molar ppm, carbon monoxide: 45 molar ppm, carbonic acid gas: 1890 molar ppm, moisture: 0.1 % by mole, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
In addition, PSA unit X1 exit generate helium in impurity concentration be shown in following table 3 and following content.
Nitrogen: 2.0 molar ppm, oxygen: lower than 1 molar ppm, hydrogen: 58 molar ppm, carbon monoxide: lower than 1 molar ppm, carbonic acid gas: lower than 1 molar ppm, moisture: lower than 1 molar ppm, as hydrocarbon methane and be converted into C2 ~ C6 hydrocarbon of C1 carbon: lower than 1 molar ppm.
[table 2]
[table 3]
The following fact can be confirmed by upper table 1.
By not only using Li-X type zeolite also to use activated alumina as the sorbent material in pressure swing adsorption process, the effect except denitrification from helium can be improved.In addition, by carrying out the absorption adopting thermal swing adsorbent method further, the nitrogen concentration in helium can be reduced in the exit of the first reactor 4 lower than 1 molar ppm.
The following fact can be confirmed by upper table 2.
By using palladium or rhodium as the first anti-applications catalyst, compared with using the situation of platinum, the hydrocarbon concentration in the exit helium of the second reactor 6 can be reduced in, can be reduced to lower than 1 molar ppm.
By using palladium, rhodium or platinum as the second anti-applications catalyst, the oxygen concn in helium can be reduced to hundreds of about ppm.
By using ruthenium, rhodium or palladium as the 3rd anti-applications catalyst, compared with using the situation of platinum, the oxygen concn in the exit helium of the 3rd reactor 9 and hydrogen concentration all can be reduced, can be reduced to lower than 1 molar ppm.
The present invention is not limited to the above-described embodiment and examples.Such as, being not limited to the helium after being discharged in air after using in the wire-drawing process of optical fiber helium recovery by the helium of purifying of the present invention, also can be at least containing hydrogen, carbon monoxide, hydrocarbon and derive from the nitrogen of air and the helium of oxygen as impurity.In addition, adopt being adsorbed on of thermal swing adsorbent method to need to make the nitrogen content in helium lower than being required during 1ppm, but according to the purity of required helium, purification devices also can not have TSA unit.
The explanation of symbol
α ... purification devices 3 ... activated carbon tower 4 ... first reactor 5 ... hydrogen supplier
6 ... second reactor 7a, 7b ... dewatering unit 8 ... carbon monoxide feedway
9 ... 3rd reactor 11 ... adsorption unit X1 ... PSA unit X2 ... TSA unit.
Claims (10)
1. the purification process of helium, described helium is at least containing hydrogen, carbon monoxide, hydrocarbon and derive from the nitrogen of air and oxygen as impurity, and the amount of its oxygen contained, than many with the amount required for the whole hydrogen, carbon monoxide and the hydrocarbon reaction that contain, is characterized in that,
The hydrocarbon in described helium is removed by charcoal absorption,
Then, by utilizing the first anti-applications catalyst to make the oxygen in described helium and hydrogen, carbon monoxide and not by the hydrocarbon reaction of described charcoal absorption, thus carbonic acid gas and water is generated with the state of residual aerobic,
Then, be that the condition of more than 2 times of oxygen volumetric molar concentration adds hydrogen in described helium according to not making the hydrogen volumetric molar concentration in described helium,
Then, utilize the second anti-applications catalyst to make oxygen in described helium and H-H reaction, thus generate water with the state of residual aerobic,
Then, the moisture containing ratio of described helium is reduced by dewatering unit,
In described helium, carbon monoxide is added higher than the condition of 2 times of the volumetric molar concentration of oxygen according to the volumetric molar concentration of the carbon monoxide made in described helium,
Then, utilize the 3rd anti-applications catalyst to make oxygen in described helium and reaction of carbon monoxide, thus generate carbonic acid gas with the state remaining carbon monoxide,
Then, use sorbent material by least one carbonoxide, carbonic acid gas, nitrogen and the water in the described helium of pressure swing adsorption process absorption removing,
Use palladium or rhodium as described first anti-applications catalyst,
Use palladium, platinum or rhodium as described second anti-applications catalyst,
Use ruthenium, palladium or rhodium as described 3rd anti-applications catalyst,
During by described pressure swing adsorption process absorption, use activated alumina and zeolite as sorbent material.
2. the purification process of helium as claimed in claim 1, is characterized in that, uses ruthenium or rhodium as described 3rd anti-applications catalyst.
3. the purification process of helium as claimed in claim 1, is characterized in that, uses X-type zeolite as described sorbent material.
4. the purification process of helium as claimed in claim 2, is characterized in that, uses X-type zeolite as described sorbent material.
5. the purification process of the helium according to any one of Claims 1 to 4, is characterized in that, after the described pressure swing adsorption process absorption of employing, the thermal swing adsorbent method absorption using sorbent material to pass through-10 DEG C ~-50 DEG C removes at least nitrogen in the impurity of described helium.
6. the purification devices of helium, described helium is at least containing hydrogen, carbon monoxide, hydrocarbon and derive from the nitrogen of air and oxygen as impurity, the amount of its oxygen contained is than many with the amount required for the whole hydrogen, carbon monoxide and the hydrocarbon reaction that contain, and it is characterized in that, described purification devices has:
Import the activated carbon tower of described helium,
Import the first reactor of the described helium flowed out from described activated carbon tower,
Import the second reactor of the described helium flowed out from described first reactor,
The condition being more than 2 times of oxygen volumetric molar concentration according to the hydrogen volumetric molar concentration in the described helium do not made in described second reactor of importing adds the hydrogen supplier of hydrogen in described helium,
Import the 3rd reactor of the described helium flowed out from described second reactor,
In described helium, add the carbon monoxide feedway of carbon monoxide higher than the condition of 2 times of oxygen volumetric molar concentration according to the carbon monoxide volumetric molar concentration in the described helium made in described 3rd reactor of importing,
The dewatering unit of the moisture containing ratio of the described helium of reduction between described second reactor and described 3rd reactor, and
The adsorption unit be connected with described 3rd reactor;
Palladium or rhodium are housed as the first anti-applications catalyst in described first reactor,
Palladium, platinum or rhodium are housed as the second anti-applications catalyst in described second reactor,
Ruthenium, palladium or rhodium are housed as the 3rd anti-applications catalyst in described 3rd reactor,
Described adsorption unit has the psa unit using sorbent material to be adsorbed at least one carbonoxide, carbonic acid gas, nitrogen and water in described helium by pressure swing adsorption process,
Described psa unit uses activated alumina and zeolite as sorbent material.
7. the purification devices of helium as claimed in claim 6, is characterized in that, ruthenium or rhodium is housed as the 3rd anti-applications catalyst in described 3rd reactor.
8. the purification devices of helium as claimed in claim 6, is characterized in that, described psa unit uses activated alumina and X-type zeolite as sorbent material.
9. the purification devices of helium as claimed in claim 7, is characterized in that, described psa unit uses activated alumina and X-type zeolite as sorbent material.
10. the purification devices of the helium according to any one of claim 6 ~ 9, it is characterized in that, described adsorption unit has after the described pressure swing adsorption process adsorbing contaminant of employing, uses sorbent material to adsorb the thermal swing adsorbent unit of at least nitrogen in the impurity of described helium by the thermal swing adsorbent method of-10 DEG C ~-50 DEG C.
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| TWI625297B (en) * | 2014-03-28 | 2018-06-01 | 住友精化股份有限公司 | Purification method and purification system for helium gas |
| ES2865823T3 (en) * | 2015-12-24 | 2021-10-18 | Air Liquide Oil And Gas Services Ltd | Method of controlling pressure in an underground storage volume |
| JP7017897B2 (en) * | 2017-10-05 | 2022-02-09 | 住友精化株式会社 | Catalyzed oxidation system and carbon dioxide purification method |
| CN108821251A (en) * | 2018-07-10 | 2018-11-16 | 安徽万瑞冷电科技有限公司 | Fiber manufacturing cooling tube helium recovery system and control method |
| CN113697785A (en) * | 2020-05-22 | 2021-11-26 | 中国石油化工股份有限公司 | Method for preparing helium by combining oxidation method with membrane separation |
| CN113548649A (en) * | 2021-08-18 | 2021-10-26 | 广州市粤佳气体有限公司 | Helium purification low-temperature adsorption process |
| CN114100591B (en) * | 2021-11-12 | 2023-08-22 | 中触媒新材料股份有限公司 | Continuous dehydration and activation device and method for molecular sieve adsorbent |
| CN114229810B (en) * | 2021-12-15 | 2023-11-03 | 华能核能技术研究院有限公司 | Helium purification system and method for thermal aging test of high-temperature gas cooled reactor internals |
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| JPS61163106A (en) * | 1985-01-11 | 1986-07-23 | Hitachi Ltd | Process and device for recovering inert gas |
| GB8726804D0 (en) * | 1987-11-16 | 1987-12-23 | Boc Group Plc | Separation of gas mixtures including hydrogen |
| JP2761918B2 (en) * | 1989-04-15 | 1998-06-04 | 日本酸素株式会社 | Recovery method of argon by pressure swing method |
| JP2977606B2 (en) * | 1990-11-29 | 1999-11-15 | 日本パイオニクス株式会社 | Noble gas purification method |
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| JP3884328B2 (en) * | 2002-06-03 | 2007-02-21 | 大陽日酸株式会社 | Adsorption cylinder design method and pressure fluctuation adsorption separation apparatus for pressure fluctuation adsorption separation |
| JP5372607B2 (en) * | 2009-05-29 | 2013-12-18 | 住友精化株式会社 | Helium purification method and helium purification apparatus |
| 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 |
| CN101941684A (en) * | 2009-07-10 | 2011-01-12 | 琳德股份公司 | Helium purifying method |
| TWI478761B (en) * | 2010-02-25 | 2015-04-01 | Sumitomo Seika Chemicals | Purifying method and purifying apparatus for argon gas |
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