CN102311103A - The purification process of helium and purification devices - Google Patents
The purification process of helium and purification devices Download PDFInfo
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- CN102311103A CN102311103A CN2011101984606A CN201110198460A CN102311103A CN 102311103 A CN102311103 A CN 102311103A CN 2011101984606 A CN2011101984606 A CN 2011101984606A CN 201110198460 A CN201110198460 A CN 201110198460A CN 102311103 A CN102311103 A CN 102311103A
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Abstract
The present invention can be purified to highly purified method and apparatus with helium through reducing the impurity containing ratio that reclaims helium effectively with low cost thereby provide.When the nitrogen and the oxygen that contain hydrogen, carbon monoxide at least, derive from air are carried out purifying as the helium of impurity, make oxygen, hydrogen and reaction of carbon monoxide in the helium, make oxygen residual and generate carbonic acid gas and water.Then, the hydrogen volumetric molar concentration is reached be higher than 2 times value of oxygen volumetric molar concentration, make oxygen and H-H reaction, make hydrogen residual and generate water through adding hydrogen.Then, after carrying out dehydration operation, make hydrogen and reactive metal oxide in the helium, thereby generate water.Then, adsorb nitrogen, carbonic acid gas and water in the impurity at least, then the adsorption of nitrogen at least of the alternating temperature absorption method through-10 ℃～-50 ℃ through the pressure swing adsorption process that uses the zeolites sorbent material.
Description
Technical field
The present invention relates to be suitable for contain hydrogen, carbon monoxide, the nitrogen that derives from air and oxygen carry out purifying as the helium of impurity method and apparatus at least to what for example in the manufacturing process of optical fiber, use helium that the back reclaims and so on.
Background technology
After for example in the wire-drawing process of optical fiber, using, using, be distributed to the helium in the atmosphere, sometimes with its recycling.Above-mentioned recovery helium contains the hydrogen of in the wire-drawing process of optical fiber, sneaking into, carbon monoxide, through being distributed to the nitrogen that derives from air of sneaking in the atmosphere and oxygen etc. after using as impurity, therefore need carry out purifying improves purity.
So, known following method: through with liquid nitrogen as refrigeration source the helium of cryogenic operations before with purifying in contained impurity liquefaction remove, through sorbent material (with reference to patent documentation 1) removed in the trace impurity absorption of remnants.Also known following method: add hydrogen in the helium before purifying, make this hydrogen with as the oxygen in the air compsn of impurity reaction and generate moisture, remove remaining impurities (with reference to patent documentation 2) through membrane separating method after removing this moisture.Also known following method: make that contained impurity contacts with alloy degasser in the rare gas such as helium before the purifying, thereby be removed (with reference to patent documentation 3).
Patent documentation 1: japanese patent laid-open 10-311674 communique
Patent documentation 2: Japanese Patent Laid is opened the 2003-246611 communique
Patent documentation 3: japanese patent laid-open 4-209710 communique
Summary of the invention
In the method for patent documentation 1 record, because need carry out cryogenic operations, so cooling energy increases with liquid nitrogen; In the method for patent documentation 2 records, because need the membrane sepn module, so equipment cost is high; The recovery income of the helium of any method is all less.In addition, in the method for patent documentation 2 record, remove deoxidation through in as the helium of purifying object, adding hydrogen, but and reckon without fully removing of hydrogen, may cause detrimentally affect because of hydrogen causes the material of deterioration aggravation to the meeting of optical fiber starting material and so on.In the method for patent documentation 3 record because alloy degasser ability little, be the situation that the low-purity helium of ppm level is purified to ultra-high purity so can only be used for impurity concentration, can't directly be used to sneak into the situation of more impurity.
Method of the present invention is characterised in that; When the nitrogen and the oxygen that contain hydrogen, carbon monoxide at least, derive from air are carried out purifying as the helium of impurity, utilize catalyzer to make oxygen in the said helium, hydrogen, and reaction of carbon monoxide, thereby generate carbonic acid gas and water with the state of residual aerobic; Then add hydrogen; Make the hydrogen volumetric molar concentration in the said helium reach 2 times the value that is higher than the oxygen volumetric molar concentration, then utilize catalyzer to make oxygen and H-H reaction in the said helium, thereby have the state of hydrogen to generate water with residual; Then reduce the moisture containing ratio of said helium through dehydration operation; Then make hydrogen and reactive metal oxide in the said helium, thereby generate water, then; Pressure swing adsorption process through using the zeolites sorbent material adsorbs nitrogen, carbonic acid gas and water in the impurity in the said helium at least, adsorbs the nitrogen in the impurity in the said helium at least through-10 ℃～-50 ℃ alternating temperature absorption method then.
According to the present invention, at first utilize catalyzer to make a part, hydrogen and the reaction of carbon monoxide of contained oxygen as impurity in the helium, generate carbonic acid gas and water with the state of residual aerobic.By this, hydrogen in the helium and carbon monoxide and oxygen reaction, thereby be removed.Then, make oxygen and the H-H reaction of being added in the helium, thereby have the state of hydrogen to generate water with residual.The addition of this hydrogen with in theory with helium in the required hydrogen amount of institute aerobic reaction compare slightly excessively, can reduce residual hydrogen amount through reaction by this with oxygen.Then, reduce the moisture containing ratio of helium through dehydration operation.By this, oxygen and water in the helium are removed, and can reduce the absorption load of moisture.Then make hydrogen and reactive metal oxide in the helium, thereby generate water.Implemented dehydration operation before being reflected at of this hydrogen and MOX reacted, can prevent that therefore reaction from being suppressed by moisture.By this, the hydrogen in the helium is removed, and can tackle the situation that requires to reduce hydrogen.In addition, the major impurity of helium is nitrogen, a spot of carbonic acid gas and a spot of water.Therefore, can easily reduce gas concentration lwevel and moisture containing ratio through pressure swing adsorption process.Because can improve the adsorption effect of nitrogen, so can reduce the nitrogen absorption load in the follow-up alternating temperature absorption method through in this pressure swing adsorption process, using the zeolites sorbent material.And, because can need not to adopt the alternating temperature absorption method to come adsorb oxygen, so can the adsorption temp of impurity be increased to the temperature when being higher than adsorb oxygen.Improve the recovery and the purity of helium under the situation of cooling energy that therefore, can be when not increasing adsorption treatment.
Device of the present invention is that the nitrogen and the oxygen that contain hydrogen, carbon monoxide at least, derive from air are carried out the device of purifying as the helium of impurity, it is characterized in that, comprising: first reactor drum, and importing in this first reactor drum has said helium; Second reactor drum, importing in this second reactor drum has the helium that flows out from said first reactor drum; The hydrogen concentration setting device, this hydrogen concentration setting device is set at 2 times the value that is higher than the oxygen volumetric molar concentration through the hydrogen volumetric molar concentration that interpolation hydrogen will import in the said helium in said second reactor drum; Water extracter, this water extracter reduces from the moisture containing ratio of the said helium of said second reactor drum outflow through carrying out dehydration operation; The 3rd reactor drum, importing in the 3rd reactor drum has the said helium that has reduced the moisture containing ratio through said water extracter; Adsorption unit, this adsorption unit is connected with said the 3rd reactor drum; In said first reactor drum, be filled with catalyzer; Make that oxygen, hydrogen and the carbon monoxide in the said helium reacts in said first reactor drum; Thereby generate water and carbonic acid gas; In said second reactor drum, be filled with catalyzer; Make oxygen and the H-H reaction in the said helium in said second reactor drum, thereby have the state of hydrogen to generate water, in said the 3rd reactor drum, be filled with MOX with residual; Make the hydrogen generation oxidation in the said helium in said the 3rd reactor drum and generate water; Said adsorption unit has PSA unit and TSA unit, and this PSA unit adsorbs nitrogen, carbonic acid gas and water in the impurity from the said helium that said the 3rd reactor drum flows out at least through the pressure swing adsorption process that uses the zeolites sorbent material, and this TSA unit adsorbs the nitrogen in the impurity in the said helium at least through-10 ℃～-50 ℃ alternating temperature absorption method.
If adopt device of the present invention, but the method for embodiment of the present invention then.
Utilize the present invention; Can be under the situation that need not a large amount of purifying energy reduce nitrogen and the oxygen of sneaking into hydrogen, carbon monoxide at least, deriving from air effectively as the impurity containing ratio in the helium of impurity, thereby the method and apparatus that can helium be purified to highly purified practicality with low cost is provided.
Description of drawings
Fig. 1 is the structure explanatory view of the helium purification devices of embodiment of the present invention.
Fig. 2 is the structure explanatory view of the pressure-swing absorption apparatus in the helium purification devices of embodiment of the present invention.
Fig. 3 is the structure explanatory view of the alternating temperature adsorption unit in the helium purification devices of embodiment of the present invention.
The explanation of symbol
α: purification devices, 2: well heater, 3: the first reactor drums, 4: the second reactor drums, 5: hydrogen concentration setting device, 6: water extracter, 7: the three reactor drums, 9: adsorption unit, 10:PSA unit, 20:TSA unit
Embodiment
Helium purification devices α shown in Figure 1 comprises: as the supply source 1 of the helium of purifying object, well heater 2, first reactor drum 3, second reactor drum 4, hydrogen concentration setting device 5, water extracter 6, the 3rd reactor drum 7, water cooler 8, adsorption unit 9.
From supply source 1 supply with as the helium of purifying object through not shown dedustings such as strainer, via gas transport unit such as gas blower (omitting diagram) importing well heater 2.Helium as the purifying object is considered to contain hydrogen, carbon monoxide at least, derive from air nitrogen and oxygen is as impurity, but also can contain other trace impurity.Among the present invention, hydrogen and carbon monoxide as impurity contained in the helium as the purifying object are included in hydrogen and the carbon monoxide that trace contains in the air, but mainly are not to derive from air, but in the environment for use of helium, sneak into.For example; Be distributed under the situation of the helium recovery in the atmosphere after will in the wire-drawing process of light, using; Except the nitrogen that derives from air that contains the hydrogen of in wire-drawing process, sneaking into and carbon monoxide and sneak into when reclaiming with the oxygen, also contain the trace impurity of negligible degree such as the carbonic acid gas that derives from this air and hydrocarbon in the helium.Sneak in the helium as the purifying object under the situation of air and can contain argon; But because the content of airborne argon is lower than oxygen and nitrogen; And the purposes of purified helium has been utilized as replacing with argon gas under the situation of the characteristic of rare gas element, so can argon not ignored it as impurity.Not had special qualification by the concentration of the impurity in the helium of purifying, for example is about 1 mole of %～60 mole %.For the reaction in each reactor drum 3,4,7 is carried out fully, the temperature that heats with 2 pairs of helium of well heater is preferably more than 250 ℃, and from the angle that prevents that life of catalyst from shortening, said temperature is preferably below 400 ℃.
The helium of heater via 2 heating is imported into first reactor drum 3.Be filled with the catalyzer that makes oxygen and hydrogen and reaction of carbon monoxide in first reactor drum 3.By this, contained oxygen, hydrogen and carbon monoxide reacts in the helium in first reactor drum 3, thereby generates water and carbonic acid gas with the state of residual aerobic.As long as the catalyzer that is filled in first reactor drum 3 makes oxygen and hydrogen and reaction of carbon monoxide, do not have especially and limit, for example can use with precious metals such as platinum, platinum alloy, palladium be carried on aluminum oxide etc. and catalyzer.In addition, the helium of recovery contains the hydrocarbon as combustible component, and this hydrocarbon is oxidized carbonic acid gas and the water of resolving in first reactor drum 3, but because its volumetric molar concentration is few, is merely about several molar ppm, so can impact hardly residual oxygen amount.
Be imported into second reactor drum 4 from first reactor drum, 3 effusive helium.The effect of hydrogen concentration setting device 5 is to be set at 2 times the value that is higher than the oxygen volumetric molar concentration through the hydrogen volumetric molar concentration that interpolation hydrogen will import in the helium in second reactor drum 4.The hydrogen concentration setting device 5 of this embodiment has density measuring device 5a, hydrogen supply source 5b, hydrogen amount regulator 5c, unit 5d.Density measuring device 5a measures the oxygen volumetric molar concentration in the helium that imports second reactor drum 4, and its measured signal is sent to unit 5d.Unit 5d will reach the required corresponding wave of hydrogen amount of 2 times value that is higher than measured oxygen volumetric molar concentration with the hydrogen volumetric molar concentration in making helium and be sent to hydrogen amount regulator 5.Hydrogen amount regulator 5c carries out the aperture adjustment to the stream from hydrogen supply source 5b to second reactor drum 4, thereby supplies with the hydrogen of the amount corresponding with wave.By this, the hydrogen volumetric molar concentration as in the helium of purifying object in second reactor drum 4 reaches 2 times the value that is higher than the oxygen volumetric molar concentration.Better be through utilizing hydrogen concentration setting device 5 in helium, to add hydrogen; Make hydrogen volumetric molar concentration in the helium reach 2.05 times～2.10 times value of oxygen volumetric molar concentration; Through this value is reached more than 2.05 times; Can reduce oxygen reliably, reach below 2.10 times through making this value, the hydrogen concentration in the helium can be not too high.
Be filled with the catalyzer that makes oxygen and H-H reaction in second reactor drum 4.By this, oxygen and H-H reaction in the helium in second reactor drum 4 have the state of hydrogen to generate water with residual.As long as the catalyzer that is filled in second reactor drum 4 makes oxygen and H-H reaction, do not have especially and limit, for example can use with precious metals such as platinum, platinum alloy, palladium be carried on aluminum oxide etc. and catalyzer.
The helium that has reduced the moisture containing ratio through water extracter 6 is imported into the 3rd reactor drum 7.In the 3rd reactor drum 7, be filled with MOX, make the hydrogen generation oxidation in the said helium in the 3rd reactor drum 7 and generate water.By this, hydrogen in the helium in the 3rd reactor drum 7 and reactive metal oxide and generate water.As long as the MOX that is filled in the 3rd reactor drum 7 can generate water with H-H reaction; Preferably be carried on the commercially available article of aluminum oxide etc., for example can use with cupric oxide and zinc oxide be carried on aluminum oxide and MOX or with nickel oxide be carried on aluminum oxide and MOX.Temperature of reaction in the 3rd reactor drum 7 is preferably about 200～300 ℃.
The 3rd reactor drum 7 is situated between and is connected with adsorption unit 9 with water cooler 8., the 3rd reactor drum 7 effusive helium are imported into adsorption unit 9 after being cooled device 8 coolings.Adsorption unit 9 has PSA unit 10 and TSA unit 20.PSA unit 10 adsorbs nitrogen, carbonic acid gas and water in the impurity in the helium at least through the pressure swing adsorption process under the normal temperature that uses the zeolites sorbent material.TSA unit 20 adsorbs the nitrogen in the impurity in the helium at least through-10 ℃～-50 ℃ alternating temperature absorption method.
The inlet 13a of adsorption tower 13 is situated between respectively and is connected in the atmosphere with transforming valve 13e and sourdine 13f.
The outlet 13k of adsorption tower 13 is situated between respectively and is connected with outflow pipeline 13m with transforming valve 13l; Jie is connected with the pipeline 13o that boosts with transforming valve 13n; Jie cleans out duct 13q and is connected with all pressing with transforming valve 13p, is situated between to go into duct 13s with transforming valve 13r with equal pressure cleanings and be connected.
Flow out pipeline 13m Jie and be connected with TSA unit 20, make the constant pressure of the helium that imports TSA unit 20 with pressure regulator valve 13t.
The pipeline 13o that boosts is situated between and is connected with outflow pipeline 13m with flowrate control valve 13u, flow indication accommodometer 13v, and the flow among the pipeline 13o that boosts is adjusted to constant, thereby prevents to import the fluctuations in discharge of the helium of TSA unit 20.
All press to clean out duct 13q and all press cleaning to go into duct 13s Jie to interconnect with a pair of connecting tube 13w, each connecting tube 13w is provided with transforming valve 13x.
Carry out absorption process, decompression I operation (purge gas goes out operation), decompression II operation (body of all calming the anger goes out operation), desorption step, matting (purge gas is gone into operation), the I operation of boosting (body of all calming the anger is gone into operation), the II operation of boosting in first of PSA unit 10～the 4th adsorption tower 13 respectively successively.
That is, in first adsorption tower 13 only transforming valve 13b and transforming valve 13l open, the helium of supplying with from the 3rd reactor drum 7 imports first adsorption tower 13 from compressor 12 through transforming valve 13b.By this, in the helium that is imported in first adsorption tower 13 at least nitrogen, carbonic acid gas, moisture be adsorbed on sorbent material, thereby carry out absorption process, the helium after the impurity containing ratio reduces is delivered to TSA unit 20 from first adsorption tower 13 through flowing out pipeline 13m.At this moment, a part that is sent to the helium that flows out pipeline 13m is delivered to other adsorption tower (being second adsorption tower 13 in this embodiment), the II operation of in second adsorption tower 13, boosting through the pipeline 13o that boosts, flowrate control valve 13u.
Then, close transforming valve 13b, the 13l of first adsorption tower 13, open transforming valve 13p, open the transforming valve 13r of other adsorption tower (being the 4th adsorption tower 13 in this embodiment), open 1 among the transforming valve 13x.By this, the less helium of the impurity containing ratio on first adsorption tower, 13 tops is delivered to the 4th adsorption tower 13 through all pressing cleaning to go into duct 13s, and the I operation reduces pressure in first adsorption tower 13.At this moment, transforming valve 13e opens in the 4th adsorption tower 13, carries out matting.
Then; Under the state of the transforming valve 13r of transforming valve 13p that opens first adsorption tower 13 and the 4th adsorption tower 13; Close the transforming valve 13e of the 4th adsorption tower 13, thereby reclaim gas to the four the adsorption towers 13 mutual homogeneous of internal pressure or decompression II operation of homogeneous roughly between first adsorption tower 13 and the 4th adsorption tower 13.At this moment, transforming valve 13x can according to circumstances open 2.
Then, open the transforming valve 13e of first adsorption tower 13, close transforming valve 13p, thereby carry out the desorption step of impurity from the sorbent material desorb, impurity is released in the atmosphere through sourdine 13f with gas.
Then, open the transforming valve 13r of first adsorption tower 13, close transforming valve 13b, the 13l of second adsorption tower 13 of the state after absorption process finishes, open transforming valve 13p.By this, the less helium of the impurity containing ratio on second adsorption tower, 13 tops is delivered to first adsorption tower 13 through all pressing cleaning to go into duct 13s, in first adsorption tower 13, carries out matting.The used gas of matting in first adsorption tower 13 is released in the atmosphere through transforming valve 13e, sourdine 13f.At this moment, the I operation that reduces pressure in second adsorption tower 13.Then, under the state of the transforming valve 13r of the transforming valve 13p that opens second adsorption tower 13 and first adsorption tower 13, close the transforming valve 13e of first adsorption tower, thereby boost the I operation.At this moment, transforming valve 13x can according to circumstances open 2.
Then, close the transforming valve 13r of first adsorption tower 13, temporarily be in the holding state of no operation.The II operation of boosting that this holding state continues to the 4th adsorption tower 13 finishes.The end of boosting of the 4th adsorption tower 13; After absorption process switches to the 4th adsorption tower 13 from the 3rd adsorption tower 13; Open the transforming valve 13n of first adsorption tower; Deliver to the part of the helium that flows out pipeline 13m from the other adsorption tower (being the 4th adsorption tower 13 this embodiment) that is in absorption process and deliver to first adsorption tower 13 through the pipeline 13o that boosts, flowrate control valve 13u, the II operation of in first adsorption tower 13, boosting.
Through in first～the 4th adsorption tower 13, carrying out each above-mentioned operation respectively successively repeatedly, the helium after the impurity containing ratio reduces is delivered to TSA unit 20 continuously.
Also have, PSA unit 10 is not limited to unit shown in Figure 2, and for example the tower number can be the number beyond 4, and for example 2 or 3.
The inlet 23a of adsorption tower 23 is situated between respectively and is communicated in the atmosphere with transforming valve 23c.
The outlet 23e of adsorption tower 23 is situated between respectively and is connected with outflow pipeline 23g with transforming valve 23f, and Jie is boosted with cooling with transforming valve 23h and is connected with pipeline 23i, and being situated between is connected with cleaning tube road 23k with transforming valve 23j.
Flow out the part of pipeline 23g formation pre-cooler 21, the helium of sending here from PSA unit 10 is cooled off from flowing out the effusive purified helium of pipeline 23g.Purified helium flows out through transforming valve 23l from flowing out pipeline 23g.
Cooling is boosted and is connected with under meter 23m, flowrate control valve 23o, transforming valve 23n and outflow pipeline 23g with pipeline 23i, cleaning tube road 23k Jie.
Heat exchanger 24 adopts multitube, has the outer tube 24a, cooling agent supply source 24b, the cooling agent that surround pipe in many that constitute adsorption tower 23 and uses radiator 24e with radiator 24c, perolene supply source 24d, perolene.In addition; Be provided with a plurality of transforming valve 24f, be used for the cooling agent supplied with from cooling agent supply source 24b is changed between with radiator 24e round-robin state through outer tube 24a, perolene with radiator 24c round-robin state and from the perolene of perolene supply source 24d supply through outer tube 24a, cooling agent.In addition, by constituting the part of water cooler 22 with radiator 24c ramose pipeline from cooling agent, the cooling agent cooling that helium is supplied with from cooling agent supply source 24b at water cooler 22, this cooling agent is back to a jar 24g.
Carry out absorption process, desorption step, matting, refrigerating work procedure, the operation of boosting in first, second adsorption tower 23 of TSA unit 20 respectively successively.
That is, in the TSA unit 20, after the helium of supplying with from PSA unit 10 is cooled, import first adsorption tower 23 pre-cooler 21, water cooler 22 through transforming valve 23b.At this moment, first adsorption tower 23 is in and is cooled to-10 ℃～-50 ℃ state through circulating cooling agent in heat exchanger 24, and transforming valve 23c, 23h, 23j close, and transforming valve 23f opens, and contained nitrogen is adsorbed on sorbent material in the helium at least.By this, in first adsorption tower 23, carry out absorption process, the purifying helium after the impurity containing ratio reduces flows out through transforming valve 23l from adsorption tower 23.
Carry out during the absorption process in first adsorption tower 23, carry out desorption step, matting, refrigerating work procedure, the operation of boosting in second adsorption tower 23.
That is, in second adsorption tower 23, absorption process in order to implement desorption step, is closed transforming valve 23b, 23f after finishing, and opens transforming valve 23c.By this, in second adsorption tower 23, impure helium is released in the atmosphere, and pressure drops to about normal atmosphere.In this desorption step; The transforming valve 24f that the heat exchange department 24 of refrigerant cycle is arranged when the absorption process in second adsorption tower 23 is switched to closing condition and stops the circulation of cooling agent, with cooling agent is discharged and the transforming valve 24f that gets back to cooling agent supply source 24b switches to open mode from heat exchange department 24.
Then; In order in second adsorption tower 23, to implement matting; The transforming valve 23n of the transforming valve 23c of second adsorption tower 23,23j and cleaning tube road 23k is set as open mode, and 23k imports second adsorption tower 23 to the part of heated purifying helium through the cleaning tube road through the heat exchange in the heat exchange type pre-cooler 21.By this, in second adsorption tower 23, implement the desorb and the cleaning of adopting the purifying helium of the impurity of self-absorbent, the used helium of this cleaning is released into the atmosphere with impurity from transforming valve 23c.In this matting, make the transforming valve 24f of perolene round-robin heat exchange department 24 switch to open mode with being used in second adsorption tower 23.
Then; In order in second adsorption tower 23, to implement refrigerating work procedure; The transforming valve 23n of the transforming valve 23j of second adsorption tower 23 and cleaning tube road 23k is set as closing condition; The transforming valve 23h of second adsorption tower 23 and the transforming valve 23n that cooling is boosted with pipeline 23i are set as open mode, and boosting through cooling from the part of first adsorption tower, 23 effusive purifying helium imports second adsorption tower 23 with pipeline 23i.By this, refrigerative purifying helium having been carried out in second adsorption tower, 23 inside is released in the atmosphere through transforming valve 23c.In this refrigerating work procedure, will be used to make perolene round-robin transforming valve 24f switch to closing condition and the circulation that stops perolene, with perolene is discharged and the transforming valve 24f that gets back to perolene supply source 24d switches to open mode from heat exchange department 24.After perolene discharge to finish, the transforming valve 24f of the heat exchange department 24 that is used to make refrigerant cycle in second adsorption tower 23 is switched to open mode, make it be the refrigerant cycle state.This refrigerant cycle state continuance to the operation of following of boosting, absorption process thereafter finish.
Then,, close the transforming valve 23c of second adsorption tower 23, import a part, thereby boosted in the inside of second adsorption tower 23 from first adsorption tower, 23 effusive purifying helium in order in second adsorption tower 23, to implement to boost operation.This operation of boosting continue to second adsorption tower 23 interior pressure and first adsorption tower 23 interior pressure about equally.After the operation of boosting finishes; The transforming valve 23h that closes second adsorption tower 23 boosts with the transforming valve 23n of pipeline 23i with cooling; Form all transforming valve 23b, 23c, 23f, 23h, the 23j closing state of second adsorption tower 23 by this, second adsorption tower 23 keeps holding state to the absorption process of following.
The absorption process of the absorption process of second adsorption tower 23 and first adsorption tower 23 is likewise implemented.Carry out during the absorption process in second adsorption tower 23, likewise carry out desorption step, matting, refrigerating work procedure, the operation of boosting with second adsorption tower 23 in first adsorption tower 23.
Also have, TSA unit 20 is not limited to unit shown in Figure 3, and for example the tower number can be the number more than 2, and for example 3 or 4.
Utilize above-mentioned purification devices α, at first in first reactor drum 3, utilize catalyzer to make oxygen contained in the helium, hydrogen and reaction of carbon monoxide, with the state generation carbonic acid gas and the water of residual aerobic as impurity.By this, hydrogen in the helium and carbon monoxide and oxygen reaction, thereby be removed.Then, in second reactor drum 4, make oxygen and the H-H reaction of being added in the helium, thereby have the state of hydrogen to generate water with residual.The addition of this hydrogen can be set at feasible few through the hydrogen amount residual with the reaction of oxygen.Then, reduce the moisture containing ratio of helium through dehydration operation.By this, the water in the helium is removed, and can reduce the water adsorption load of adsorption unit 9.Then, in the 3rd reactor drum 7, make hydrogen and reactive metal oxide in the helium, thereby generate water, being reflected at of this hydrogen and MOX implemented dehydration operation before reacting, and therefore can prevent to react and suppressed by moisture.By this, the hydrogen in the helium is removed, and can tackle the situation that requires to reduce hydrogen.In addition, the major impurity of helium is nitrogen, a spot of carbonic acid gas and a spot of water.Therefore, can easily reduce gas concentration lwevel and moisture containing ratio through the pressure swing adsorption process that adopts PSA unit 10.Can improve the adsorption effect of nitrogen through in this pressure swing adsorption process, using the zeolites sorbent material, can reduce the nitrogen absorption load in the follow-up alternating temperature absorption method.And, because can need not to adopt the alternating temperature absorption method to come adsorb oxygen, so can the adsorption temp of impurity be increased to the temperature when being higher than adsorb oxygen.Improve the recovery and the purity of helium under the situation of cooling energy that therefore, can be when not increasing adsorption treatment.
Use above-mentioned purification devices α to carry out the purifying of helium.In the used recovery helium, the moisture of carbonic acid gas, 20 molar ppm that contains carbon monoxide, 300 molar ppm of hydrogen, 300 molar ppm of oxygen, 4500 molar ppm of the nitrogen of 23.43 moles of %, 6.28 moles of % is as impurity.Contain argon in the helium that reclaims, but it is ignored, other trace ingredients is also ignored.
The flow that this helium is counted 3.75L/min with standard state imports first reactor drum 3.In first reactor drum 3, fill the platina catalyzer that 45mL is carried on aluminum oxide, reaction conditions is 280 ℃ of temperature, normal atmosphere, space velocity 5000/h.
Mensuration is from the remaining oxygen amount of first reactor drum, 3 effusive helium, and the hydrogen that makes an addition to helium is imported second reactor drum 4 with the flow of 0.456L/min.It is identical with first reactor drum 3 with temperature of reaction in second reactor drum 4 to be filled in the catalyzer of second reactor drum 4, and catalytic amount is 50.6ml, and space velocity is 5000/h.
Use thermal regeneration formula dewatering unit as water extracter 6, carry out from by dewatered dehydration operation second reactor drum, the 4 effusive helium, the moisture containing ratio of helium is reduced to 90 molar ppm.
To import the 3rd reactor drum 7 from water extracter 6 effusive helium.In the 3rd reactor drum 7, fill cupric oxide and the zinc oxide (southern chemical catalyst Co., Ltd. (ズ one De ケ ミ one catalyst) system) that 210mL is carried on aluminum oxide.Temperature of reaction is 250 ℃, and space velocity is 1000/h.
After will cooling off with water cooler 8 from the 3rd reactor drum 7 effusive helium, reduce the containing ratio of impurity with adsorption unit 9.
Will be through the PSA unit helium of 10 purifying import TSA unit 20.TSA unit 20 is two tower, is filled with the CaX type zeolite of 1.5L as sorbent material in each tower, and adsorptive pressure is 0.8MPa, and adsorption temp is-35 ℃, and desorption pressures is 0.1MPa, and desorption temperature is 40 ℃.
The composition of 20 effusive purified helium is shown in following table 1 from the TSA unit.Because contained argon is ignored in will the helium as the purifying object, so the helium purity in the table 1 is to have removed argon and the purity of trying to achieve.
The oxygen concn of purified helium uses dyne technology company in the Thailand, and (Teledyne Technologies, Inc.) system micro amount of oxygen densitometer model 311 is measured.Methane concentration uses the system GC-FID of Shimadzu Scisakusho Ltd (SHIMADZU Corporation) to measure; Carbon monoxide and concentration of carbon dioxide use the system GC-FID of Shimadzu Scisakusho Ltd to measure via methanator equally.Hydrogen concentration is used GL scientific company (GL Science, Inc.) system GC-PDD mensuration; Nitrogen concentration is measured with the system GC-PDD of Shimadzu Scisakusho Ltd.(GE Sensing&Inspection Technologies, Inc.) the dew point instrument MST-5 of system measures moisture with detecting scientific & technical corporation with the GE sensing.
The oxygen that consists of of the impurity in the helium in the exit of PSA unit 10 is lower than 1ppm, nitrogen 380ppm, hydrogen and is lower than 1ppm, carbon monoxide and is lower than 1ppm, carbonic acid gas and is lower than that 1ppm, methane are lower than 1ppm, moisture is lower than 1ppm.
Except the MOX that will be filled in the 3rd reactor drum 7 changes the cupric oxide (Sigma aldrich Co., Ltd. (シ グ マ ァ Le De リ ッ チ) system) that is carried on aluminum oxide into, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
Except the sorbent material that uses in the TSA unit 20 is changed into the LiX type zeolite, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
Except the adsorption temp in the TSA unit 20 being changed into-50 ℃, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
Embodiment 5
Except the catalyzer that will be filled in first reactor drum 3 and second reactor drum 4 changes into the palladium that is carried on aluminum oxide, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
Comparative example 1
Be used for except that the 3rd reactor drum 7 of dehydrogenation except not using, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
Comparative example 2
Except the dehydration operation that does not adopt the thermal regeneration water extracter, with embodiment 1 purifying helium likewise.The composition of the helium that this is purified is shown in following table 1.
[table 1]
Can be confirmed that by above-mentioned table 1 among each embodiment, helium purity is higher than each comparative example, hydrogen concentration is lower than comparative example 1,2.
The present invention is not limited to the above-described embodiment and examples.For example; The helium that carries out purifying through the present invention is not limited to after in the wire-drawing process of optical fiber, using, be distributed to the helium that the helium recovery in the atmosphere gets; When the helium that gets being distributed to the helium recovery in the atmosphere after will in the cooling of the pressure in the manufacturing process of semiconductor wafer purposes, using etc. carries out purifying; Also can use the present invention, so long as contain hydrogen, carbon monoxide at least, the nitrogen and the oxygen that derive from air gets final product as the helium of impurity.
Claims (2)
1. the purification process of a helium is characterized in that,
When the nitrogen and the oxygen that contain hydrogen, carbon monoxide at least, derive from air are carried out purifying as the helium of impurity,
Utilize catalyzer to make oxygen, hydrogen and reaction of carbon monoxide in the said helium, thereby generate carbonic acid gas and water with the state of residual aerobic,
Then add hydrogen, make the hydrogen volumetric molar concentration in the said helium reach 2 times the value that is higher than the oxygen volumetric molar concentration,
Then utilize catalyzer to make oxygen and H-H reaction in the said helium, thereby have the state of hydrogen to generate water with residual,
Then reduce the moisture containing ratio of said helium through dehydration operation,
Then make hydrogen and reactive metal oxide in the said helium, thereby generate water,
Then, adsorb nitrogen, carbonic acid gas and water in the impurity in the said helium at least through the pressure swing adsorption process that uses the zeolites sorbent material,
At least adsorb the nitrogen in the impurity in the said helium through-10 ℃～-50 ℃ alternating temperature absorption method then.
2. the purification devices of a helium, this device are that the nitrogen and the oxygen that contain hydrogen, carbon monoxide at least, derive from air are carried out the device of purifying as the helium of impurity, it is characterized in that, comprising:
First reactor drum, importing in this first reactor drum has said helium;
Second reactor drum, importing in this second reactor drum has the helium that flows out from said first reactor drum;
The hydrogen concentration setting device, this hydrogen concentration setting device is set at 2 times the value that is higher than the oxygen volumetric molar concentration through the hydrogen volumetric molar concentration that interpolation hydrogen will import in the said helium in said second reactor drum;
Water extracter, this water extracter reduces from the moisture containing ratio of the said helium of said second reactor drum outflow through carrying out dehydration operation;
The 3rd reactor drum, importing in the 3rd reactor drum has the said helium that has reduced the moisture containing ratio through said water extracter;
Adsorption unit, this adsorption unit is connected with said the 3rd reactor drum;
In said first reactor drum, be filled with catalyzer, make that oxygen, hydrogen and the carbon monoxide in the said helium reacts in said first reactor drum, thereby generate water and carbonic acid gas,
In said second reactor drum, be filled with catalyzer, make oxygen and the H-H reaction in the said helium in said second reactor drum, thereby have the state of hydrogen to generate water with residual,
In said the 3rd reactor drum, be filled with MOX, make the hydrogen generation oxidation in the said helium in said the 3rd reactor drum and generate water,
Said adsorption unit has PSA unit and TSA unit; This PSA unit adsorbs nitrogen, carbonic acid gas and water in the impurity from the said helium that said the 3rd reactor drum flows out at least through the pressure swing adsorption process that uses the zeolites sorbent material, and this TSA unit adsorbs the nitrogen in the impurity in the said helium at least through-10 ℃～-50 ℃ alternating temperature absorption method.
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| JP2010155823 | 2010-07-08 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523822A (en) * | 2012-07-02 | 2014-01-22 | 住友精化株式会社 | A helium purifying method and a purifying device |
| 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 |
| CN114229810A (en) * | 2021-12-15 | 2022-03-25 | 华能核能技术研究院有限公司 | Helium purification system and method for high-temperature gas-cooled reactor internals thermal aging test |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5614808B2 (en) * | 2011-01-18 | 2014-10-29 | 住友精化株式会社 | Helium gas purification method and purification apparatus |
| JP7148748B1 (en) * | 2022-03-11 | 2022-10-05 | 大陽日酸株式会社 | gas purifier |
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| CN85102708A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Inert gas engaging hydrogen, oxygen scavenging agent |
| CN1237124A (en) * | 1997-09-04 | 1999-12-01 | 液化空气日本有限公司 | Method and apparatus for purification of argon |
| CN1260231A (en) * | 1998-12-04 | 2000-07-19 | 气体产品与化学公司 | Purification for gas |
| JP2003246611A (en) * | 2002-02-26 | 2003-09-02 | Sumitomo Seika Chem Co Ltd | Helium purifying apparatus |
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- 2011-06-16 JP JP2011134075A patent/JP5683390B2/en not_active Expired - Fee Related
- 2011-07-04 CN CN201110198460.6A patent/CN102311103B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN85102708A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Inert gas engaging hydrogen, oxygen scavenging agent |
| CN1237124A (en) * | 1997-09-04 | 1999-12-01 | 液化空气日本有限公司 | Method and apparatus for purification of argon |
| CN1260231A (en) * | 1998-12-04 | 2000-07-19 | 气体产品与化学公司 | Purification for gas |
| JP2003246611A (en) * | 2002-02-26 | 2003-09-02 | Sumitomo Seika Chem Co Ltd | Helium purifying apparatus |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523822A (en) * | 2012-07-02 | 2014-01-22 | 住友精化株式会社 | A helium purifying method and a purifying device |
| 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 |
| CN114229810A (en) * | 2021-12-15 | 2022-03-25 | 华能核能技术研究院有限公司 | Helium purification system and method for high-temperature gas-cooled reactor internals thermal aging test |
| 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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| Publication number | Publication date |
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| JP5683390B2 (en) | 2015-03-11 |
| CN102311103B (en) | 2014-10-15 |
| JP2012031050A (en) | 2012-02-16 |
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