CN102190290A - Refining method of argon gas and refining device - Google Patents
Refining method of argon gas and refining device Download PDFInfo
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- CN102190290A CN102190290A CN2011100484133A CN201110048413A CN102190290A CN 102190290 A CN102190290 A CN 102190290A CN 2011100484133 A CN2011100484133 A CN 2011100484133A CN 201110048413 A CN201110048413 A CN 201110048413A CN 102190290 A CN102190290 A CN 102190290A
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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Abstract
The present invention provides a practical method for reducing load of an afterward absorption treatment, reducing energy required in refining and refining high-purity argon gas through effectively reducing impurity content of the argon gas. When the argon gas which at least contains oxygen, hydrogen, carbon monoxide and nitrogen as impurities, the molar concentration of the oxygen in the nitrogen gas is set to a value which exceeds a summation between the molar concentration of carbon monoxide and the molar concentration of hydrogen. Afterwards, the oxygen is caused to react with the carbon monoxide and the hydrogen for generating carbon oxide and water with a state of residual oxygen. Afterwards, the water content is reduced through dewatering operation. Then, the oxygen and carbon oxide in the impurities are at least adsorbed through a pressure revolving adsorption method of carbon adsorbent, and afterwards, nitrogen in the impurities is adsorbed at least through a thermal revolving adsorption method at the temperature of -10 DEG C to -50 DEG C.
Description
Technical field
The present invention relates to process for purification and device that impurity contains the argon gas of aerobic, hydrogen, carbon monoxide and nitrogen at least
Background technology
Silicon single-crystal pullup stove for example, ceramic post sintering stove, system steel with equipment such as vacuum deaerator plant, silicon for solar cell plasma body melting appartus, polysilicon foundry furnaces in, argon gas is used as furnace atmosphere gas etc.Cause purity drop from the argon gas of this kind equipment recycling because of sneaking into hydrogen, carbon monoxide, air etc.Therefore, for the purity of the argon gas that improves recovery, implement to make the processing of the impurity that adsorbents adsorb sneaks into.Also have,, proposed to make oxygen and combustiblecomponents in the impurity to react the technical scheme (referring to patent documentation 1,2) of the pre-treatment that is used as adsorption treatment in order to carry out the absorption of this impurity effectively.
In the method that patent documentation 1 is disclosed, oxygen amount in the argon gas is adjusted to only than making hydrogen, a little less slightly degree of stoichiometry amount that combustiblecomponents perfect combustions such as carbon monoxide are required, then, so that having precedence over the palladium or the gold of the reaction of carbon monoxide and oxygen, the reaction of hydrogen and oxygen is catalyzer, make oxygen and carbon monoxide in the argon gas, reactions such as hydrogen, there is the state of carbon monoxide to generate carbonic acid gas and water with residual by this, then, make contained carbonic acid gas of adsorbents adsorb argon gas and water at normal temperatures, afterwards, under-10 ℃～-50 ℃ temperature, make contained carbon monoxide of adsorbents adsorb argon gas and nitrogen.
In the method that patent documentation 2 is disclosed, making the oxygen amount in the argon gas is the amount that is enough to make combustiblecomponents perfect combustions such as hydrogen, carbon monoxide, then, use palladium series catalyst to make reactions such as oxygen in the argon gas and carbon monoxide, hydrogen, state with residual aerobic generates carbonic acid gas and water by this, then, makes contained carbonic acid gas of adsorbents adsorb argon gas and water at normal temperatures, afterwards, under the temperature about-170 ℃, make contained oxygen of adsorbents adsorb argon gas and nitrogen.
Patent documentation 1: No. 3496079 communique of Japanese Patent
Patent documentation 2: No. 3737900 communique of Japanese Patent
Summary of the invention
In the method for patent documentation 1 record, make the oxygen amount in the argon gas be less than the needed stoichiometry amounts of perfect combustion such as making hydrogen, carbon monoxide in pretreatment stage, use makes the reaction of hydrogen and oxygen have precedence over the catalyst for reaction of carbon monoxide and oxygen, and the state with residual carbon monoxide generates carbonic acid gas and water by this.But, unreacted carbon monoxide and water vapor generation water gas shift reaction and regeneration hydrogen, existence can't be tackled the defective of the situation that requires to reduce hydrogen.In addition, in the method for patent documentation 1 record, the stage of oxygen in making impurity and the reacted adsorption treatment of combustiblecomponents, make adsorbents adsorb carbonic acid gas and water at normal temperatures after, make adsorbents adsorb carbon monoxide and nitrogen at-10 ℃～-50 ℃.In the time of will under such low temperature, having adsorbed the adsorbent reactivation of carbon monoxide and nitrogen, need bigger energy, therefore be unfavorable for industrial production because carbon monoxide is compared with nitrogen from the sorbent material disengaging.
In the method for patent documentation 2 records, making the oxygen amount in the argon gas in pretreatment stage is the amount that is enough to make perfect combustions such as hydrogen, carbon monoxide, and the state with residual oxygen generates carbonic acid gas and water by this.But the temperature in the time of need making absorption for adsorb oxygen is reduced to about-170 ℃.That is since in the pre-treatment of adsorption treatment residual oxygen, so the power consumption of the cooling during adsorption treatment increases the problem that exists refining load to increase.
The process for purification and the refining plant that the purpose of this invention is to provide the argon gas that can solve above-mentioned prior art problems.
Method of the present invention is to contain aerobic at least as impurity, hydrogen, the process for purification of the argon gas of carbon monoxide and nitrogen, it is characterized in that, oxygen volumetric molar concentration in described argon gas is 1/2 when following of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, be set value by adding oxygen into surpassing 1/2, then, the use catalyzer makes oxygen and carbon monoxide and the H-H reaction in the described argon gas, state with residual oxygen generates carbonic acid gas and water, then, reduce moisture containing ratio in the described argon gas by dehydration operation, then, by using carbon is that the pressure swing adsorption process of sorbent material adsorbs the oxygen and carbon dioxide in the impurity in the described argon gas at least, afterwards, adsorb nitrogen in the impurity in the described argon gas at least by the hot swing adsorption process under-10 ℃～-50 ℃.
The present invention is by making oxygen and carbon monoxide and the H-H reaction in the argon gas, and state generation carbonic acid gas and water with residual oxygen then, reduce the moisture containing ratio of argon gas by dehydration operation.By this, the major impurity of argon gas becomes oxygen, carbonic acid gas and nitrogen, need not adsorption moisture during therefore with pressure swing adsorption process absorption impurity, and the absorption load is alleviated, in addition, using the high carbon of adsorption effect of oxygen as the sorbent material of pressure swing adsorption process is sorbent material.By this, use the oxygen adsorption effect of the unitary pressure swing adsorption process of PSA to be enhanced, therefore, the unitary hot swing adsorption process of use TSA thereafter just need not adsorb oxygen, compares the adsorption temp of the impurity that can improve hot swing adsorption process during with adsorb oxygen.Thus, though in the pre-treatment of adsorption treatment residual oxygen, can not increase cooling power consumption yet, can improve the rate of recovery and the purity of argon gas.
Based on the oxygen adsorption effect of pressurize swing adsorption process, better be that described carbon is that sorbent material is a carbonaceous molecular sieve among the present invention.
Device of the present invention is to contain aerobic at least as impurity, hydrogen, the refining plant of the argon gas of carbon monoxide and nitrogen, it is characterized in that, possesses the reactor that is imported into described argon gas, concentration adjusting device, drying machine and the adsorption unit that links to each other with described drying machine, the oxygen volumetric molar concentration of this concentration adjusting device in being imported into the described argon gas of described reactor is that 1/2 of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum added oxygen when following and be set value into surpassing 1/2, and this drying machine carries out the moisture containing ratio that dehydration operation reduces the described argon gas that flows out from described reactor; To described reactor catalyst filling, in described reactor, make oxygen and carbon monoxide and H-H reaction in the described argon gas, the state residual with oxygen generates carbonic acid gas and water; Described adsorption unit has PSA unit and TSA unit, this PSA unit is that the pressure swing adsorption process of sorbent material adsorbs oxygen and the carbonic acid gas in the impurity in the described argon gas at least by using carbon, and this TSA unit adsorbs nitrogen in the impurity in the described argon gas at least by the hot swing adsorption process under-10 ℃～-50 ℃.
Utilize device of the present invention can implement method of the present invention.
The present invention can provide and can make with extra care required energy, make with extra care the method and apparatus of the practicality of argon gas with high purity with the load, the minimizing that reduce adsorption treatment thereafter by the impurity containing ratio that reduces effectively in the argon gas.
Description of drawings
Fig. 1 is the structural representation of refining plant of the argon gas of embodiments of the present invention.
Fig. 2 is the structural representation of the pressure-swing adsorption unit in the refining plant of argon gas of embodiments of the present invention.
Fig. 3 is the structural representation of temperature revolution adsorption unit of refining plant of the argon gas of embodiments of the present invention.
Nomenclature
α: refining plant, 3: reactor, 4: concentration adjusting device, 5: drying machine, 9: adsorption unit, 10:PSA unit, 20:TSA unit.
Embodiment
The refining plant α of argon gas shown in Figure 1 is the device that will be reclaimed, be made with extra care, enable to utilize again by the used argon gas of for example this class argon gas feed source 1 supply of polysilicon foundry furnace, possesses well heater 2, reactor 3, concentration adjusting device 4, drying machine 5, water cooler 8 and adsorption unit 9.
The argon gas of being supplied with by supply source α is through not shown dedustings such as strainer, be imported into well heater 2 by air transporting arrangements such as gas blower (not shown) again.Impurity as the contained trace of the argon gas of refining object is at least oxygen, hydrogen, carbon monoxide and nitrogen, also can contain other impurity such as carbonic acid gas, hydrocarbon, water.There is no particular limitation for the concentration for the treatment of the impurity in the purified argon gas, for example is about 5 molar ppm～40000 molar ppm.In order to finish the reaction in each reactor 3,6, the Heating temperature of the argon gas of well heater 2 is preferably more than 250 ℃, from the angle that prevents that life of catalyst from shortening, better is below 450 ℃.
The argon gas that heater via 2 heated is imported into reactor 3.The oxygen volumetric molar concentration of concentration adjusting device 4 in the argon gas that is imported into reactor 3 is 1/2 when following of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, adds oxygen and is set value into surpassing 1/2.The concentration adjusting device 4 of present embodiment has density measuring device 4a, oxygen supply source 4b, oxygen amount setter 4c and controller 4d.Density measuring device 4a measures oxygen volumetric molar concentration, carbon monoxide volumetric molar concentration and the hydrogen volumetric molar concentration in the argon gas that is imported into reactor 3, and this measured signal is delivered to controller 4d.Controller 4d is 1/2 when following of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum in measured oxygen volumetric molar concentration, correspondence is reached the control signal that surpasses the required oxygen amount of 1/2 value deliver to oxygen amount setter 4c.Oxygen amount setter 4c is to doing the aperture adjustment from oxygen supply source 4b to the stream of reactor 3, with the oxygen of supply with the corresponding amount of control signal.By this, be set to 1/2 value as the oxygen volumetric molar concentration in the argon gas of refining object above carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum.
In reactor 3, fill the catalyzer that makes oxygen and hydrogen and reaction of carbon monoxide.By this, by make oxygen and carbon monoxide and the H-H reaction in the argon gas in reactor 3, the state residual with oxygen generates carbonic acid gas and water.Also have, contain hydrocarbon from the argon gas of recovery such as polysilicon foundry furnace, but its volumetric molar concentration is generally below 1/100 of total volumetric molar concentration of hydrogen and carbon monoxide as combustiblecomponents.Thus, only surpass 1/2 of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum slightly, then can generate carbonic acid gas and water with the residual state of oxygen if usually the oxygen volumetric molar concentration is set at.Be packed into the catalyzer of reactor 3 so long as make oxygen and the catalyzer of carbon monoxide and H-H reaction then there is no particular limitation, for example can use platinum, platinum alloy, palladium even load in the catalyzer of aluminum oxide etc.
Drying machine 5 is by carrying out the moisture containing ratio of dehydration operation minimizing from reactor 3 effusive argon gas.Drying machine 5 can use commercially available drying machine, for example can use the argon gas pressurization is removed moisture with sorbent material, under reduced pressure the adding pressure type dewatering unit of reproducing adsorbent; Argon gas pressurization cooling is removed the freezing type dewatering unit of agglomerative moisture; Remove the contained moisture of argon gas with dewatering agent, the thermal dehydration agent makes its regenerated thermal regeneration formula dewatering unit etc.; Thermal regeneration formula dewatering unit is reducing aspect the moisture containing ratio comparatively desirablely effectively, preferably the moisture in the argon gas can be removed about device of about 99%.
Adsorption unit 9 links to each other with drying machine 5 by water cooler 8.Drying machine 5 processed and the argon gas that reduced the moisture containing ratio is imported into adsorption unit 9 after water cooler 8 coolings.Absorption is adorned 9 and is put and have PSA unit 10 and TSA unit 20.This PSA unit 10 is that pressure swing adsorption process under the normal temperature of sorbent material adsorbs oxygen and the carbonic acid gas in the impurity in the argon gas at least by using carbon, and this TSA unit 20 adsorbs nitrogen in the impurity in the argon gas at least by the hot swing adsorption process under-10 ℃～-50 ℃.
The outlet 13k of adsorption tower 13 links to each other with outflow pipe arrangement 13m by transforming valve 131 separately, link to each other with the pipe arrangement 13o that boosts by transforming valve 13n, link to each other with all pressing washing outlet side line 13q by transforming valve 13p, link to each other with all pressing cleaning inlet side pipe arrangement 13s by flowrate control valve 13r.
Flow out pipe arrangement 13m and link to each other with TSA unit 20 by pressure regulator valve 13t, the pressure of argon gas that is imported into TSA unit 20 is by constant.
The pipe arrangement 13o that boosts by flowrate control valve 13u, flow indication accommodometer 13v with flow out pipe arrangement 13m and link to each other, the flow among the pipe arrangement 13o that boosts is adjusted to constant, the flow that prevents to be imported into the argon gas of TSA unit 20 by this changes.
All press washing outlet side line 13q and all press cleaning inlet side pipe arrangement 13s to interconnect, be provided with transforming valve 13x at each connecting pipings 13w by a pair of connecting pipings 13w.
The 1st of PSA unit 10～the 4th adsorption tower 13 carries out absorption process, decompression I operation (purge gas output operation), decompression II operation (body of all calming the anger output operation), desorption operation, matting (purge gas input operation), the I operation of boosting (body of all calming the anger input operation), the II operation of boosting separately successively.
That is, in the 1st adsorption tower 13, only open transforming valve 13b and transforming valve 131, the argon gas of supplying with from reactor 3 is imported into the 1st adsorption tower 13 from compressor 12 through transforming valve 13b.By this, carbonic acid gas at least in the argon gas that imports in the 1st adsorption tower 13 and moisture are adsorbed the absorption process of agent absorption, and the argon gas that the containing ratio of impurity has obtained reducing is sent to TSA unit 20 from the 1st adsorption tower 13 through flowing out pipe arrangement 13m.At this moment, a part that is sent to the argon gas that flows out pipe arrangement 13m is sent to other adsorption tower (present embodiment is the 2nd adsorption tower 13), the II operation of boosting through the pipe arrangement 13o that boosts, flowrate control valve 13u in the 2nd adsorption tower 13.
Then, close the transforming valve 13b, 131 of the 1st adsorption tower 13, open transforming valve 13p, open the flowrate control valve 13r of other adsorption towers (being the 4th adsorption tower 13 in the present embodiment), open 1 among the transforming valve 13x.By this, the less argon gas of the impurity containing ratio on the top of the 1st adsorption tower 13 cleans inlet side pipe arrangement 13s and is sent to the 4th adsorption tower 13 through all pressing, in the 1st adsorption tower 13 I operation that reduces pressure.At this moment, transforming valve 13e is opened in the 4th adsorption tower 13, carries out matting.
Then, under the state of the flowrate control valve 13r of transforming valve 13p that opens the 1st adsorption tower 13 and the 4th adsorption tower 13, close the transforming valve 13e of the 4th adsorption tower 13, implement the decompression II operation of the recovery of gas by this at the 4th adsorption tower 13, the internal pressure between the 1st adsorption tower 13 and the 4th adsorption tower 13 reaches mutual homogeneous or reaches basic homogeneous.At this moment, transforming valve 13x can be according to circumstances 2 all open.
Then, open the transforming valve 13e of the 1st adsorption tower 13, close transforming valve 13p, carry out by this from the desorption operation of sorbent material desorption impurity, impurity is discarded in the atmosphere through sound damper 13f with gas.
Then, open the flowrate control valve 13r of the 1st adsorption tower 13, close the transforming valve 13b, 131 of the 2nd adsorption tower 13 of the state of having finished absorption process, open transforming valve 13p.By this, the less argon gas of the impurity containing ratio on the top of the 2nd adsorption tower 13 is sent to the 1st adsorption tower 13 through all pressing cleaning inlet side pipe arrangement 13s, carries out matting at the 1st adsorption tower 13.The gas that is used to matting at the 1st adsorption tower 13 is discarded in the atmosphere through transforming valve 13e, sound damper 13f.At this moment, the I operation that in the 2nd adsorption tower 13, reduces pressure.Then, under the state of the flowrate control valve 13r of transforming valve 13p that opens the 2nd adsorption tower 13 and the 1st adsorption tower 13, close the transforming valve 13e of the 1st adsorption tower, the I operation of boosting by this.At this moment, transforming valve 13x can be according to circumstances 2 all open.
Afterwards, close the flowrate control valve 13r of the 1st adsorption tower 13, temporarily be in the holding state of no operation.The II operation of boosting of this state continuance to the 4 adsorption towers 13 finishes.If the end of boosting of the 4th adsorption tower 13, absorption process switches to the 4th adsorption tower 13 from the 3rd adsorption tower 13, then open the transforming valve 13n of the 1st adsorption tower, a part of delivering to the argon gas that flows out pipe arrangement 13m from other adsorption towers (present embodiment is the 4th adsorption tower 13) that are in absorption process is sent to the 1st adsorption tower 13 through the pipe arrangement 13o that boosts, flowrate control valve 13u, in the 1st adsorption tower 13 II operation of boosting.
Above-mentioned each operation repeats respectively successively at the 1st～the 4th adsorption tower 13, has reduced the argon gas of impurity containing ratio by this and has been 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 also be for example 2 or 3 except 4.
TSA unit 20 can use known device.For example, TSA unit 20 shown in Figure 3 is 2 tower, has the heat exchange type pre-cooler 21 of the argon gas precooling that will send from PAS unit 10; Will be through the further refrigerative heat exchange type of pre-cooler 21 refrigerative argon gas water cooler 22; Cover the heat exchange department 24 of the 1st, the 2nd adsorption tower 23, each adsorption tower 23.Heat exchange department 24 cools off sorbent material with refrigerant when absorption process, add heat-adsorbent with heating agent when the desorption operation.Each adsorption tower 23 has a plurality of interior pipe of having filled sorbent material.This sorbent material uses the sorbent material that is suitable for nitrogen absorption, preferably use exchange ion to be divalent cationic X type zeolite or y-type zeolite, for example can use the zeolite that has carried out ion-exchange with calcium (Ca) or lithium (Li) is sorbent material, also have, this divalent positively charged ion is more preferably at least a kind that is selected from magnesium (Mg), calcium (Ca), strontium (Sr), the barium (Ba).
The inlet 23a of adsorption tower 23 passes in the atmosphere by open and close valve 23c separately.
The outlet 23e of adsorption tower 23 links to each other with outflow pipe arrangement 23g by open and close valve 23f separately, and boosting with cooling by open and close valve 23h links to each other with pipe arrangement 23i, links to each other with pipe arrangement 23k with cleaning by open and close valve 23j.
Flow out the part of pipe arrangement 23g formation pre-cooler 21, utilize from flowing out the argon gas that the cooling of the effusive purified of pipe arrangement 23g argon gas transports from PSA unit 10.The purified argon gas flows out from flowing out pipe arrangement 23g through primary side pressure controlled valve 231.
Cooling is boosted with pipe arrangement 23i, is cleaned with pipe arrangement 23k and pass through under meter 23m, flowrate control valve 23o, open and close valve 23n and flow out pipe arrangement 23g to link to each other.
In the 1st, the 2nd adsorption tower 23 of TSA unit 20, carry out absorption process, desorption operation, matting, refrigerating work procedure, the operation of boosting respectively successively.
That is, in TSA unit 20, the argon gas of supplying with from PSA unit 10 is imported into the 1st adsorption tower 23 by open and close valve 23b after pre-cooler 21, water cooler 22 coolings.At this moment, the 1st adsorption tower 23 circulates to form by refrigerant in heat exchanger 24 and is cooled to-10 ℃～-50 ℃ state, and open and close valve 23c, 23h, 23j are closed, and open and close valve 23f is opened, and the contained nitrogen of argon gas is adsorbed agent absorption at least.By this, carry out absorption process at the 1st adsorption tower 23, the refining argon gas that the containing ratio of impurity has obtained reducing flows out through primary side pressure controlled valve 231 from adsorption tower 23.
During in the 1st adsorption tower 23, carrying out absorption process, carry out desorption operation, matting, refrigerating work procedure, the operation of boosting at the 2nd adsorption tower 23.
That is, in the 2nd adsorption tower 23, after absorption process finished, in order to implement the desorption operation, open and close valve 23b, 23f were closed, and open and close valve 23c is opened.By this, the helium that contains impurity in the 2nd adsorption tower 23 is released in the atmosphere, and pressure is reduced to normal atmosphere substantially.In this desorption operation, to when carrying out absorption process, the 2nd adsorption tower 23 make the open and close valve 24f of refrigerant round-robin heat exchange department 24 switch to closing condition, stop the circulation of refrigerant, will extract the open and close valve 24f that refrigerants turn back to refrigerant supply source 24b out from heat exchange department 24 and switch to open mode.
Then, in order to implement matting at the 2nd adsorption tower 23, make open and close valve 23c, the 23j of the 2nd adsorption tower 23 and cleaning with the open and close valve 23n of pipe arrangement 23k in opened condition, the part of the warmed-up refining argon gas of heat exchange in heat exchange type pre-cooler 21 is imported into the 2nd adsorption tower 23 by cleaning with pipe arrangement 23k.By this, implement the cleaning of impurity from the desorption and the refining argon gas of utilization of sorbent material at the 2nd adsorption tower 23, the argon gas that is used to this cleaning is discarded to the atmosphere with impurity from open and close valve 23c.In this matting, will be used to make the open and close valve 24f of heating agent round-robin heat exchange department 24 to switch to open mode at the 2nd adsorption tower 23.
Then, in order to implement refrigerating work procedure at the 2nd adsorption tower 23, the open and close valve 23n that makes the open and close valve 23j of the 2nd adsorption tower 23 and clean with pipe arrangement 23k is closing condition, the open and close valve 23h of the 2nd adsorption tower 23 and cooling are boosted with the open and close valve 23n of pipe arrangement 23i in opened condition, and boosting through cooling from the part of the 1st adsorption tower 23 effusive refining argon gas is imported into the 2nd adsorption tower 23 with pipe arrangement 23i.By this, the refining argon gas that has cooled off the 2nd adsorption tower 23 inside is discarded in the atmosphere through open and close valve 23c.In this refrigerating work procedure, will be used to make heating agent round-robin open and close valve 24f to switch to closing condition heating agent circulation is stopped, will extract the open and close valve 24f that heating agents are back to heating agent supply source 24d out from heat exchange department 24 and switch to open mode.The extraction of heating agent will be used to make the open and close valve 24f of refrigerant round-robin heat exchange department 24 to switch to open mode at the 2nd adsorption tower 23 after finishing, and form the refrigerant recurrent state.This refrigerant recurrent state lasts till the operation and again till down the end of absorption process of boosting then.
Then, in order to implement to boost operation at the 2nd adsorption tower 23, the open and close valve 23c of the 2nd adsorption tower 23 is closed, and is imported into from the part of the 1st adsorption tower 23 effusive refining argon gas, is boosted in the inside of the 2nd adsorption tower 23.The interior pressure that this operation of boosting lasts till the 2nd adsorption tower 23 is with till the interior pressure of the 1st adsorption tower 23 equates substantially.The operation of boosting one end, the open and close valve 23n that the open and close valve 23h of the 2nd adsorption tower 23 and cooling are boosted with pipe arrangement 23i just is closed, whole open and close valve 23b, 23c, 23f, 23h, the 23j of the 2nd adsorption tower 23 are closing state by this, and the 2nd adsorption tower 23 is holding state until next absorption process.
The absorption process of the absorption process of the 2nd adsorption tower 23 and the 1st absorption process 23 is similarly implemented.During the 2nd adsorption tower 23 carries out absorption process, similarly carry out desorption operation, matting, refrigerating work procedure, the operation of boosting at the 1st adsorption tower 23 and the 2nd adsorption tower 23.
Also have, TSA unit 20 is not limited to unit shown in Figure 3, and for example the tower number can for example can be 3 or 4 for more than 2.
Utilize when above-mentioned refining plant α is refining to contain the argon gas of oxygen, hydrogen, carbon monoxide and nitrogen at least, oxygen volumetric molar concentration in this argon gas is 1/2 when following of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, by after adding oxygen the oxygen volumetric molar concentration being set at 1/2 value above carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, the use catalyzer makes oxygen and carbon monoxide and the H-H reaction in this argon gas, state with residual aerobic generates carbonic acid gas and water by this, then, reduce moisture containing ratio in this argon gas by dehydration operation.By this, the major impurity of argon gas becomes oxygen, carbonic acid gas and nitrogen, and therefore used thereafter pressure swing adsorption process need not adsorption moisture when adsorbing impurity, and the absorption load is alleviated, in addition, using the high carbon of adsorption effect of oxygen as the sorbent material of pressure swing adsorption process is sorbent material.By this, the oxygen adsorption effect of applying pressure swing adsorption process is enhanced, and therefore, used thereafter hot swing adsorption process just need not adsorb oxygen, compares the adsorption temp of the impurity that can improve hot swing adsorption process during with adsorb oxygen.Thus, though in the pre-treatment of adsorption treatment residual oxygen, can not increase cooling power consumption yet, can improve the rate of recovery and the purity of argon gas.
Embodiment 1
Use above-mentioned refining plant α to carry out the refining of argon gas.Contain the oxygen of 500 molar ppm, the hydrogen of 20 molar ppm, the carbon monoxide of 1800 molar ppm, the nitrogen of 1000 molar ppm, the carbonic acid gas of 20 molar ppm, the moisture of 20 molar ppm respectively as impurity in the argon gas.With the flow feeding reaction device 3 of this argon gas with 3.74L/min, the flow with 3.4mL/min adds oxygen in this argon gas under standard state again under standard state.Fill the platina catalyzer of 45mL alumina load in reactor 3, reaction conditions is 300 ℃ of temperature, normal atmosphere, space velocity 5000/h.
To use freezing type dewatering unit to be cooled to-35 ℃ from reactor 3 effusive argon gas, remove moisture, carry out dehydration operation by this, reduce the moisture containing ratio of argon gas as drying machine 5.
After water cooler 8 coolings, reduce the containing ratio of impurity from drying machine 5 effusive argon gas by adsorption unit 9.10 employings 3 of PSA unit are tower, fill the carbonaceous molecular sieve (Japanese rock visit chemical company (Japanese エ Application バ イ ロ ケ ミ カ Le ズ) system 3k-172) of 1.25L as the cylindric moulding carbon of the diameter 2mm of sorbent material at each tower, adsorptive pressure is that 0.9MPa, desorption pressure are 0.1MPa.
To import TSA unit 20 by 10 purified argon gas through the PSA unit.It is 2 tower that TSA unit 20 adopts, and fills the CaX type zeolite of 1.5L as sorbent material at each tower, adsorptive pressure be 0.8MPa, adsorption temp for-35 ℃, desorption pressure be that 0.1MPa, desorption temperature are 40 ℃.
20 effusive compositions through the purified argon gas are shown in following table 1 from the TSA unit.In addition, oxygen concn in the purified argon gas records with U.S. Taylor dyne (Teledyne) corporate system micro amount of oxygen densitometer model 311, and carbon monoxide and concentration of carbon dioxide use the system GC-FID of Shimadzu Corporation to record by methanation device (methanizer).Hydrogen concentration uses Japanese GL science corporate system GC-PID to record.
Embodiment 2
Except the interpolation flow that makes oxygen under the standard state for the 5.00mL/min, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Embodiment 3
Except will changing MgX type zeolite at the sorbent material that TSA unit 20 uses, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Embodiment 4
Except will changing at the adsorption temp of TSA unit 20-50 ℃, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Comparative example 1
Except the interpolation flow that makes oxygen under the standard state for the 1mL/min, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Comparative example 2
Except will changing CaA type zeolite at the sorbent material that PSA unit 10 uses, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Comparative example 3
Except the dehydration operation that does not carry out drying machine, refining similarly to Example 1 argon gas.This composition through the purified argon gas is shown in following table 1.
Table 1
Can confirm that from last table 1 each embodiment compares with each comparative example, purity of argon height, oxygen concn are lower than comparative example 2,3, and carbon monoxide concentration is lower than comparative example 1, hydrogen concentration is lower than comparative example 1,3.
Claims (3)
1. the process for purification of argon gas, it is to contain aerobic at least as impurity, hydrogen, the process for purification of the argon gas of carbon monoxide and nitrogen, it is characterized in that, oxygen volumetric molar concentration in described argon gas is 1/2 when following of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, be set value by adding oxygen into surpassing 1/2, then, the use catalyzer makes oxygen and carbon monoxide and the H-H reaction in the described argon gas, state with residual oxygen generates carbonic acid gas and water, then, reduce moisture containing ratio in the described argon gas by dehydration operation, then, by using carbon is that the pressure swing adsorption process of sorbent material adsorbs the oxygen and carbon dioxide in the impurity in the described argon gas at least, afterwards, adsorbs nitrogen in the impurity in the described argon gas at least by the hot swing adsorption process under-10 ℃～-50 ℃.
2. the process for purification of argon gas as claimed in claim 1 is characterized in that, described carbon is that sorbent material is a carbonaceous molecular sieve.
3. the refining plant of argon gas, it is to contain aerobic at least as impurity, hydrogen, the refining plant of the argon gas of carbon monoxide and nitrogen, it is characterized in that, possesses the reactor that is imported into described argon gas, concentration adjusting device, drying machine and the adsorption unit that links to each other with described drying machine, the oxygen volumetric molar concentration of this concentration adjusting device in being imported into the described argon gas of described reactor is that 1/2 of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum added oxygen when following and be set value into surpassing 1/2, and this drying machine carries out the moisture containing ratio that dehydration operation reduces the described argon gas that flows out from described reactor; To described reactor catalyst filling, in described reactor, make oxygen and carbon monoxide and H-H reaction in the described argon gas, the state residual with oxygen generates carbonic acid gas and water; Described adsorption unit has PSA unit and TSA unit, this PSA unit is that the pressure swing adsorption process of sorbent material adsorbs oxygen and the carbonic acid gas in the impurity in the described argon gas at least by using carbon, and this TSA unit adsorbs nitrogen in the impurity in the described argon gas at least by the hot swing adsorption process under-10 ℃～-50 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159192A (en) * | 2011-12-13 | 2013-06-19 | 住友精化株式会社 | Purifying method and purifying device of helium |
| CN103569979A (en) * | 2012-08-09 | 2014-02-12 | 住友精化株式会社 | Purifying method and purifying device for argon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5748272B2 (en) * | 2010-07-07 | 2015-07-15 | 住友精化株式会社 | Helium gas purification method and purification apparatus |
| CN115105925B (en) * | 2022-05-25 | 2023-10-31 | 山西皆利气体科技有限公司 | Double-reflux multi-tower vacuum pressure swing adsorption method and adsorption system |
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| CN1093678A (en) * | 1993-03-02 | 1994-10-19 | 普拉塞尔技术有限公司 | The purifying of crude argon |
| JPH07138007A (en) * | 1993-11-17 | 1995-05-30 | Nippon Sanso Kk | Purification of argon gas and apparatus therefor |
| CN1346788A (en) * | 2001-09-14 | 2002-05-01 | 温州瑞气空分设备有限公司 | Process for purifying gas |
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| JPS60122709A (en) * | 1983-12-07 | 1985-07-01 | Hitachi Ltd | Method for recovering argon |
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| JP2761917B2 (en) * | 1989-04-15 | 1998-06-04 | 日本酸素株式会社 | Argon recovery method |
| JP2782356B2 (en) * | 1989-04-21 | 1998-07-30 | 日本酸素株式会社 | Argon recovery method |
| JPH03164410A (en) * | 1990-07-30 | 1991-07-16 | Sumitomo Seika Chem Co Ltd | Production of concentrated argon |
| MY116855A (en) * | 1996-02-28 | 2004-04-30 | Air Prod & Chem | Argon recovery from silicon crystal furnace |
| JP3737900B2 (en) * | 1999-02-10 | 2006-01-25 | エア・ウォーター株式会社 | Purification method of exhaust gas argon from single crystal production furnace |
| US6527831B2 (en) * | 2000-12-29 | 2003-03-04 | Praxair Technology, Inc. | Argon purification process |
| US7645431B2 (en) * | 2007-10-23 | 2010-01-12 | Air Products And Chemicals, Inc. | Purification of noble gases using online regeneration of getter beds |
| JP2009234868A (en) * | 2008-03-27 | 2009-10-15 | Nippon Steel Corp | Apparatus and method for purifying argon gas |
| JP5403685B2 (en) * | 2010-02-25 | 2014-01-29 | 住友精化株式会社 | Argon gas purification method and purification apparatus |
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2011
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- 2011-02-02 JP JP2011020725A patent/JP5665120B2/en not_active Expired - Fee Related
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093678A (en) * | 1993-03-02 | 1994-10-19 | 普拉塞尔技术有限公司 | The purifying of crude argon |
| JPH07138007A (en) * | 1993-11-17 | 1995-05-30 | Nippon Sanso Kk | Purification of argon gas and apparatus therefor |
| JP3496079B2 (en) * | 1993-11-17 | 2004-02-09 | 日本酸素株式会社 | Method and apparatus for purifying argon gas |
| CN1346788A (en) * | 2001-09-14 | 2002-05-01 | 温州瑞气空分设备有限公司 | Process for purifying gas |
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| CN103159192A (en) * | 2011-12-13 | 2013-06-19 | 住友精化株式会社 | Purifying method and purifying device of helium |
| CN103569979A (en) * | 2012-08-09 | 2014-02-12 | 住友精化株式会社 | Purifying method and purifying device for argon |
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| TW201136654A (en) | 2011-11-01 |
| KR20110097648A (en) | 2011-08-31 |
| TWI478761B (en) | 2015-04-01 |
| KR101720799B1 (en) | 2017-03-28 |
| CN102190290B (en) | 2014-10-29 |
| JP2011195434A (en) | 2011-10-06 |
| JP5665120B2 (en) | 2015-02-04 |
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