CN102190290B - Refining method of argon gas and refining device - Google Patents
Refining method of argon gas and refining device Download PDFInfo
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- CN102190290B CN102190290B CN201110048413.3A CN201110048413A CN102190290B CN 102190290 B CN102190290 B CN 102190290B CN 201110048413 A CN201110048413 A CN 201110048413A CN 102190290 B CN102190290 B CN 102190290B
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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
- B01D53/047—Pressure swing adsorption
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- C01B23/0052—Physical processing only by adsorption in solids
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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 impurity and at least contain process for purification and the device of the argon gas of aerobic, hydrogen, carbon monoxide and nitrogen
Background technology
Such as silicon single-crystal pullup stove, ceramic sintering furnace, processed for steel in the equipment such as vacuum deaerator plant, silicon for solar cell plasma body melting appartus, polysilicon foundry furnace, argon gas is used as furnace atmosphere gas etc.From the argon gas of this kind equipment recycling, because sneaking into hydrogen, carbon monoxide, air etc., cause purity drop.Therefore,, in order to improve the purity of the argon gas of recovery, implement to make sorbent material to adsorb the processing of the impurity of sneaking into.Also have, in order effectively to carry out the absorption of this impurity, proposed to make oxygen in impurity to react the technical scheme (referring to patent documentation 1,2) of the pre-treatment that is used as adsorption treatment with combustiblecomponents.
In the method disclosing at patent documentation 1, by the oxygen flow regulation in argon gas to only than making hydrogen, the slightly a little less degree of stoichiometry amount that the combustiblecomponents perfect combustions such as carbon monoxide are required, then, so that the reaction of hydrogen and oxygen has precedence over palladium or the gold of the reaction of carbon monoxide and oxygen, it is catalyzer, make oxygen and carbon monoxide in argon gas, the reactions such as hydrogen, to remain the state of carbon monoxide, generate carbonic acid gas and water by this, then, make at normal temperatures contained carbonic acid gas and the water of sorbent material absorption argon gas, afterwards, at the temperature of-10 ℃～-50 ℃, make contained carbon monoxide and the nitrogen of sorbent material absorption argon gas.
In the method disclosing at patent documentation 2, making the oxygen amount in argon gas is the amount that is enough to make the combustiblecomponents perfect combustions such as hydrogen, carbon monoxide, then, use palladium series catalyst that the oxygen in argon gas is reacted with carbon monoxide, hydrogen etc., state with residual aerobic generates carbonic acid gas and water by this, then, makes at normal temperatures contained carbonic acid gas and the water of sorbent material absorption argon gas, afterwards, at the temperature of-170 ℃ of left and right, make contained oxygen and the nitrogen of sorbent material absorption argon gas.
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 that patent documentation 1 is recorded, in pretreatment stage, make the oxygen amount in argon gas be less than the needed stoichiometry amounts of perfect combustion such as making hydrogen, carbon monoxide, use makes the reaction of hydrogen and oxygen have precedence over the catalyzer of the 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 cannot be tackled the defect of the situation that requires to reduce hydrogen.In addition, in the method that patent documentation 1 is recorded, the stage of the oxygen in making impurity and the reacted adsorption treatment of combustiblecomponents, make at normal temperatures after sorbent material absorbing carbon dioxide and water, at-10 ℃～-50 ℃, make sorbent material absorption carbon monoxide and nitrogen.When having adsorbed the adsorbent reactivation of carbon monoxide and nitrogen under such low temperature, due to carbon monoxide, compare with nitrogen from sorbent material and depart from and need larger energy, be therefore unfavorable for industrial production.
In the method that patent documentation 2 is recorded, in pretreatment stage, making the oxygen amount in argon gas is the amount that is enough to make the 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 to making to adsorb for adsorb oxygen is down to-170 ℃ of left and right.That is, due to residual oxygen in the pre-treatment of adsorption treatment, so cooling power consumption during adsorption treatment increases, the problem that exists refining load to increase.
The process for purification and the refining plant that the object of this invention is to provide the argon gas of the problem that can solve above-mentioned prior art.
Method of the present invention is at least containing aerobic 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, by adding oxygen, be set the value into surpassing 1/2, then, use catalyzer to make oxygen and carbon monoxide and the H-H reaction in described argon gas, state with residual oxygen generates carbonic acid gas and water, then, by dehydration operation, reduce the moisture containing ratio in described argon gas, then, the pressure swing adsorption process that is sorbent material by use carbon at least adsorbs the oxygen and carbon dioxide in the impurity in described argon gas, afterwards, by the hot swing adsorption process at-10 ℃～-50 ℃, at least adsorb the nitrogen in the impurity in described argon gas.
The present invention is by making oxygen and carbon monoxide and the H-H reaction in 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, during therefore with pressure swing adsorption process absorption impurity, without adsorption moisture, absorption load is alleviated, in addition, as the sorbent material of pressure swing adsorption process, using the high carbon of adsorption effect of oxygen is sorbent material.By this, use the oxygen adsorption effect of the pressure swing adsorption process of PSA unit to be enhanced, therefore, the hot swing adsorption process of use TSA unit thereafter, just without adsorb oxygen, is compared 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.
Oxygen adsorption effect based on improving pressure swing adsorption process in the present invention is better that described carbon is that sorbent material is carbonaceous molecular sieve.
Device of the present invention is at least containing aerobic 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 being connected with described drying machine, the oxygen volumetric molar concentration of this concentration adjusting device in the described argon gas that is imported into 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 as the value over 1/2, this drying machine carries out dehydration operation minimizing from the moisture containing ratio of the described argon gas of described reactor outflow, to described reactor catalyst filling, in described reactor, make oxygen and carbon monoxide and H-H reaction in described argon gas, the state residual with oxygen generates carbonic acid gas and water, described adsorption unit has PSA unit and TSA unit, the pressure swing adsorption process that this PSA unit is sorbent material by use carbon at least adsorbs oxygen and the carbonic acid gas in the impurity in described argon gas, and this TSA unit at least adsorbs the nitrogen in the impurity in described argon gas by the hot swing adsorption process at-10 ℃～-50 ℃.
Utilize device of the present invention can implement method of the present invention.
The present invention can provide the practical method and apparatus that can be refined required energy, refine argon gas with high purity to reduce load, the minimizing of adsorption treatment thereafter by the impurity containing ratio effectively reducing in argon gas.
Accompanying drawing explanation
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 device 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 the argon gas shown in Fig. 1 reclaims, refines, enables the device of recycling by the used argon gas by for example this class argon gas feed source 1 of polysilicon foundry furnace is supplied with, and 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 the not shown dedustings such as strainer, be imported into well heater 2 by the air transporting arrangements such as gas blower (not shown) again.The contained micro-impurity of argon gas as refining object is at least oxygen, hydrogen, carbon monoxide and nitrogen, also can contain other impurity such as carbonic acid gas, hydrocarbon, water.For the concentration for the treatment of the impurity in refining argon gas, there is no particular limitation, for example, be 5 molar ppm left and right, molar ppm～40000.In order to complete the reaction in each reactor 3,6, the Heating temperature of the argon gas of well heater 2 more than 250 ℃, from preventing the angle of the lost of life of catalyzer, is preferably better 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 the value into surpassing 1/2.The concentration adjusting device 4 of present embodiment has density measuring device 4a, oxygen supply source 4b, oxygen flow regulation device 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 to the control signal that surpasses the required oxygen amount of 1/2 value and deliver to oxygen flow regulation device 4c.Oxygen flow regulation device 4c is to doing aperture adjustment from oxygen supply source 4b to the stream of reactor 3, to supply with the oxygen of the amount corresponding with control signal.By this, as the oxygen volumetric molar concentration in the argon gas of refining object, be set to 1/2 the value over carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum.
In the interior filling of reactor 3, make the catalyzer of oxygen and hydrogen and reaction of carbon monoxide.By this, by make oxygen and carbon monoxide and the H-H reaction in argon gas in reactor 3, the state residual with oxygen generates carbonic acid gas and water.Also have, from the argon gas of the recovery such as polysilicon foundry furnace, contain the hydrocarbon as combustiblecomponents, but its volumetric molar concentration is generally below 1/100 of total volumetric molar concentration of hydrogen and carbon monoxide.Thus, if conventionally oxygen volumetric molar concentration is set as only slightly surpassing 1/2 of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, can generate carbonic acid gas and water with the residual state of oxygen.Be packed into the catalyzer of reactor 3 so long as make oxygen and the catalyzer of carbon monoxide and H-H reaction there is no particular limitation, can use such as platinum, platinum alloy, palladium even load in the catalyzer of aluminum oxide etc.
Drying machine 5 is by carrying out dehydration operation minimizing from the moisture containing ratio of the argon gas of reactor 3 outflows.Drying machine 5 can use commercially available drying machine, for example, can use argon pressurization is removed to moisture with sorbent material, under reduced pressure the adding pressure type dewatering unit of reproducing adsorbent; By the cooling freezing type dewatering unit of removing the moisture condensing of argon pressurization; With dewatering agent, remove the contained moisture of argon gas, thermal dehydration agent makes the thermal regeneration formula dewatering unit of its regeneration etc.; Thermal regeneration formula dewatering unit is reducing aspect moisture containing ratio comparatively desirablely effectively, preferably the moisture in argon gas can be removed to the device of approximately 99% left and right.
Adsorption unit 9 is connected with drying machine 5 by water cooler 8.Drying machine 5 processed and the argon gas that reduced moisture containing ratio is imported into adsorption unit 9 after water cooler 8 is cooling.Absorption fills 9 and puts and have 10HeTSA unit, PSA unit 20.This PSA unit 10 is that pressure swing adsorption process under the normal temperature of sorbent material at least adsorbs oxygen and the carbonic acid gas in the impurity in argon gas by using carbon, and this TSA unit 20 at least adsorbs the nitrogen in the impurity in argon gas by the hot swing adsorption process at-10 ℃～-50 ℃.
PSA unit 10 can be used known device.For example, the PSA unit 10 shown in Fig. 2 is 4 tower, has compressor 12 and 4 the 1st～4th adsorption towers 13 of the argon gas compression of flowing out from reactor 3, and at each adsorption tower 13, filling carbon is sorbent material.This carbon is that sorbent material is from improving the preferred carbonaceous molecular sieve of oxygen adsorption effect.
Compressor 12 is connected with the entrance 13a of each adsorption tower 13 by transforming valve 13b.The entrance 13a of adsorption tower 13 is connected in atmosphere by transforming valve 13e and sound damper 13f separately.
The outlet 13k of adsorption tower 13 is connected with outflow pipe arrangement 13m by transforming valve 131 separately, by transforming valve 13n, be connected with the pipe arrangement 13o that boosts, by transforming valve 13p, be connected with all pressing washing outlet side line 13q, by flowrate control valve 13r, be connected with all pressing cleaning inlet side pipe arrangement 13s.
Flow out pipe arrangement 13m and be connected with TSA unit 20 by pressure regulator valve 13t, be imported into the pressure of argon gas of TSA unit 20 by constant.
The pipe arrangement 13o that boosts by flowrate control valve 13u, flow indication accommodometer 13v with flow out pipe arrangement 13m and be connected, the flow boosting in pipe arrangement 13o is adjusted to constant, the flow that prevents from being by this imported into the argon gas of TSA unit 20 changes.
All press washing outlet side line 13q and all press cleaning inlet side pipe arrangement 13s to interconnect by a pair of connecting pipings 13w, at each connecting pipings, 13w is provided with transforming valve 13x.
The 1st～4th adsorption tower 13 of PSA unit 10 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, at least carbonic acid gas in the argon gas importing 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.Now, 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 in the 2nd adsorption tower 13 through the pipe arrangement 13o that boosts, flowrate control valve 13u.
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 present embodiment), open 1 in 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.Now, in the 4th adsorption tower 13, transforming valve 13e is opened, and carries out matting.
Then, opening under the state of the transforming valve 13p of the 1st adsorption tower 13 and the flowrate control valve 13r of the 4th adsorption tower 13, close the transforming valve 13e of the 4th adsorption tower 13, at the 4th adsorption tower 13, implement by this decompression II operation of the recovery of gas, until the internal pressure between the 1st adsorption tower 13 and the 4th adsorption tower 13 reaches mutual homogeneous or reaches basic homogeneous.Now, 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 atmosphere through sound damper 13f together with gas.
Then, open the flowrate control valve 13r of the 1st adsorption tower 13, closed the transforming valve 13b, 131 of the 2nd adsorption tower 13 of the state of 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 cleans inlet side pipe arrangement 13s and is sent to the 1st adsorption tower 13 through all pressing, and at the 1st adsorption tower 13, carries out matting.The gas that is used to matting at the 1st adsorption tower 13 is discarded in atmosphere through transforming valve 13e, sound damper 13f.Now, the I operation that reduces pressure in the 2nd adsorption tower 13.Then, under the state of opening the transforming valve 13p of the 2nd adsorption tower 13 and the flowrate control valve 13r of the 1st adsorption tower 13, close the transforming valve 13e of the 1st adsorption tower, the I operation of boosting by this.Now, transforming valve 13x can be according to circumstances 2 all open.
Afterwards, close the flowrate control valve 13r of the 1st adsorption tower 13, temporary transient in the holding state without 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 is switched to the 4th adsorption tower 13 from the 3rd adsorption tower 13, 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 in absorption process (present embodiment is the 4th adsorption tower 13) 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～4th adsorption tower 13, has reduced by this argon gas of impurity containing ratio and has been delivered to continuously TSA unit 20.
Also have, PSA unit 10 is not limited to the unit shown in Fig. 2, and for example tower number, except 4, can also be for example 2 or 3.
TSA unit 20 can be used known device.For example, the TSA unit 20 shown in Fig. 3 is 2 tower, has the heat exchange type pre-cooler 21 of the argon gas precooling of sending from PAS unit 10; By through the further cooling heat exchange type water cooler 22 of the cooling argon gas of pre-cooler 21; Cover the heat exchange department 24 of the 1st, the 2nd adsorption tower 23, each adsorption tower 23.Heat exchange department 24 with the cooling sorbent material of refrigerant, is used heating medium for heating sorbent material when absorption process when desorption operation.Each adsorption tower 23 has a plurality of inner tubes of having filled sorbent material.This sorbent material is used the sorbent material that is suitable for nitrogen absorption, preferably using exchange ion is the cationic X-type zeolite of divalent or y-type zeolite, for example can use with the zeolite that calcium (Ca) or lithium (Li) have carried out ion-exchange 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), barium (Ba).
Water cooler 22 is connected with the entrance 23a of each adsorption tower 23 by open and close valve 23b.
The entrance 23a of adsorption tower 23 passes in atmosphere by open and close valve 23c separately.
The outlet 23e of adsorption tower 23 is connected with outflow pipe arrangement 23g by open and close valve 23f separately, by open and close valve 23h, is connected with pipe arrangement 23i with cooling boosting, and by open and close valve 23j, is connected with pipe arrangement 23k with cleaning.
Flow out a part for pipe arrangement 23g formation pre-cooler 21, utilize the cooling argon gas transporting from PSA unit 10 of refining argon gas flowing out from flowing out pipe arrangement 23g.Refining argon gas flows out from flowing out pipe arrangement 23g through primary side pressure controlled valve 231.
Cooling boosting is connected by under meter 23m, flowrate control valve 23o, open and close valve 23n and outflow pipe arrangement 23g with pipe arrangement 23k with pipe arrangement 23i, cleaning.
Heat exchange department 24 adopts multitubes, by outer tube 24a, refrigerant supply source 24b, refrigerant for, scatterer 24c, heating agent supply source 24d, heating agent form with scatterer 24e, a plurality of inner tubes of this outer tube 24a encirclement formation adsorption tower 23.In addition, be provided with a plurality of open and close valve 24f, this open and close valve 24f passes through outer tube 24a for switching the refrigerant of supplying with from refrigerant supply source 24b, refrigerant is used the state of scatterer 24e circulation with the state of scatterer 24c circulation and the heating agent of supplying with from heating agent supply source 24d by outer tube 24a, heating agent.Also have, by form a part for water cooler 22 with the pipe arrangement of scatterer 24c branch from refrigerant, utilize refrigerant cooling argon gas in water cooler 22 of being supplied with by refrigerant supply source 24b, this refrigerant is back to container 24g.
In the 1st, the 2nd adsorption tower 23 of TSA unit 20, carry out successively respectively absorption process, desorption operation, matting, refrigerating work procedure, the operation of boosting.
That is,, in TSA unit 20, the argon gas of supplying with from PSA unit 10, after pre-cooler 21, water cooler 22 are cooling, is imported into the 1st adsorption tower 23 by open and close valve 23b.Now, the 1st adsorption tower 23 is circulated and is formed the state that is cooled to-10 ℃～-50 ℃ by refrigerant in heat exchanger 24, and open and close valve 23c, 23h, 23j are closed, and open and close valve 23f is opened, and at least the contained nitrogen of argon gas is adsorbed agent absorption.By this, at the 1st adsorption tower 23, carry out absorption process, 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.
Carry out absorption process in the 1st adsorption tower 23 during, at the 2nd adsorption tower 23, carry out desorption operation, matting, refrigerating work procedure, the operation of boosting.
That is, in the 2nd adsorption tower 23, after absorption process finishes, in order to implement desorption operation, open and close valve 23b, 23f are 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 atmosphere, and pressure is down 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 the heat exchange department 24 of refrigerant circulation switch to closing condition, stop the circulation of refrigerant, the open and close valve 24f that turns back to refrigerant supply source 24b from heat exchange department 24 extraction refrigerants is switched 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 the open and close valve 23n of cleaning use pipe arrangement 23k in opened condition, a part for the warmed-up refining argon gas of heat exchange in heat exchange type pre-cooler 21 uses pipe arrangement 23k to be imported into the 2nd adsorption tower 23 by cleaning.By this, at the 2nd adsorption tower 23, implement impurity from the desorption of sorbent material and utilize the cleaning of refining argon gas, the argon gas that is used to this cleaning is discarded to atmosphere together with impurity from open and close valve 23c.In this matting, at the 2nd adsorption tower 23 by for making the open and close valve 24f of the heat exchange department 24 of heating agent circulation switch to open mode.
Then, in order to implement refrigerating work procedure at the 2nd adsorption tower 23, make the open and close valve 23j of the 2nd adsorption tower 23 and clean to be closing condition with the open and close valve 23n of pipe arrangement 23k, make the open and close valve 23h of the 2nd adsorption tower 23 and the open and close valve 23n of the cooling use pipe arrangement 23i that boosts in opened condition, a part for the refining argon gas flowing out from the 1st adsorption tower 23 is imported into the 2nd adsorption tower 23 through cooling boosting with pipe arrangement 23i.By this, the refining argon gas of cooling the 2nd adsorption tower 23 inside is discarded in atmosphere through open and close valve 23c.In this refrigerating work procedure, will heating agent circulation be stopped for making the open and close valve 24f of heating agent circulation switch to closing condition, the open and close valve 24f that is back to heating agent supply source 24d from heat exchange department 24 extraction heating agents is switched to open mode.After the extraction of heating agent finishes, at the 2nd adsorption tower 23, by for making the open and close valve 24f of the heat exchange department 24 of refrigerant circulation switch to open mode, form refrigerant circulation state.This refrigerant circulation state continuance is till boost operation and the end of absorption process down more 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 a part for the refining argon gas flowing out from the 1st adsorption tower 23 is imported into, and makes by this inside of the 2nd adsorption tower 23 boost.Till this operation of boosting lasts till that the interior pressure of the 2nd adsorption tower 23 and the interior pressure of the 1st adsorption tower 23 equate substantially.The operation of boosting one end, the open and close valve 23h of the 2nd adsorption tower 23 and cooling boosting are just closed with the open and close valve 23n of pipe arrangement 23i, whole open and close valve 23b, 23c, 23f, 23h, the 23j of the 2nd adsorption tower 23 are the state of closing 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, at the 1st adsorption tower 23 and the 2nd adsorption tower 23, similarly carry out desorption operation, matting, refrigerating work procedure, the operation of boosting.
Also have, TSA unit 20 is not limited to the unit shown in Fig. 3, and for example tower number can for more than 2, for example, can be 3 or 4.
Utilize when above-mentioned refining plant α is refining at least contains the argon gas of oxygen, hydrogen, carbon monoxide and nitrogen, 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 adding oxygen, oxygen volumetric molar concentration is set as surpassing after 1/2 value of carbon monoxide volumetric molar concentration and hydrogen volumetric molar concentration sum, use catalyzer to make 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, by dehydration operation, reduce the moisture containing ratio in this argon gas.By this, the major impurity of argon gas becomes oxygen, carbonic acid gas and nitrogen, therefore thereafter during pressure swing adsorption process absorption impurity used without adsorption moisture, absorption load is alleviated, in addition, as the sorbent material of pressure swing adsorption process, using the high carbon of adsorption effect of oxygen is sorbent material.By this, the oxygen adsorption effect of working pressure swing adsorption process is enhanced, and therefore, hot swing adsorption process used, just without adsorb oxygen, is compared the adsorption temp of the impurity that can improve hot swing adsorption process during with adsorb oxygen thereafter.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.In argon gas, as impurity, contain respectively the oxygen of 500 molar ppm, the carbon monoxide of the hydrogen of 20 molar ppm, 1800 molar ppm, the carbonic acid gas of the nitrogen of 1000 molar ppm, 20 molar ppm, the moisture of 20 molar ppm.Under standard state by this argon gas the flow feeding reaction device 3 with 3.74L/min, then the flow with 3.4mL/min adds oxygen in this argon gas under standard state.In reactor 3, fill the platina catalyzer of 45mL alumina load, reaction conditions is 300 ℃ of temperature, normal atmosphere, space velocity 5000/h.
Be used as the freezing type dewatering unit of drying machine 5 to be cooled to-35 ℃ the argon gas flowing out from reactor 3, remove moisture, carry out by this dehydration operation, reduce the moisture containing ratio of argon gas.
The argon gas flowing out from drying machine 5, after water cooler 8 is cooling, reduces the containing ratio of impurity by adsorption unit 9.10 employings 3 of PSA unit are tower, at each tower, fill 1.25L as the carbonaceous molecular sieve (3k-172 processed of Japanese Yan Bai chemical company (Japanese エ Application バ イ ロ ケ ミ カ Le ズ)) of the cylindric moulding carbon of the diameter 2mm of sorbent material, adsorptive pressure is that 0.9MPa, desorption pressure are 0.1MPa.
The argon gas refining through PSA unit 10 imported to TSA unit 20.It is 2 tower that TSA unit 20 adopts, and at each tower, fills 1.5L as the CaX type zeolite of sorbent material, adsorptive pressure be 0.8MPa, adsorption temp for-35 ℃, desorption pressure be that 0.1MPa, desorption temperature are 40 ℃.
From TSA unit, 20 compositions through refining argon gas that flow out are shown in following table 1.In addition, oxygen concn in refining argon gas records by U.S. Taylor dyne (Teledyne) company micro amount of oxygen densitometer processed model 311, and the concentration of carbon monoxide and carbonic acid gas is used the GC-FID processed of Shimadzu Corporation to record by methanation device (methanizer).Hydrogen concentration is used the Japanese GL science GC-PID processed of company to record.
Embodiment 2
Except the interpolation flow that makes oxygen under standard state for 5.00mL/min, refining argon gas similarly to Example 1.This composition through refining argon gas is shown in following table 1.
Embodiment 3
Except the sorbent material using in TSA unit 20 being changed into MgX type zeolite, refine similarly to Example 1 argon gas.This composition through refining argon gas is shown in following table 1.
Embodiment 4
Except the adsorption temp in TSA unit 20 being changed into-50 ℃, refine similarly to Example 1 argon gas.This composition through refining argon gas is shown in following table 1.
Comparative example 1
Except the interpolation flow that makes oxygen under standard state for 1mL/min, refining argon gas similarly to Example 1.This composition through refining argon gas is shown in following table 1.
Comparative example 2
Except the sorbent material using in PSA unit 10 being changed into CaA type zeolite, refine similarly to Example 1 argon gas.This composition through refining argon gas is shown in following table 1.
Comparative example 3
Except not carrying out the dehydration operation of drying machine, refine similarly to Example 1 argon gas.This composition through refining argon gas is shown in following table 1.
Table 1
From upper table 1, can confirm, each embodiment compares with each comparative example, and purity of argon is high, and oxygen concn is lower than comparative example 2,3, carbon monoxide concentration lower than comparative example 1, hydrogen concentration lower than comparative example 1,3.
Claims (2)
1. the process for purification of argon gas, it is at least containing aerobic 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, by adding oxygen, be set the value into surpassing 1/2, then, use catalyzer to make oxygen and carbon monoxide and the H-H reaction in described argon gas, state with residual oxygen generates carbonic acid gas and water, then, by dehydration operation, reduce the moisture containing ratio in described argon gas, then, by being that sorbent material has been used the pressure swing adsorption process of carbonaceous molecular sieve at least to adsorb the oxygen and carbon dioxide in the impurity in described argon gas as carbon, afterwards, by the hot swing adsorption process at-10 ℃～-50 ℃, at least adsorb the nitrogen in the impurity in described argon gas.
2. the refining plant of argon gas, it is at least containing aerobic 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 being connected 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 the value into surpassing 1/2, this drying machine carries out dehydration operation minimizing from the moisture containing ratio of the described argon gas of described reactor outflow, to described reactor catalyst filling, in described reactor, make oxygen and carbon monoxide and H-H reaction in 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 by being that sorbent material has been used the pressure swing adsorption process of carbonaceous molecular sieve at least to adsorb oxygen and the carbonic acid gas in the impurity in described argon gas as carbon, this TSA unit at least adsorbs the nitrogen in the impurity in described argon gas by the hot swing adsorption process at-10 ℃～-50 ℃, and described PSA unit is connected by pressure regulator valve with described TSA unit.
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| KR (1) | KR101720799B1 (en) |
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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 |
| JP5743215B2 (en) * | 2011-12-13 | 2015-07-01 | 住友精化株式会社 | Helium gas purification method and purification apparatus |
| JP5896467B2 (en) * | 2012-08-09 | 2016-03-30 | 住友精化株式会社 | Argon 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 |
Citations (3)
| 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 |
| CN1346788A (en) * | 2001-09-14 | 2002-05-01 | 温州瑞气空分设备有限公司 | Process for purifying gas |
| JP3496079B2 (en) * | 1993-11-17 | 2004-02-09 | 日本酸素株式会社 | Method and apparatus for purifying argon gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60122709A (en) * | 1983-12-07 | 1985-07-01 | Hitachi Ltd | Method for recovering argon |
| JPH0624962B2 (en) * | 1985-11-15 | 1994-04-06 | 日本酸素株式会社 | Method for recovering high-purity argon from exhaust gas from a single crystal manufacturing furnace |
| 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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Patent Citations (3)
| 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 |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平7-138007A 1995.05.30 |
| JP特许第3496079B2 2003.11.28 |
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| TW201136654A (en) | 2011-11-01 |
| KR20110097648A (en) | 2011-08-31 |
| CN102190290A (en) | 2011-09-21 |
| KR101720799B1 (en) | 2017-03-28 |
| TWI478761B (en) | 2015-04-01 |
| JP2011195434A (en) | 2011-10-06 |
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