CN101185826B - Immobile gas processing method and refining method and gas processing bucket - Google Patents
Immobile gas processing method and refining method and gas processing bucket Download PDFInfo
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- CN101185826B CN101185826B CN2007101546770A CN200710154677A CN101185826B CN 101185826 B CN101185826 B CN 101185826B CN 2007101546770 A CN2007101546770 A CN 2007101546770A CN 200710154677 A CN200710154677 A CN 200710154677A CN 101185826 B CN101185826 B CN 101185826B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0094—Combined chemical and physical processing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0068—Organic compounds
- C01B2210/007—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0015—Chemical processing only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0052—Physical processing only by adsorption in solids
- C01B23/0084—Physical processing only by adsorption in solids in getters
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Abstract
The invention relates to a processing method and a refining method for an inactive gas, as well as a gas processing drum. The invention can eliminate the impurities from the inactive gas including hydro-impurities such as methane which is hard to be eliminated with high effect and high eliminating capability. The inactive gas including hydro-impurities is contacted with a processing agent including metallic nickel and/or nickel oxide under the condition of heating so as to eliminate the hydro-impurities from the inactive gas. Besides, the inactive gas is contacted with a gas-absorption material or an adsorbent so as to eliminate impure gases (hydrogen, CO2 and water) which are produced when the inactive gas is contacted with the processing agent and which are easy to be eliminated. Besides, the gas processing drum is filled in such a way of separating the processing agent including metallic nickel and/or nickel oxide with the gas-absorption material through gaps or idle filling materials.
Description
Technical field
The present invention relates to processing method and the process for purification and the gas treatment tube of inactive gas; More particularly; Relate to the inactive gas that contains the hydrocarbon impurities that is difficult to remove is contacted with the inorganic agent of nickel metal and/or nickel oxide under the condition of heating; Efficient processing method of easily removing difficult except that hydro carbons; The process for purification that the impurity of removing easily that is produced by above-mentioned processing is contacted with gettering material or adsorbent and remove, and the gas treatment tube that can implement these methods efficiently.
Background technology
In semi-conductor industry, rare gas such as helium, neon, argon gas, krypton gas are used by frequent, and these gases require to have high purity.These gases are the rare gas that only contains trace in the air, except from air, extracting, do not have other effective modulator approaches, and for example, argon gas, krypton gas can make through the fractionation of liquia air.But, have micro-methane in the air, because the boiling point of methane is-164 ℃; If from argon gas (boiling point :-186 ℃) or krypton gas (boiling point :-153 ℃), remove methane to extremely low concentration through fractionation; Then must repeat repeatedly rectifying separation, expense is very high, otherwise very difficult.
In addition; As the method for from the rare gas of modulation as stated, removing methane; Have rare gas contact with gettering materials such as zirconium or titaniums under the condition of heating and catch the method for removing, in rare gas, filling oxygen makes methyl hydride combustion change into carbon dioxide and water, it is contacted with synthetic zeolite adsorbs the method for removing carbon dioxide and water etc.
In addition, disclose in the japanese kokai publication hei 7-270067 communique and utilize boiling-point difference to separate each composition after making air cooling, liquefaction.Disclose in the japanese kokai publication hei 10-114508 communique and under extremely low temperature, removed nitrogen contained in the argon gas stream and methane.Disclose in the japanese kokai publication hei 2003-170018 communique and the hydrogen that contains methane has at high temperature been contacted with the gettering material that with the zirconium is main component remove methane.
Summary of the invention
But; Because the ability that the method that inactive gas such as rare gas is contacted with gettering material under the condition of heating is removed methane is (with respect to per unit gettering material; The amount of removing of methane) lower, and gettering material costs an arm and a leg, thereby operating cost is high and suitable.
In addition; The method that in inactive gas such as rare gas, fills oxygen must charge into excess of oxygen with respect to the content of methane, except being difficult to adjust the quantity delivered of oxygen; After methane conversion becomes carbon dioxide and water; Also must therewith remove superfluous oxygen, thereby the consumption of adsorbent etc. is very big, therefore suitable.
So; Problem to be solved by this invention is that inactive gas processing method, the process for purification of from the inactive gas such as rare gas that contain troublesome impurity methane (hydrocarbon) as stated, removing methane (hydrocarbon) and the gas treatment tube that can implement these methods efficiently are provided low-cost high-efficiency.
Present inventors have carried out particular study in order to address these problems; The result finds; Through make the inactive gas that contains hydrocarbon impurities such as methane under the condition of heating with metallic nickel and/or nickel oxide, hydro carbons (changing into the impurity of removing easily) can be efficiently easily removed in the above-mentioned nickel contact of preferred high-specific surface area; And the ability of removing is also very high, thereby has reached inactive gas processing method of the present invention and process for purification and gas treatment tube.
That is, the present invention is a kind of processing method of inactive gas, it is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent of nickel metal and/or nickel oxide, from this inactive gas, removes hydro carbons.
In addition, the present invention is a kind of process for purification of inactive gas, it is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent of nickel metal, and then it is contacted with gettering material.
In addition, the present invention is a kind of process for purification of inactive gas, it is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent that contains nickel oxide, and then it is contacted with adsorbent or gettering material.
In addition; The present invention still is a kind of gas treatment tube; It is characterized in that making inorganic agent and the gettering material of nickel metal and/or nickel oxide to isolate each other and fill, and the heater that is used to heat this inorganic agent and this gettering material is housed through gap or inert fill material.
The processing method of inactive gas of the present invention and process for purification; Owing to use more cheap and can expect to obtain good hydro carbons and remove ability (with respect to per unit inorganic agent than gettering material; The amount of removing of hydro carbons) metallic nickel, nickel oxide perhaps contain their Raney nickel as the inorganic agent raw material of removing the troublesome impurity hydro carbons, and operating cost is descended.And,, thereby can carry out removing of hydro carbons efficiently and handle and refinement treatment because apparatus structure is simple.
Description of drawings
Fig. 1 a, Fig. 1 b shows the structural map of an example of gas treatment tube of the present invention.
The specific embodiment
Inactive gas processing method of the present invention and process for purification and gas treatment tube are applicable to from inactive gas such as the nitrogen that contains hydrocarbon impurities such as methane at least, helium, neon, argon gas, krypton gas, xenon or are selected from processing method, process for purification and the gas treatment tube of removing hydro carbons the two or more mists of these inactive gas at least.Hydro carbons such as methane contained in the inactive gas are generally below the 200ppm.And, in the inactive gas, can also contain impurity such as hydrogen, oxygen, carbon monoxide, carbon dioxide, water with hydro carbons.
As long as the inorganic agent that uses in processing method of the present invention, process for purification and the gas process cartridge contains metallic nickel and/or nickel oxide; For example, the nickel compound that can enumerate easy oxidized reduction such as the hydroxide that makes with Raney nickel, nickel, carbonate, nitrate, acylate is the raw material oxidation of main component or the inorganic agent of reduction gained.In addition, the metal ingredient as beyond the nickel can also contain metals such as a spot of chromium, iron, cobalt, copper.These raw materials can use separately, and, also can use, but from improving the purpose equal angles of nickel surface and the contacting efficiency of gas, usually to load on its load form use on the catalyst carrier etc. with its load form that loads on the catalyst carrier etc.
As the method that makes Ni on carrier; For example, can enumerate support powders such as making diatomite, alumina, sial, alumina silicate or calcium silicates and be dispersed in the aqueous solution of nickel salt, add alkali again the nickel composition is deposited on the support powder; Filter and use as required water washing then; The gained filter cake after 80～150 ℃ of following dryings, is cured under the temperature more than 300 ℃ again, then this is cured the method that thing is pulverized; Perhaps with NiCO
3, Ni (OH)
2, Ni (NO
3)
2Deng inorganic salts, NiC
2O
4, Ni (CH
3COO)
2After curing and pulverize Deng organic salt, the method that makes itself and hear resistance cementing agent mix and cure.
It normally processes formed body through extrusion modling, compression molding etc., and it is directly used or is ground into suitable size as required and uses.As forming method, can adopt dry method or wet method.At this moment, can also use a spot of water, lubricant etc.
In addition, as nickel class catalyst, for example N-111 (Ni-diatomite) (day wave (strain) produce) waits on salely on market, therefore also can therefrom select use.In a word, so long as reduced nickel, nickel oxide etc. are disperseed imperceptibly, its surface area is increased, thereby itself and the high form of gas contacting efficiency are got final product.
The BET specific area of inorganic agent is generally 10～300m
2/ g is preferably 30～250m
2/ g.In addition, with respect to whole inorganic agents, the content ratio of metallic nickel and nickel oxide is generally 5～95wt%, is preferably 20～95wt%.If the content of nickel is lower than 5wt%, then the ability of removing of hydro carbons is very low, in addition, if be higher than 95wt%, sintering takes place when then existing by hydrogen reduction, thereby makes the active possibility that descends.
When the inactive gas processing method of embodiment of the present invention, inorganic agent raw materials such as the inorganic agent of above-mentioned nickel metal and/or nickel oxide or Raney nickel, nickel compound are filled in the process cartridge.These inorganic agents of filling in the process cartridge or the filling length of inorganic agent raw material are generally 10～2000mm in practical application.If fill and be shorter in length than 10mm, then there is the possibility of the rate of the removing decline of hydrocarbon impurities, in addition, if be longer than 2000mm, the excessive possibility of the pressure loss can appear then.
During nickel compound beyond the inorganic agent raw material of filling in the process cartridge contains nickel metal or nickel oxide; Removing before the processing of hydro carbons; Usually to carry out by the processing of hydrogen reducing, by the processing of dioxygen oxidation, perhaps under the condition of heating, feeding the activation processing of inactive gas, make it be converted into inorganic agent.When carrying out these processing; For example; Can be through under the temperature below 350 ℃, with 0.1～200cm/ about second, the empty tube linear velocity (LV) of preferred 1～50cm/ second in process cartridge, feed hydrogen and nitrogen mist, oxygen and nitrogen mist or nitrogen and carry out.
In the present invention, process object gas is generally 200～800 ℃ with the temperature that contacts of inorganic agent, is preferably 300～600 ℃.If above-mentioned contact temperature is more than 200 ℃, then can make the hydro carbons in the process object gas be converted into hydrogen, carbon dioxide, water etc. efficiently, if below 800 ℃, then can not produce excessive load to process cartridge.
Pressure when gas is contacted with inorganic agent also has no particular limits, and can be any processing of normal pressure, decompression, pressurization, carries out but depress in normal pressure to adding of 1.0MPa usually.The empty tube linear velocity (LV) of gas is according to the concentration of hydro carbons in the gas supplied and operating condition etc. and different during processing, can not carry out specificly entirely, but is generally 100cm/ below second, is preferably 30cm/ below second.
In processing method of the present invention, contact with metallic nickel under the condition of heating through making the inactive gas that for example contains methane, make it catch the carbon in the methane, and generation hydrogen remove from downstream row.At this moment, according to the difference of treatment conditions, the situation that generates micro CO, carbon dioxide and remove from downstream row can appear also.In addition, contact with nickel oxide under the condition of heating through making the inactive gas that for example contains methane, generation carbon dioxide and water also remove from downstream row.But, processing method of the present invention, for example, even can be used as to existing small quantity of hydrogen also can not produce the carrier gas supply method that dysgenic reaction system is supplied with.
Inactive gas process for purification of the present invention; Through the inactive gas that contains hydrogen, carbon dioxide, water etc. by above-mentioned inactive gas disposal methods is further contacted with gettering material and/or adsorbent, can remove hydrogen, carbon dioxide, water etc.Through inactive gas is as above handled, can improve the ability of removing of per unit weight gettering material, and prolonged the service life of gettering material.In addition, in the system of using adsorbent,, can make the hydrocarbon conversion in the inactive gas become carbon dioxide and water, it can be removed through adsorbent through inactive gas is as above handled.
In addition, the inactive gas before handling, except that methane etc. the hydro carbons, even also contain foreign gases such as hydrogen, oxygen, carbon monoxide, carbon dioxide, water, these gases also can be removed at an easy rate.
When the inactive gas process for purification of embodiment of the present invention; Can be with above-mentioned metallic nickel, nickel oxide, Raney nickel or nickel compound; In process cartridge, jointly fill gettering material as its downstream; In addition, also can refining tube that be filled with gettering material and/or the absorbing cylinder that is filled with adsorbent be set in the downstream of process cartridge.In addition, as gettering material, can enumerate for example zirconium, vanadium and iron, titanium etc.In addition, as adsorbent, can enumerate zeolite, active carbon etc.Carry out inactive gas refining before, also can be through carrying out activation processing to gettering material and adsorbent feeding inactive gas under the condition of heating or under the condition of heating, vacuumize.
In the process for purification of inactive gas of the present invention; When making it under the condition of heating, the inactive gas that will contain hydrocarbon impurities contacts with metallic nickel when removing hydro carbons; Because producing hydrogen as stated removes from downstream row, thereby preferably is provided for removing the gettering material of hydrogen.In addition, contact with nickel oxide when removing hydro carbons,, thereby preferably be provided for removing the adsorbent or the gettering material of carbon dioxide and water owing to generation carbon dioxide and water remove from downstream row when the inactive gas that will contain hydrocarbon impurities makes it under the condition of heating.
The filling length of the adsorbent of filling in the filling length of the gettering material of filling in the refining tube and the absorbing cylinder is generally 10～2000mm in practical application.In addition, refining object gas is generally 200～800 ℃ with the temperature that contacts of gettering material, is preferably 300～600 ℃, and refining object gas is generally 0～100 ℃ with the temperature that contacts of adsorbent, is preferably 10～50 ℃.In addition, pressure also being had no particular limits, can be normal pressure, decompression, any refinement treatment of pressurization, adsorption treatment, carries out but depress in normal pressure to adding of 1.0MPa usually.
In addition; The ability of removing when inactive gas being contacted with gettering material remove hydrogen impurity under the condition of heating; Because it is high in the extreme that the ability of removing when removing hydro carbons such as methane is compared, thereby the present invention makes the inorganic agent of nickel metal and the process for purification that gettering material makes up worry can improve operating cost.In addition; After making inactive gas contact the carbon dioxide of removing as impurity and water with zeolite at normal temperatures, in the heating zeolite, feed regeneration gas, make carbon dioxide and water take off absorption; Can make zeolite regeneration; Therefore, the present invention makes the process for purification of the inorganic agent that contains nickel oxide and adsorbent combination, needn't worry to improve operating cost.
Gas treatment tube of the present invention is the gas treatment equipment that can implement said method efficiently; Shown in the structure legend of Fig. 1 a and Fig. 1 b; The nickel metal of process cartridge (refining tube) and/or the inorganic agent of nickel oxide 1 are isolated each other through gap 3 or inert fill material 4 with gettering material 2 and are filled, and are equipped with and are used for heater 5 that inorganic agent and gettering material are heated.The filling ratio of inorganic agent and gettering material, in weight ratio, be generally 1: 2～1000, be preferably 1: 3～100.In addition, as inert fill material, can use pottery system packing materials such as alumina, silica, sial, magnesia usually.In addition, the filling length of the gap of inorganic agent and gettering material or inert fill material is generally 2～1000mm, is preferably 5～500mm.In addition, Fig. 1 a, 6 among Fig. 1 b representes temperature sensor.When above-mentioned gap or filling curtailment 2mm, inorganic agent will contact with gettering material, exists to make gettering material remove the possibility of ability drop, when surpassing 1000mm, will cause the gas treatment tube to become suitable very greatly and not.
The shape of gas treatment tube of the present invention is generally cylindrical shape, and its size internal diameter usually is 10～500mm, and length is 20～2500mm.The inorganic agent of filling in the gas treatment tube and the total of gettering material are filled length, are generally 10～2000mm, are preferably 50～1000mm.In addition,, can enumerate for example carbon steel, manganese steel, chromium steel, molybdenum steel, stainless steel, nickel steel etc. as the material that constitutes the gas treatment tube, wherein, stainless steels such as preferred SUS316, SUS316L.
Below, through embodiment the present invention is explained more specifically, but the present invention is not limited to these embodiment.
[embodiment 1]
(modulation of inorganic agent)
With adopting commercially available Raney nickel (to contain metallic nickel and nickel oxide, Ni:45～47wt%, Cr:2～3wt%, Cu:2～3wt%, diatomite: 27～29wt%, graphite: 4～5wt%, specific area: 150m
2/ g, the formed body of diameter 5mm, high 4.5mm) is used as the raw material of inorganic agent.This Raney nickel is to make it can be processed into the stabilisation Raney nickel of non-ignitable state in air carrying out mild oxidation after the reduction.To be filled in internal diameter be that 23mm, length are that filling length is 200mm in the stainless steel process cartridge of 1000mm with being crushed to this Raney nickel of 8～10 purposes.The heater of this process cartridge is heated, make the temperature of catalyst (inorganic agent) reach 420 ℃, simultaneously, feed hydrogen, carry out reducing in 3 hours after the processing, be cooled to normal temperature with 2500ml/ minute flow.
(methane remove processing)
Then, after the heater of process cartridge heated, feed the argon gas that contains the 150ppm methane impurities, carry out the processing of removing of methane with 3300ml/ minute flow.In addition, in removing processing procedure, argon gas contacts temperature maintenance at about 420 ℃ with inorganic agent.During this period, the part of the gas got rid of from process cartridge is taken a sample, whether be removed through gas Chromatographic Determination methane; The result; Even in through 1000 hours, also can remove methane, it removes ability (amount of removing of every 1g inorganic agent methane) for more than the 358cc/g agent.
[embodiment 2]
(modulation of inorganic agent)
To be crushed to 8～10 orders with embodiment 1 same commercially available stabilisation Raney nickel, and likewise be filled in the process cartridge with embodiment 1, making and filling length is 200mm.The heater of this process cartridge is heated; Make the temperature of inorganic agent reach 420 ℃, simultaneously, with 3300ml/ minute the flow aerating oxygen and the mist of argon gas; A little increases concentration of oxygen; Make its by originally 20% increase to 100% when finishing concentration, carry out 8 hours oxidation processes after, be cooled to normal temperature.
(methane remove processing)
Then, after the heater of process cartridge heated, feed the argon gas that contains the 150ppm methane impurities, carry out the processing of removing of methane with 3300ml/ minute flow.In addition, in removing processing procedure, argon gas contacts temperature maintenance at about 420 ℃ with inorganic agent.During this period, the part of the gas got rid of from process cartridge is taken a sample, whether be removed through gas Chromatographic Determination methane; The result; Even in through 1000 hours, also can remove methane, it removes ability (amount of removing of every 1g inorganic agent methane) for more than the 358cc/g agent.
[comparative example 1]
(modulation of gettering material)
Adopt zirconium cavernous body and block vanadium (purity is more than 95%), after mixing with zirconium 70wt%, vanadium 30wt%, in high-frequency induction furnace, carry out melting, obtain the alloy of about 5kg.This alloy is pulverized with the ball mill under the ar gas environment, and screening 14～20 purposes are as gettering material.It is filled in internal diameter is that 23mm, length are that filling length is 220mm in the refining tube of stainless steel of 1000mm.Heater of this refining tube is heated, makes the temperature of gettering material reach 500 ℃, simultaneously, feed argon gas with 3300ml/ minute flow, carry out 6 hours activation processing after, normal temperature is put in cooling.
(methane remove processing)
Then, after the heater of refining tube heated, feed the argon gas that contains the 150ppm methane impurities, carry out the processing of removing of methane with 3300ml/ minute flow.In addition, in removing processing procedure, argon gas contacts temperature maintenance at about 420 ℃ with gettering material.During this period, to taking a sample, whether be removed through gas Chromatographic Determination methane from the part of the refining gas of getting rid of; The result; After 160 hours, just can not remove methane again, it is removed ability (amount of removing of every 1g gettering material methane) and is the 14.8cc/g material.
In addition, will contain the argon gas of 260ppm hydrogen impurity, and likewise feed in the refining tube with above-mentioned, and likewise carry out the processing of removing of hydrogen, result, the ability of removing of hydrogen are the 85cc/g material.
[comparative example 2]
Removing in the processing of the methane of embodiment 1, except make contain methane impurities argon gas under the temperature of normal temperature (about 25 ℃) with inorganic agent (handling through reduction) contacts, likewise carry out the processing of removing of methane with embodiment 1.Consequently, the ability of removing of inorganic agent (amount of removing of every 1g inorganic agent methane) is for below the 1cc/g agent.
[comparative example 3]
Removing in the processing of the methane of embodiment 2, except make the argon gas that contains methane impurities under the temperature of normal temperature (about 25 ℃) with inorganic agent (through oxidation processes) contacts, likewise carry out the processing of removing of methane with embodiment 2.Consequently, the ability of removing of inorganic agent (amount of removing of every 1g inorganic agent methane) is for below the 1cc/g agent.
(making of gas treatment tube)
At internal diameter is that 37.1mm, length are the upper reaches of process cartridge of the stainless steel (SUS316L) of 1000mm, fills the commercially available stabilisation Raney nickel after likewise pulverizing with embodiment 1, and filling length is 100mm.And fill and the comparative example 1 same gettering material of modulating in downstream in the gap of 20mm at interval, and filling length is 220mm, produces the gas treatment tube shown in Fig. 1 a.
The heater of this gas treatment tube is heated, makes the temperature of inorganic agent reach 500 ℃, simultaneously, feed argon gas from downstream with 8400ml/ minute flow, carry out 6 hours activation processing after, be cooled to normal temperature.
(refinement treatment of argon gas)
After then making the heater of gas treatment tube be heated to about 420 ℃; Flow from the porch (upper reaches) of gas treatment tube with 8400ml/ minute feeds the argon gas that contains hydrogen, oxygen, carbon monoxide, carbon dioxide, each 10ppm of water and methane 50ppm as impurity, carries out the refinement treatment of argon gas.During this period; Part to the gas got rid of from the gas treatment tube is taken a sample; Measure contained impurity (hydrogen, oxygen, carbon monoxide, carbon dioxide, water) in the argon gas through atmospheric pressure mass-synchrometer (API-MS), after long-time (500 hours), can not detect these impurity.In addition, the argon gas made from extra care recycles it after adding impurity once more.
[embodiment 4]
(making of gas treatment equipment)
With 5 <img commercially available file=" 2007101546770_0.GIF " he=" 64 " img-content=" drawing " img-format=" tif " inline=" no " orientation=" portrait " wi=" 64 " />to be filled in internal diameter be that 37.1mm, length are in the stainless steel absorbing cylinder of 800mm to suitable synthetic zeolite (adsorbent), making and filling length is 100mm.Then; Will with the same process cartridge of making (wherein, internal diameter is 37.1mm, and fillings length is 100mm) (upper reaches) of embodiment 1 and 2 tubes of this absorbing cylinder (downstream); Coupling together, and make each can carry out oxidation processes, activation processing respectively with absorbing cylinder mode arranged side by side.In process cartridge, likewise carry out the oxidation processes of inorganic agent with embodiment 2, in absorbing cylinder, the temperature of adsorbent is heated to 350 ℃, simultaneously, feed argon gas with 8400ml/ minute flow, carry out 8 hours activation processing, then each is cooled to room temperature.
(refinement treatment of argon gas)
After making the heater of process cartridge be heated to about 420 ℃; The argon gas that will contain hydrogen, oxygen, carbon monoxide, carbon dioxide, each 10ppm of water and methane 50ppm as impurity; With 8400ml/ minute the flow feeding process cartridge and the absorbing cylinder of one of which side, carry out the refinement treatment of argon gas.During this period; Part to the gas got rid of from absorbing cylinder is taken a sample; Measure contained impurity (hydrogen, oxygen, carbon monoxide, carbon dioxide, water, methane) in the argon gas through atmospheric pressure mass-synchrometer (API-MS), after 20 hours, can not detect these impurity.
Then, absorbing cylinder is switched to opposite side, proceed the refinement treatment of argon gas, simultaneously, the adsorbent of used absorbing cylinder is regenerated through activation, after 20 hours, once more absorbing cylinder is switched.Through carrying out this operation repeatedly, carry out the refinement treatment of argon gas, after long-time (500 hours), can not detect impurity (hydrogen, oxygen, carbon monoxide, carbon dioxide, water, methane).In addition, the argon gas made from extra care recycles it after adding impurity once more.
[embodiment 5]
In the argon gas refinement treatment of embodiment 3,4; Except use contain hydrogen, oxygen, carbon monoxide, carbon dioxide, each 10ppm of water and methane 50ppm nitrogen, helium, the inactive gas of neon as the refinement treatment object, likewise carry out refinement treatment with embodiment 3,4.Consequently, any one occasion all can not detect impurity after long-time (500 hours).
Know that by above the processing method of the embodiment of the invention, process for purification and gas treatment equipment can efficiently easily be removed the methane impurities that is difficult to remove contained in the inactive gas with the good ability of removing.
Claims (6)
1. the processing method of an inactive gas; It is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent of nickel metal and/or nickel oxide; From this inactive gas, remove hydro carbons; Wherein with respect to whole inorganic agents, the content ratio of metallic nickel and nickel oxide is 5～95wt%.
2. the processing method of the described inactive gas of claim 1, wherein the BET specific area of inorganic agent is 10～300m
2/ g.
3. the processing method of the described inactive gas of claim 1, wherein hydro carbons is a methane.
4. the processing method of the described inactive gas of claim 1, wherein inactive gas is 200～800 ℃ with the temperature that contacts of inorganic agent.
5. the process for purification of an inactive gas; It is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent of nickel metal; And then it is contacted with gettering material, wherein with respect to whole inorganic agents, the content ratio of metallic nickel is 5-95wt%.
6. the process for purification of an inactive gas; It is characterized in that making the inactive gas of hydrocarbon-containifirst impurity under the condition of heating, to contact with the inorganic agent that contains nickel oxide; And then it is contacted with adsorbent or gettering material; Wherein with respect to whole inorganic agents, the content ratio of nickel oxide is 5-95wt%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006273980A JP5002230B2 (en) | 2006-10-05 | 2006-10-05 | Inert gas purification method |
| JP2006-273980 | 2006-10-05 | ||
| JP2006273980 | 2006-10-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101185826A CN101185826A (en) | 2008-05-28 |
| CN101185826B true CN101185826B (en) | 2012-07-04 |
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| CN2007101546770A Expired - Fee Related CN101185826B (en) | 2006-10-05 | 2007-09-21 | Immobile gas processing method and refining method and gas processing bucket |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5002230B2 (en) |
| KR (1) | KR20080031780A (en) |
| CN (1) | CN101185826B (en) |
| TW (1) | TWI409216B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2199269A1 (en) | 2008-12-22 | 2010-06-23 | Total Petrochemicals Research Feluy | Method to purify olefin-containing hydrocarbon feedstocks |
| AU2010299162B2 (en) * | 2009-09-25 | 2015-04-09 | Osaka Gas Co., Ltd. | Method and Apparatus for Removing Low-Concentration Methane. |
| CN102302923A (en) * | 2011-05-03 | 2012-01-04 | 南京华东电子真空材料有限公司 | Combined getter |
| ITMI20120676A1 (en) * | 2012-04-24 | 2013-10-25 | Getters Spa | METHOD AND REGENERABLE PURIFICATION OF AMBIENT TEMPERATURE PURIFICATION FOR DIAZOTO MONOXIDE |
| JP2017094293A (en) * | 2015-11-26 | 2017-06-01 | 日本パイオニクス株式会社 | Electrical unit |
| CN108187613A (en) * | 2017-12-20 | 2018-06-22 | 北京汇能兴业科技有限公司 | One kind is suitable for the regenerated Adsorption of Organic agent of high-temperature S removal |
| CN111422839A (en) * | 2020-04-24 | 2020-07-17 | 苏州星烁纳米科技有限公司 | Inert gas treatment device and manufacturing method |
| CN111905803B (en) * | 2020-08-24 | 2023-01-17 | 大连华邦化学有限公司 | Inert gas purification catalyst, raw material composition and preparation method |
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- 2007-09-04 KR KR1020070089352A patent/KR20080031780A/en not_active Application Discontinuation
- 2007-09-21 CN CN2007101546770A patent/CN101185826B/en not_active Expired - Fee Related
- 2007-10-03 TW TW096137046A patent/TWI409216B/en active
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| US5194233A (en) * | 1990-09-14 | 1993-03-16 | Japan Pionics Co., Ltd. | Process for purification of rare gas |
| CN1033443C (en) * | 1993-04-29 | 1996-12-04 | 工程吸气公司 | Improved process for the removal of gaseous impurities from a stream of hydrogen |
| CN1181991A (en) * | 1996-07-22 | 1998-05-20 | 液体空气乔治洛德方法利用和研究有限公司 | O2/CO removal from inert gas by adsorption on porous metal oxide |
| CN1190262C (en) * | 2001-12-30 | 2005-02-23 | 武汉钢铁集团氧气有限责任公司 | Material for removing impurity in inert gas and its use method |
| CN1498851A (en) * | 2002-11-01 | 2004-05-26 | 日本派欧尼株式会社 | Refining method of inert gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008088043A (en) | 2008-04-17 |
| JP5002230B2 (en) | 2012-08-15 |
| TWI409216B (en) | 2013-09-21 |
| TW200829507A (en) | 2008-07-16 |
| KR20080031780A (en) | 2008-04-11 |
| CN101185826A (en) | 2008-05-28 |
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