CN115432678B - Preparation method of high-purity argon - Google Patents
Preparation method of high-purity argon Download PDFInfo
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- CN115432678B CN115432678B CN202110427575.1A CN202110427575A CN115432678B CN 115432678 B CN115432678 B CN 115432678B CN 202110427575 A CN202110427575 A CN 202110427575A CN 115432678 B CN115432678 B CN 115432678B
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052786 argon Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 16
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 11
- 238000005070 sampling Methods 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
- C01B2210/0004—Chemical processing by oxidation
-
- 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
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/0017—Carbon-based materials
-
- 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
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/002—Other molecular sieve materials
-
- 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
- C01B2210/0029—Obtaining noble gases
- C01B2210/0034—Argon
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of high-purity argon, which relates to the technical field of gas purification and comprises the steps of filling M-CuCoFeO with argon 4 /Al 2 O 3 Oxygen carrierThe argon discharged after reaction is adsorbed on an adsorbent through a pressure swing adsorption method, and the purified argon is collected, wherein M is Ag or Pd, the adsorbent is formed by mixing LiX type zeolite molecular sieves and 3A type carbon molecular sieves, the purity of the argon treated by the method is more than or equal to 99.9999%, the recovery rate of the argon is more than or equal to 91%, and the method has wide application prospect.
Description
Technical Field
The invention relates to the technical field of gas purification, in particular to a preparation method of high-purity argon.
Background
In the production and preparation process of monocrystalline silicon, at present, a pure argon atmosphere crystal pulling process is mostly adopted. Argon is an inert gas that surrounds the liquid levels of monocrystalline and polycrystalline silicon as a shielding gas to protect the monocrystalline and polycrystalline silicon from oxidation. In addition, because argon flows in the single crystal furnace, the argon can also volatilize matters, and can prevent the single crystal silicon or polysilicon liquid from being polluted, thereby affecting the product quality of the single crystal silicon. In addition, the argon gas forms uniform laminar flow from top to bottom to sweep the surface of the crystal, so that the latent heat of crystallization can be taken away, and the normal growth of monocrystalline silicon can be ensured.
However, the purity of the argon required by the production of the monocrystalline silicon is required to reach 99.999 percent, the consumption is large, and the argon can be subjected to CO and H after one-time production process of the monocrystalline silicon 2 And the like, and the purity is reduced and the gas cannot be reused. The high-purity argon is disposable in the production process of monocrystalline silicon, and the production cost is inevitably increased. If can be CO, H 2 And the argon polluted by the impurity gas is purified, so that the high-purity argon is obtained again, the production cost can be reduced, and the industry development is promoted.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of high-purity argon.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of high-purity argon gas comprises the following steps:
argon is filled with M-CuCoFeO 4 /Al 2 O 3 And (3) an oxygen carrier fixed bed reactor, wherein the carbon dioxide and water in the argon discharged after the reaction are adsorbed on an adsorbent by a pressure swing adsorption method, and the purified argon is collected, wherein M is Ag or Pd, and the adsorbent is formed by mixing a LiX type zeolite molecular sieve and a 3A type carbon molecular sieve.
The pressure swing adsorption method may be a known method.
Further, M is Pd.
Further, the temperature of the fixed bed reactor is 150-200 ℃.
Further, the mass ratio of the LiX type zeolite molecular sieve to the 3A type carbon molecular sieve is 1-5:1-5.
Further, the M-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
s1: adding inorganic copper salt, inorganic cobalt salt and inorganic ferric salt into water, stirring and mixing uniformly to obtain uniform solution, adding polyethylene glycol, citric acid and porous Al 2 O 3 Stirring and heating to 80-95 ℃, and reacting for 10-15h to obtain gel;
s2: drying the gel at 100-120deg.C for 10-15h;
s3: calcining for 2-5h at 300-500 ℃ again, calcining for 2-5h at 700-900 ℃ again, cooling, grinding and sieving to obtain a precursor;
s4: dispersing the precursor in methanol aqueous solution containing palladium acetate or silver nitrate, carrying out ultrasonic treatment for 20-30min, filtering, placing under a high-pressure mercury lamp for irradiation for 10-20h, washing with water, and drying.
Further, the inorganic copper salt is any one of copper nitrate, copper sulfate and copper chloride;
the inorganic cobalt salt is any one of cobalt nitrate, cobalt sulfate and cobalt chloride;
the inorganic ferric salt is any one of ferric nitrate, ferric sulfate and ferric chloride.
Further, the amounts of the substances of the inorganic copper salt, the inorganic cobalt salt and the inorganic iron salt are the same.
Further, the ratio of the sum of the amounts of the substances of the inorganic copper salt, inorganic cobalt salt, inorganic iron salt to the amount of the substance of the citric acid is 1:1-1.2.
Further, the speed of primary temperature rise in the step S3 is 10-15 ℃/min, and the speed of secondary temperature rise is 3-5 ℃/min.
Further, the mass concentration of the aqueous methanol solution in S4 is 1-5%.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of high-purity argon, which can lead single crystal silicon to be subjected to CO and H 2 The purity of the argon polluted by the impurity gas is more than or equal to 99.9999%, the high-efficiency low-cost recovery, purification and circulation of the argon in the monocrystalline silicon production are realized, and compared with the single-use pressure swing adsorption method, the separation effect is better, the argon recovery rate is higher, and the Pd-CuCoFeO in the invention 4 /Al 2 O 3 Oxygen carrier at CO, H 2 Oxygen required by combustion can be provided during combustion of the impurity gas, no additional oxygen is needed, and oxygen pollution caused by insufficient combustion is avoided 4 The oxygen migration energy barrier is low, the oxygen vacancy formation energy is low, the reaction can be carried out at low temperature, the reduction depth is high, and the addition of palladium atoms can further improve the CuCoFeO 4 Improving CO and H oxygen supply activity 2 Reaction rate of the impurity gas, al 2 O 3 Al while improving oxygen carrier activity by utilizing synergistic effect of bimetal 3+ The stability of the oxygen carrier is also improved by adding the method, the purity of the argon treated by the method is more than or equal to 99.9999 percent, the recovery rate of the argon is more than or equal to 91 percent, and the method has wide application prospect.
Drawings
FIG. 1 shows the Pd-CuCoFeO prepared in example 1 of the present invention 4 /Al 2 O 3 From the SEM image of the oxygen carrier, FIG. 1 shows Pd-CuCoFeO 4 /Al 2 O 3 The surface particles of the oxygen carrier are orderly arranged, and are loose and porous.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention.
Example 1:
a preparation method of high-purity argon gas comprises the following steps:
argon (0.01% H) 2 +0.01% CO+99.99% argon) at a flow rate of 12L/min through a Pd-CuCoFeO charge 4 /Al 2 O 3 The oxygen carrier temperature is 150 ℃ in a fixed bed reactor, and the discharged argon after reaction is subjected to pressure swing adsorption to enable carbon dioxide and water in the fixed bed reactor to be adsorbed on LiX type zeolite molecular sieves and 3A type carbon molecular sieves according to the mass ratio of 1:1, collecting purified argon, sampling for gas content detection, wherein the purity of the argon is more than or equal to 99.9999%, and the recovery rate of the argon is 91.38%.
Wherein Pd-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amount of substances into water, stirring and mixing uniformly to obtain a uniform solution, and adding polyethylene glycol, citric acid and porous Al 2 O 3 Wherein the amount of the citric acid is 1.2 times of the sum of the amounts of the copper nitrate, the cobalt nitrate and the ferric nitrate, stirring and heating to 80 ℃, reacting for 12 hours to obtain gel, drying the gel at 120 ℃ for 10 hours, heating to 300 ℃ for calcination for 4 hours at a speed of 15 ℃/min, heating to 900 ℃ for 5 hours at a speed of 3 ℃/min, cooling, grinding and screening to obtain a precursor, adding palladium acetate into a methanol aqueous solution with the mass of 10 times of the palladium acetate, wherein the mass concentration of the methanol aqueous solution is 5%, dispersing the precursor in the methanol aqueous solution, carrying out ultrasonic treatment for 30 minutes, filtering, irradiating for 15 hours under a high-pressure mercury lamp, washing with water, and drying.
Example 2:
a preparation method of high-purity argon gas comprises the following steps:
argon (0.01% H) 2 +0.01% CO+99.99% argon) at a flow rate of 10L/min through a Pd-CuCoFeO charge 4 /Al 2 O 3 Fixed bed reactor with oxygen carrier temperature of 150 ℃ and after reactionThe carbon dioxide and water in the argon discharged later are adsorbed on a LiX zeolite molecular sieve and a 3A carbon molecular sieve according to the mass ratio of 1:1, collecting purified argon, sampling for gas content detection, wherein the purity of the argon is more than or equal to 99.9999%, and the recovery rate of the argon is 91.20%.
Wherein Pd-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amount of substances into water, stirring and mixing uniformly to obtain a uniform solution, and adding polyethylene glycol, citric acid and porous Al 2 O 3 Wherein the amount of the citric acid is 1.1 times of the sum of the amounts of the copper nitrate, the cobalt nitrate and the ferric nitrate, stirring and heating to 80 ℃, reacting for 10 hours to obtain gel, drying the gel at 100 ℃ for 10 hours, heating to 300 ℃ for calcining for 2 hours at the speed of 10 ℃/min, heating to 700 ℃ for 2 hours at the speed of 3 ℃/min, cooling, grinding and screening to obtain a precursor, adding palladium acetate into a methanol aqueous solution with the mass concentration of 1% which is 5 times that of the palladium acetate, dispersing the precursor in the methanol aqueous solution, carrying out ultrasonic treatment for 20 minutes, filtering, radiating for 10 hours under a high-pressure mercury lamp, washing with water, and drying.
Example 3:
a preparation method of high-purity argon gas comprises the following steps:
argon (0.01% H) 2 +0.01% CO+99.99% argon) at a flow rate of 15L/min by being charged with Pd-CuCoFeO 4 /Al 2 O 3 The oxygen carrier temperature is 150 ℃ in a fixed bed reactor, and the discharged argon after reaction is subjected to pressure swing adsorption to enable carbon dioxide and water in the fixed bed reactor to be adsorbed on LiX type zeolite molecular sieves and 3A type carbon molecular sieves according to the mass ratio of 1:1, collecting purified argon, sampling for gas content detection, wherein the purity of the argon is more than or equal to 99.9999%, and the recovery rate of the argon is 91.33%.
Wherein Pd-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
copper nitrate, cobalt nitrate and ferric nitrate are added in the same amountAdding into water, stirring to obtain uniform solution, adding polyethylene glycol, citric acid, and porous Al 2 O 3 Wherein the amount of the citric acid is 1.2 times of the sum of the amounts of the copper nitrate, the cobalt nitrate and the ferric nitrate, stirring and heating to 95 ℃, reacting for 15 hours to obtain gel, drying the gel at 120 ℃ for 15 hours, heating to 500 ℃ for calcination for 5 hours at a speed of 15 ℃/min, heating to 900 ℃ for 5 hours at a speed of 5 ℃/min, cooling, grinding and screening to obtain a precursor, adding palladium acetate into a methanol aqueous solution with the mass concentration of 5% which is 10 times that of the palladium acetate, dispersing the precursor in the methanol aqueous solution, performing ultrasonic treatment for 30 minutes, filtering, irradiating for 20 hours under a high-pressure mercury lamp, washing with water, and drying.
Example 4:
a preparation method of high-purity argon gas comprises the following steps:
argon (0.01% H) 2 +0.01% CO+99.99% argon) at a flow rate of 10L/min through a Pd-CuCoFeO charge 4 /Al 2 O 3 The oxygen carrier temperature is 200 ℃ in a fixed bed reactor, and the discharged argon after reaction is subjected to pressure swing adsorption to enable carbon dioxide and water in the fixed bed reactor to be adsorbed on LiX type zeolite molecular sieves and 3A type carbon molecular sieves according to the mass ratio of 1:1, collecting purified argon, sampling for gas content detection, wherein the purity of the argon is more than or equal to 99.9999%, and the recovery rate of the argon is 91.09%.
Wherein Pd-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amount of substances into water, stirring and mixing uniformly to obtain a uniform solution, and adding polyethylene glycol, citric acid and porous Al 2 O 3 Wherein the amount of citric acid is 1 times of the sum of the amounts of copper nitrate, cobalt nitrate and ferric nitrate, stirring and heating to 95 ℃, reacting for 10 hours to obtain gel, drying the gel at 120 ℃ for 10 hours, heating to 300 ℃ at a speed of 15 ℃/min for calcining for 5 hours, heating to 900 ℃ at a speed of 3 ℃/min for calcining for 2 hours, cooling, grinding and sieving to obtain a precursor, and adding palladium acetate to 10 times of the precursorAnd (3) dispersing the precursor in the methanol aqueous solution with the mass concentration of 1%, carrying out ultrasonic treatment for 30min, filtering, placing under a high-pressure mercury lamp for irradiation for 10h, washing with water, and drying.
Example 5:
a preparation method of high-purity argon gas comprises the following steps:
argon (0.01% H) 2 +0.01% CO+99.99% argon) at a flow rate of 15L/min by being charged with Pd-CuCoFeO 4 /Al 2 O 3 The oxygen carrier temperature is 200 ℃ in a fixed bed reactor, and the discharged argon after reaction is subjected to pressure swing adsorption to enable carbon dioxide and water in the fixed bed reactor to be adsorbed on LiX type zeolite molecular sieves and 3A type carbon molecular sieves according to the mass ratio of 1:1, collecting purified argon, sampling for gas content detection, wherein the purity of the argon is more than or equal to 99.9999%, and the recovery rate of the argon is 91.15%.
Wherein Pd-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amount of substances into water, stirring and mixing uniformly to obtain a uniform solution, and adding polyethylene glycol, citric acid and porous Al 2 O 3 Wherein the amount of the citric acid is 1.2 times of the sum of the amounts of the copper nitrate, the cobalt nitrate and the ferric nitrate, stirring and heating to 80 ℃, reacting for 15 hours to obtain gel, drying the gel at 100 ℃ for 15 hours, heating to 500 ℃ for calcining for 2 hours at a speed of 10 ℃/min, heating to 700 ℃ for 5 hours at a speed of 5 ℃/min, cooling, grinding and screening to obtain a precursor, adding palladium acetate into a methanol aqueous solution with the mass concentration of 5% which is 5 times that of the palladium acetate, dispersing the precursor in the methanol aqueous solution, carrying out ultrasonic treatment for 20 minutes, filtering, radiating for 20 hours under a high-pressure mercury lamp, washing with water, and drying.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that no porous Al was added 2 O 3 。
The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amounts of substances into water, stirring and mixing uniformly to obtain a uniform solution, adding polyethylene glycol and citric acid, wherein the amount of the citric acid is 1.2 times of the sum of the amounts of the copper nitrate, cobalt nitrate and ferric nitrate substances, stirring and heating to 80 ℃, reacting for 12 hours to obtain gel, drying the gel at 120 ℃ for 10 hours, heating to 300 ℃ for calcination at a speed of 15 ℃/min for 4 hours, heating to 900 ℃ for two times for calcination at a speed of 3 ℃/min for 5 hours, cooling, grinding and sieving to obtain a precursor, adding palladium acetate into a methanol aqueous solution with the mass of 10 times that of the precursor, dispersing the precursor in the methanol aqueous solution with the mass of 5%, filtering out the precursor after ultrasonic treatment for 30 minutes, radiating for 15 hours under a high-pressure mercury lamp, washing and drying.
And collecting purified gas, sampling to detect the gas content, wherein the purity of argon is 99.9991%, and the recovery rate of argon is 83.16%.
Comparative example 2:
comparative example 2 is substantially the same as example 1 except that no palladium atom was incorporated in the oxygen carrier.
The preparation method of the oxygen carrier comprises the following steps:
adding copper nitrate, cobalt nitrate and ferric nitrate with the same amount of substances into water, stirring and mixing uniformly to obtain a uniform solution, and adding polyethylene glycol, citric acid and porous Al 2 O 3 Wherein the amount of the citric acid is 1.2 times of the sum of the amounts of the copper nitrate, the cobalt nitrate and the ferric nitrate, stirring and heating to 80 ℃, reacting for 12 hours to obtain gel, drying the gel at 120 ℃ for 10 hours, heating to 300 ℃ for calcination for 4 hours at a speed of 15 ℃/min, heating to 900 ℃ for 5 hours at a speed of 3 ℃/min, cooling, grinding and sieving.
And collecting purified gas, sampling and detecting the gas content, wherein the purity of the argon is 99.9985%, and the recovery rate of the argon is 82.83%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A process for preparing high-purity argon gas features that the argon gas is filled in M-CuCoFeO 4 /Al 2 O 3 The method comprises the steps of (1) an oxygen carrier fixed bed reactor, wherein argon discharged after reaction is adsorbed on an adsorbent by a pressure swing adsorption method, and purified argon is collected, wherein M is Pd, and the adsorbent is formed by mixing a LiX type zeolite molecular sieve and a 3A type carbon molecular sieve;
the mass ratio of the LiX type zeolite molecular sieve to the 3A type carbon molecular sieve is 1-5:1-5;
the temperature of the fixed bed reactor is 150-200 ℃;
the M-CuCoFeO 4 /Al 2 O 3 The preparation method of the oxygen carrier comprises the following steps:
s1: adding inorganic copper salt, inorganic cobalt salt and inorganic ferric salt into water, stirring and mixing uniformly to obtain uniform solution, adding polyethylene glycol, citric acid and porous Al 2 O 3 Stirring and heating to 80-95 ℃, and reacting for 10-15h to obtain gel;
s2: drying the gel at 100-120deg.C for 10-15h;
s3: calcining for 2-5h at 300-500 ℃ again, calcining for 2-5h at 700-900 ℃ again, cooling, grinding and sieving to obtain a precursor;
s4: dispersing the precursor in methanol aqueous solution containing palladium acetate or silver nitrate, carrying out ultrasonic treatment for 20-30min, filtering, placing under a high-pressure mercury lamp for irradiation for 10-20h, washing with water, and drying.
2. The method for producing high-purity argon gas according to claim 1, wherein the inorganic copper salt is any one of copper nitrate, copper sulfate and copper chloride;
the inorganic cobalt salt is any one of cobalt nitrate, cobalt sulfate and cobalt chloride;
the inorganic ferric salt is any one of ferric nitrate, ferric sulfate and ferric chloride.
3. The method for producing high purity argon gas according to claim 1 wherein the amounts of the inorganic copper salt, the inorganic cobalt salt and the inorganic iron salt are the same.
4. The method for producing high purity argon gas according to claim 1, wherein a ratio of a sum of amounts of substances of the inorganic copper salt, the inorganic cobalt salt, the inorganic iron salt to an amount of substances of the citric acid is 1:1-1.2.
5. The method for preparing high purity argon gas according to claim 1, wherein the primary heating rate in S3 is 10-15 ℃/min and the secondary heating rate is 3-5 ℃/min.
6. The method for producing high purity argon gas according to claim 1 wherein the mass concentration of the aqueous methanol solution in S4 is 1 to 5%.
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| JP2012101976A (en) * | 2010-11-10 | 2012-05-31 | Sumitomo Seika Chem Co Ltd | Refining method and refining apparatus for argon gas |
| CN102815718A (en) * | 2012-09-03 | 2012-12-12 | 中国地质大学（武汉） | One-step method for preparing 3A type zeolite molecular sieve by kaoline |
| 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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| JP2012101976A (en) * | 2010-11-10 | 2012-05-31 | Sumitomo Seika Chem Co Ltd | Refining method and refining apparatus for argon gas |
| CN103569979A (en) * | 2012-08-09 | 2014-02-12 | 住友精化株式会社 | Purifying method and purifying device for argon |
| CN102815718A (en) * | 2012-09-03 | 2012-12-12 | 中国地质大学（武汉） | One-step method for preparing 3A type zeolite molecular sieve by kaoline |
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