CN115155244A - Electronic special gas purification method - Google Patents
Electronic special gas purification method Download PDFInfo
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- CN115155244A CN115155244A CN202210963192.0A CN202210963192A CN115155244A CN 115155244 A CN115155244 A CN 115155244A CN 202210963192 A CN202210963192 A CN 202210963192A CN 115155244 A CN115155244 A CN 115155244A
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- 238000000034 method Methods 0.000 title claims abstract description 93
- 238000000746 purification Methods 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 210
- 238000001179 sorption measurement Methods 0.000 claims abstract description 140
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 101
- 230000008569 process Effects 0.000 claims abstract description 57
- 239000003513 alkali Substances 0.000 claims abstract description 50
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 238000010306 acid treatment Methods 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 52
- 230000004048 modification Effects 0.000 claims description 38
- 238000012986 modification Methods 0.000 claims description 38
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 25
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 19
- 239000001307 helium Substances 0.000 claims description 18
- 229910052734 helium Inorganic materials 0.000 claims description 18
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 238000004868 gas analysis Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 229910000064 phosphane Inorganic materials 0.000 description 14
- 239000005922 Phosphane Substances 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910052785 arsenic Inorganic materials 0.000 description 6
- -1 arsenic alkane Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910000066 arsane Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
Abstract
The embodiment of the application provides a method for purifying electronic special gas, and belongs to the technical field of purification of semiconductor manufacturing gas. The electronic special gas is alkane gas, and the purification method comprises the following adsorption process: and (3) absorbing the special electron gas in the special electron gas raw material gas by adopting porous carbon modified by alkali treatment and/or acid treatment, so that the special electron gas and impurity gas in the special electron gas raw material gas are separated. The purification method adopts an adsorption purification treatment mode, and can avoid the problems of high purification energy consumption and high material loss; the modified porous carbon used in the method has good adsorption activity, adsorption selectivity and adsorption capacity for the special electronic gas, and can effectively adsorb the special electronic gas to realize separation of the special electronic gas and impurity gas, so that various impurity gases in the special electronic gas feed gas can be effectively removed.
Description
Technical Field
The application relates to the technical field of purification of semiconductor manufacturing gas, in particular to a method for purifying electronic special gas.
Background
High purity arsine (AsH) 3 ) And Phosphane (PH) 3 ) The isoelectron special gas is mainly applied to the manufacturing process of semiconductor integrated circuits, and the purity requirement of the isoelectron special gas is more than 99.9999 percent; trace impurities including N 2 、O 2 、Ar 2 、H 2 O、CO、CO 2 、CH 4 、C 2 H 6 Etc., the content thereof is required to be less than 100ppb.
In the current process, in order to remove the trace impurities so that the electronic characteristic gas meets the high purity requirement of the semiconductor integrated circuit manufacturing process, one or more measures such as rectification, low temperature adsorption and the like are generally required to be combined.
When the rectification method is adopted to remove the impurities in the arsine and the phosphine, the energy consumption is high and the material loss is high. Furthermore, some impurities are due to boiling points andprocess gas proximity (e.g. PH) 3 Boiling point-87.8 deg.C, and C 2 H 6 Boiling point-88.6 deg.c) and is difficult to remove by distillation.
When the low-temperature adsorption method is adopted, zeolite molecular sieves (model 3A,4A,5A, 13X) and other adsorbing materials such as activated carbon are mostly adopted, and generally, H can only be effectively removed by adsorption 2 O、CO 2 Etc. but for N 2 、O 2 、Ar 2 、H 2 And the effect of removing impurity gases is poor.
Disclosure of Invention
The application aims to provide a method for purifying the electronic special gas, which can solve the problems of high purification energy consumption and high material loss and can effectively remove various impurity gases in the electronic special gas feed gas.
The embodiment of the application is realized as follows:
the embodiment of the application provides a method for purifying electronic special gas, wherein the electronic special gas is alkane gas, and the method comprises the following steps: the porous carbon modified by alkali treatment or acid treatment is adopted to adsorb the electronic special gas in the electronic special gas raw material gas, so that the electronic special gas and the impurity gas in the electronic special gas raw material gas are separated.
The method for purifying the electronic special gas provided by the embodiment of the application has the beneficial effects that:
the porous carbon modified by alkali treatment or acid treatment is adopted for adsorption and purification treatment, and the treatment mode can avoid the problems of high purification energy consumption and high material loss. The modified porous carbon has good adsorption activity, adsorption selectivity and adsorption capacity for alkane electronic special gases such as arsine and phosphine, and can effectively adsorb the alkane electronic special gases such as arsine and phosphine to realize the separation of the electronic special gases and impurity gases, so that various impurity gases in the electronic special gas raw material gas can be effectively removed.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a process diagram of a purification apparatus used in some exemplary embodiments of the present application.
Icon: 100-group A adsorption unit; 200-B group of adsorption devices; 300-temperature controller; 400-a vacuum manometer; 500-a feed gas supply unit; 600-a high purity helium gas supply unit; 700-product gas collection unit; 800-vacuum system; 900-gas chromatograph; 1000-flow meter.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
It is to be noted that, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the meaning of "above" and "below" includes the number; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents "unit of measure" for both "numerical value a" and "numerical value b".
The applicant has noted that in the current cryogenic adsorption process, the impurity gases are usually removed by adsorption using an adsorbent. As an example, the alkane gases arsine and phosphine are N 2 、O 2 、Ar 2 、H 2 The adsorption competitive power of the impurity gases is weaker than that of arsine and phosphine, so that the adsorbent cannot adsorb N well 2 、O 2 、Ar 2 、H 2 Impurity gas is mixed, thereby leading to N 2 、O 2 、Ar 2 、H 2 And the effect of removing impurity gases is poor.
The applicant also noticed that, when the low-temperature adsorption process is adopted, the porous carbon is subjected to alkali treatment modification and/or acid treatment modification, so that functional groups on the surface of the porous carbon and ions and compounds loaded on the surface of the porous carbon are changed, and the chemical properties of the surface of the porous carbon are changed, so that the porous carbon subjected to alkali treatment modification and/or acid treatment modification has good adsorption activity, adsorption selectivity and adsorption capacity on alkane electronic special gases such as arsine and phosphine, and can realize separation of the electronic special gases and impurity gases by adsorbing the alkane electronic special gases such as arsine and phosphine, wherein the impurity gases with weak adsorption can be effectively removed by a vacuumizing mode after enrichment; moreover, after the impurity gas is removed, alkane electronic special gases such as arsine and phosphine can be efficiently analyzed from the modified porous carbon, so that the high-purity electronic special gases obtained by purification can be conveniently further collected.
Based on this, the present application proposes a method for purifying electronic specialty gas, which will be described in detail with reference to the following embodiments.
The application provides a method for purifying electronic special gas, wherein the electronic special gas is alkane gas, the process comprises an adsorption flow, and the adsorption flow comprises the following steps: and (3) absorbing the special electron gas in the special electron gas raw material gas by adopting porous carbon modified by alkali treatment and/or acid treatment, so that the special electron gas and impurity gas in the special electron gas raw material gas are separated.
It can be understood that the adsorption process is mainly used for embodying how to realize effective separation of the electronic special gas and the impurity gas in the electronic special gas feed gas, thereby ensuring that various impurity gases in the electronic special gas feed gas can be effectively removed. Before the adsorption process, the operations of filling, resolving, drying and the like can be carried out on the adsorbent as required; after the adsorption process, operations such as removal of impurity gases and analysis of the special electron gas may be performed as necessary.
Alkane electronic gases are understood herein by conventional definition and include, but are not limited to, silanes, boranes, arsines, phosphanes, and the like.
It has been found that porous carbon modified by alkali treatment and/or acid treatment generally exhibits extremely excellent adsorption activity, adsorption selectivity and adsorption capacity, particularly when used for the adsorption of arsine and phosphine feed gases.
Based on this, as an example, the electron gas is selected from arsine and phosphine. That is, the method for purifying the electronic special gas can be used for purifying the arsine, and the method for purifying the electronic special gas can also be used for purifying the phosphane.
In the present application, the porous carbon may be a porous material prepared from coal, biomass, a high molecular polymer, or the like as a raw material.
In order to ensure that the modified porous carbon has better adsorption activity, adsorption selectivity and adsorption capacity for specific gases such as arsine, phosphine and the like, specific selection can be performed on the specific surface area and the pore volume of the porous carbon, the specific surface area and the pore volume are selected as large as possible under a certain standard, and better adsorption performance is ensured. The modification of the application mainly changes the surface activity of the porous carbon, and the specific surface area and the pore volume are not influenced too much, so that the specific surface area and the pore volume defined in the exemplary scheme of the application can refer to indexes before the porous carbon is modified and can also refer to indexes after the porous carbon is modified.
Alternatively, the specific surface area of the porous carbon is more than or equal to 900m 2 /g。
Optionally, the porous carbon has a pore volume (or pore volume) of 0.4cm or more 3 /g。
The porous carbon modified by the alkali treatment and/or the acid treatment may be the porous carbon modified by the alkali treatment alone, the porous carbon modified by the acid treatment alone, the porous carbon modified by the alkali treatment first and then the acid treatment, or the porous carbon modified by the acid treatment first and then the alkali treatment.
Research shows that the lifting amount of the electronic special gas is improved to different degrees based on the porous carbon with different modification modes compared with the unmodified porous carbon. When the arsenic alkane raw material gas is adsorbed, compared with the adsorption capacity of unmodified porous carbon to arsenic alkane, the adsorption capacity of acid treatment modified porous carbon to arsenic alkane after alkali treatment modification can be improved by 50% or more, the adsorption capacity of arsenic alkane can be improved by about 5% only through alkali treatment modified porous carbon, the adsorption capacity of arsenic alkane can be improved by about 25% only through acid treatment modified porous carbon, and the adsorption capacity of arsenic alkane can be improved by about 40% through alkali treatment modified porous carbon after acid treatment modification. When the raw material gas of the phosphane is adsorbed, compared with the absorption capacity of unmodified porous carbon to the phosphane, the absorption capacity of the acid-treated modified porous carbon to the phosphane after the alkali treatment modification can be improved by 60% or more, the absorption capacity of the alkali-treated modified porous carbon to the phosphane can be improved by about 5%, the absorption capacity of the acid-treated modified porous carbon to the phosphane can be improved by about 25%, and the absorption capacity of the alkali-treated modified porous carbon to the phosphane can be improved by about 40% after the acid treatment modification. Therefore, compared with unmodified porous carbon, the porous carbon modified by alkali treatment and acid treatment has obviously improved adsorption activity, adsorption selectivity and adsorption capacity on arsine and phosphine, and the separation of the special electronic gas and the impurity gas can be effectively realized when the porous carbon modified by alkali treatment and acid treatment is used for adsorbing the raw material gas of arsine and phosphine.
In this regard, as an example, in the adsorption process, the electron specific gas in the electron specific gas raw material gas is adsorbed by using porous carbon which is subjected to alkali treatment modification and acid treatment modification in this order.
In some possible embodiments, the base used in the base treatment modification process is selected from NaOH, KOH, and NH 3 ·H 2 And O. In order to ensure better alkali treatment modification effect, the alkali is strong alkali such as NaOH, KOH and the like; further, to control costs, the base is, for example, naOH.
Optionally, during the alkali treatment modification, the concentration of the alkali in the alkali liquor is 8 to 12M (i.e. mol/L), such as but not limited to any one of 8M, 9M, 10M, 11M and 12M or a range value between any two; the mass ratio of the raw material porous carbon (namely, the raw material for preparing modified porous carbon in modification treatment, namely, unmodified porous carbon) to the alkali liquor is 1: (1.5-2.2), for example but not limited to 1:1.5, 1:1.6, 1:1.7, 1:1.7, 1:1.9, 1:2.0, 1:2.1 and 1:2.2, or a range between any two.
In the embodiment, the concentration of alkali in the alkali liquor and the mass ratio of the porous carbon to the alkali liquor are controlled according to a specific standard, so that the porous carbon is ensured to have a better alkali modification activation effect, and the porous carbon obtained through alkali treatment modification has better adsorption activity, adsorption selectivity and adsorption capacity for specific electronic gases such as arsine and phosphine.
In some possible embodiments, the acid used during the acid treatment modification is selected from HNO 3 、H 2 SO 4 And H 3 PO 4 . Ensuring better alkali treatment modification effect, the acid is HNO 3 、H 2 SO 4 And the like strong acids; further, to avoid introducing impurities after acid treatment, the acid is, for example, HNO 3 . In embodiments where the electron gas is a phosphine, the acid is, for example, HNO to avoid introduction of impurities after acid treatment 3 Or H 3 PO 4 。
Optionally, during the acid treatment modification, the concentration of the acid in the acid solution is 3 to 5M, for example, but not limited to, any one of 3M, 4M and 5M or a range between any two; the mass ratio of the alkali-modified porous carbon (which means the porous carbon modified by the alkali treatment) to the acid solution is 1: (1.5-2.2), for example but not limited to 1:1.5, 1:1.6, 1:1.7, 1:1.7, 1:1.9, 1:2.0, 1:2.1 and 1:2.2, or a range between any two.
It should be noted that, in the application, in the alkali treatment modification and acid treatment modification processes, after the acid-base treatment solution and the porous carbon are mixed, mixing operations such as stirring or shaking can be performed along with or at intervals, so that the acid-base modification component can be kept in good contact and reaction with the porous carbon all the time. After the alkali treatment modification and the acid treatment modification, in order to ensure that the modified porous carbon has better cleanliness, the modified porous carbon can be further cleaned and dried.
In some exemplary embodiments, the purification method comprises the following sequential schemes:
providing an adsorption device flow: providing an adsorption device which is filled with porous carbon and has the interior in a negative pressure state;
cooling process: refrigerating the adsorption device;
purging flow: filling helium into the adsorption device to be in a normal pressure state or a positive pressure state, balancing for a first preset time, and then vacuumizing to be in a negative pressure state;
an adsorption process: filling the electronic special gas raw material gas into an adsorption device, and adsorbing the electronic special gas by using porous carbon while keeping impurity gas in a free state;
an exhaust flow: discharging the impurity gas out of the adsorption device;
a temperature return process; heating the adsorption device to desorb the electronic special gas from the porous carbon;
a gas production process: and outputting the desorbed electronic special gas from the adsorption device.
With respect to the providing a sorption device process, as an example, the providing a sorption device process includes: filling porous carbon into an adsorption device (such as a steel cylinder with a cylinder valve), vacuumizing until the air pressure reaches below 0.1mbar, filling helium gas until the air pressure reaches 1-3 bar (bar), balancing for 3-5 min (min), and vacuumizing until the air pressure reaches below 0.1 mbar; wherein, the operations of filling helium, balancing and vacuumizing are repeated for 3 to 5 times. In this exemplary process, after the porous carbon is charged to the adsorption device, effective removal of the gas adsorbed on the porous carbon particles is ensured.
Further, after repeating the operations of filling helium gas, balancing and then vacuumizing for 3-5 times, a vacuum drying operation may be performed, and the exemplary vacuum drying operation includes: and heating the environment of the adsorption device according to the temperature above 90 ℃, and opening a vacuum system until the pressure in the adsorption device is stabilized below 0.05mbar, wherein the drying is qualified.
Regarding the cooling down procedure, as an example, the cooling down procedure includes: the environment in which the adsorption device is located is refrigerated on a scale of setting a temperature of-20 ℃ or lower for 3 to 5 (e.g., 4) hr (hours).
Regarding the purging process, as an example, in the purging process, helium gas is filled into the adsorption device until the air pressure reaches 1 to 3bar, the first preset time is 3 to 5min, and then the adsorption device is vacuumized until the air pressure reaches below 0.1 mbar; wherein, the purging process is repeated for 3-5 times between the cooling process and the adsorption process.
Regarding the adsorption process, as an example, in the adsorption process, the charging speed of the electronic special gas raw material gas is 15 to 20lpm (liter per minute), and the gas pressure in the adsorption device is below 1 bar; and (4) carrying out adsorption equilibrium for 3-5 (for example, 4) hr until the pressure gauge reading is stable, and then finishing the adsorption process.
Regarding the exhaust flow, as an example, the exhaust flow: the adsorption device exhausts the gas outwards until the pressure reduction value reaches more than 0.1 bar.
In the back-temperature process, for example, the environment in which the adsorption apparatus is located is heated to a temperature of 50 to 60 ℃ for 3 to 5 hours.
In the gas production process, for example, the gas analysis output time is 10 to 14 (for example, 12) hr, and the product is collected after the electronic specialty gas is output from the adsorption apparatus and is qualified by the gas chromatograph.
Since in the exemplary embodiment, the gas production process time and the total time from the temperature reduction process to the temperature return process are equivalent, both being about 12hr, in order to provide the purification efficiency, two sets of adsorption devices (each set of adsorption device may include one or more adsorption devices) may be configured to alternately operate, and when one set (referred to as a set a) of adsorption devices starts the gas production process, the other set (referred to as a set B) of adsorption devices may perform other processes before gas production; after group A completes the gas production process and group B completes other processes before gas production, group A ends the gas production process and performs other processes before gas production, and group B starts the gas production process. The group a adsorption devices and the group B adsorption devices operate alternately according to the above example.
Based on this, as an example, two sets of adsorption devices are used in the purification method, wherein when one set of adsorption device starts the gas production process, the other set of adsorption device starts the operation from the temperature reduction process to the temperature return process.
Referring to fig. 1, the following describes an exemplary method for purifying electronic specialty gas provided by the present application in conjunction with a specific purification apparatus.
As shown in fig. 1, the adsorption device is a steel cylinder with a cylinder valve, and the adsorption devices are divided into two groups AB, namely a group a adsorption device 100 and a group B adsorption device 200. The AB two groups of adsorption devices are respectively arranged in the environment with the temperature controller 300 and respectively correspond to the AB two groups of temperature controllers 300; the two sets of adsorption devices AB are also provided with two sets of vacuum pressure gauges 400. In addition, two sets of valves AB are respectively and correspondingly arranged in the inlet and outlet lines of the two sets of adsorption devices AB, and are respectively communicated with the raw material gas supply unit 500, the high-purity helium gas supply unit 600, the product gas collection unit 700 and the vacuum system 800, and a flow meter 1000 is further arranged on a pipeline between the raw material gas supply unit 500 and the two sets of adsorption devices AB.
Referring to fig. 1, the method for purifying the electronic special gas comprises the following steps:
adsorption devices are provided, including a group a adsorption device 100 and a group B adsorption device 200.
All valves are confirmed to be in a closed state.
Cooling: adjusting temperature controller 300 to refrigeration state, setting temperature below-20 deg.C, and maintaining for 4hr.
Purging: opening the cylinder valve at the side A, opening a valve V3A, and filling high-purity helium gas through a high-purity helium gas supply unit 600 until the pressure reaches 1-3 bar; closing V3A, balancing for 3-5 min, opening valve V4A, evacuating to below 0.05mbar by vacuum system 800, and closing V4A. Repeating the blowing process for 3-5 times.
Adsorption: opening V1A, charging feed gas (phosphorane or arsane) through the feed gas supply unit 500, controlling the speed at 15-20 lpm, controlling the pressure below 1bar, balancing the adsorption for 4hr until the reading of the vacuum pressure gauge 400 is stable, and closing V1A, wherein the feed gas is adsorbed to a greater extent without closing a cylinder valve for balancing. At this time, the specific electron gas is adsorbed on the porous carbon, and the impurity gas (N) 2 、O 2 、Ar 2 、H 2 Etc.) in a free state.
Exhausting: and slowly opening the V4A, reducing the air pressure in the steel cylinder by 0.1bar to remove free impurity gases, and then closing the V4A.
Temperature return: regulating temperature controller 300 to set 50-60 deg.C, heating the steel cylinder for 4hr, at this time, the raw material gas begins to desorb, and the pressure rises.
Gas production: the desorption process is continued for 12hr with the V2A opened, and the desorbed product gas is sent to the gas chromatograph 900 for qualified analysis, and then collected by the product gas collection unit 700.
When the group a adsorption devices 100 start to collect the produced gas, the group B adsorption devices 200 start to operate from the cooling process to the returning process in sequence.
The method for purifying the electronic special gas provided by the present application will be exemplarily described below with reference to specific experiments.
1. Preparation of porous carbon modified by acid treatment after modification by alkali treatment
(1) Modification by alkali treatment
A. Preparation of about 10M NaOH solution:
600g of NaOH were dissolved in 1.5L of deionized water.
B. 1000g of raw porous carbon particles (specific surface area of porous carbon: 1100 m) 2 Per g, pore volume of the porous carbon is 0.45cm 3 G) soaking in the solution. During this period, the beaker with the porous carbon soaked therein was placed on a shaker and shaken at room temperature for 24hr.
C. The porous carbon particles are filtered and rinsed with deionized water until the filtered water has a pH of approximately 7.
D. The porous carbon particles were dried in an oven at 105 ℃ for 24hr.
(2) Modification by acid treatment
A. Preparation of about 4M HNO 3 Solution:
370ml of 65wt% HNO 3 Prepared by dilution in 1150ml of deionised water.
B. 1000g of the porous carbon particles modified by the alkali treatment were immersed in the solution. During this period, the beaker soaked with porous carbon was placed on a shaker and shaken at room temperature for 24hr.
C. And filtering out porous carbon particles, and washing with deionized water until the pH value of filtered water is close to 7.
D. The porous carbon particles were dried in an oven at 105 ℃ for 24hr.
2. Testing the adsorption performance of different porous carbons on the special electronic gas
The method is characterized in that unmodified raw porous carbon particles used in the preparation process and the prepared porous carbon modified by alkali treatment and then acid treatment are respectively used as porous carbon adsorbents, and the detection steps of the adsorption performance are as follows:
A. and respectively putting 1000g of dry porous carbon into 2.2L steel cylinders, mounting cylinder valves, and detecting the leakage to be qualified.
B. Placing the steel cylinder in an oven with the temperature of more than 200 ℃, purging and replacing by helium, drying, vacuumizing to be less than 0.05mbar, cooling to normal temperature after stabilization, and closing a cylinder valve. The steel cylinders are taken down and then weighed on a high-precision electronic scale respectively.
C. The cylinders were separately charged with a source of phosphine gas (purity > 99.99%) until the pressure was stable at atmospheric pressure (1013 mbar A) and equilibrated for 12hr.
D. The cylinder valve is closed, and the weight is taken down.
E. And pumping out the gas in the bottle and discharging the gas to a tail gas processor. And then repeating the steps B, C and D for 2 times.
F. And (4) replacing the gas source with arsine (the purity is more than 99.99%), and repeating the steps B, C and D for 3 times.
G. The data were collated and the results are shown in table 1 below.
TABLE 1 adsorption Performance data collation
Wherein: the raw material carbon in the raw material carbon bottle refers to unmodified raw material porous carbon particles used in the preparation process; the modified carbon in the modified carbon bottle is porous carbon modified by acid treatment after alkali treatment modification prepared in the preparation process. The adsorption increase amount refers to an increase in the adsorption amount of the modified carbon relative to the adsorption amount of the raw material carbon.
As can be seen from the results in table 1, the raw porous carbon particles (before modification), the average adsorption amount for phosphane: 0.1035g of pH 3 Carbon/g, adsorption amount to arsine: 0.3025g AsH 3 Per gram of carbon. After the modification, the adsorption capacity of the phosphine is as follows: 0.158g PH 3 Per gram of carbon, an increase of about 53%; adsorption amount for arsine: 0.4975g AsH 3 Per gram of carbon, an increase of about 64%.
4. Purifying electronic special gas
(1) Providing a suction device
A. Filling and bottling: and (3) filling the treated modified porous carbon (the porous carbon modified by the alkali treatment and the acid treatment) into a steel cylinder, installing a cylinder valve, and detecting the leakage to be qualified.
B. Gas replacement: firstly, using a vacuum pump to pump the air in a steel cylinder to be below 0.1mbar, and then filling high-purity helium (the purity is more than 6N) until the pressure reaches 1-3 bar; equilibrate for 3-5 minutes and evacuate to below 0.1 mbar. And repeating the helium filling/vacuumizing steps for 3-5 times to remove the gas adsorbed on the porous carbon particles.
C. And (3) vacuum drying: and (3) heating the temperature controller to above 90 ℃, opening a vacuum system until the pressure is stabilized below 0.05mbar, and drying to be qualified.
(2) Carrying out the adsorption step (see FIG. 1)
A. All valves are confirmed to be in a closed state.
B. Cooling: adjusting the temperature controller 300 to a refrigeration state, setting the temperature below-20 deg.C, and maintaining for 4hr.
C. Purging: opening the cylinder valve at the side A, opening a valve V3A, and filling high-purity helium gas through a high-purity helium gas supply unit 600 until the pressure reaches 1-3 bar; closing V3A, balancing for 3-5 min, opening valve V4A, evacuating to below 0.05mbar by vacuum system 800, and closing V4A. And repeating the purging process for 3-5 times.
D. Adsorption: opening V1A, charging feed gas (phosphane or arsane) through the feed gas supply unit 500, controlling the speed at 15-20 lpm and the pressure at 1bar or less, balancing the adsorption for 4hr until the reading of the vacuum manometer 400 is stable, and closing V1A. At this time, the special electron gas is adsorbed on the porous carbon, and the impurity gas (N) 2 、O 2 、Ar 2 、H 2 Etc.) in a free state.
E. Exhausting: and slowly opening the V4A, reducing the air pressure in the steel cylinder by 0.1bar to remove free impurity gases, and then closing the V4A.
F. Temperature return: regulating temperature controller 300 to set 50-60 deg.C, heating the steel cylinder for 4hr, at this time, the raw material gas begins to desorb, and the pressure rises.
G. Gas production: the V2A is opened, the desorption process is continued for 12hr, and the desorbed product gas is sent to the gas chromatograph 900 for qualified analysis, and then collected by the product gas collection unit 700.
When the group a adsorption device 100 starts to collect the produced gas, the group B adsorption device 200 starts to operate from the cooling process to the temperature return process in sequence.
Analyzing and comparing the raw material gas and the product gas by using a gas chromatograph, and detecting impurity gas (N) in the raw material gas 2 、O 2 、Ar 2 、H 2 ) The concentration of (b) was reduced from the ppm level to the ppb level, and the specific purification results of several sets of parallel experiments are shown below.
TABLE 2 EXPERIMENT 1 (phosphane feed gas)
TABLE 3 experiment 2 (phosphine feed gas)
TABLE 4 experiment 3 (arsine feed gas)
TABLE 5 EXPERIMENT 4 (arsine feed gas)
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Claims (10)
1. A method for purifying electronic special gas, which is characterized in that the electronic special gas is alkane gas, and the method comprises the following steps:
an adsorption process: and (3) adsorbing the special electron gas in the special electron gas raw material gas by adopting porous carbon modified by alkali treatment and/or acid treatment, so that the special electron gas and impurity gas in the special electron gas raw material gas are separated.
2. The purification method of claim 1, wherein the electronic specialty gas is selected from the group consisting of arsine and phosphine.
3. The purification method according to claim 1, wherein the porous carbon satisfies at least one of the following conditions (1) and (2):
(1) The specific surface area is more than or equal to 900m 2 /g；
(2) The pore volume is more than or equal to 0.4cm 3 /g。
4. The purification method according to claim 1, wherein the porous carbon sequentially subjected to alkali treatment modification and acid treatment modification is used for adsorbing the electronic special gas in the electronic special gas raw material gas.
5. The purification method according to claim 1, wherein at least one of the following conditions (1) and (2) is satisfied:
(1) In the alkali treatment modification process, the alkali used is selected from NaOH, KOH and NH 3 ·H 2 O；
(2) In the acid treatment modification process, the acid used is selected from HNO 3 、H 2 SO 4 And H 3 PO 4 。
6. The purification method according to claim 5, wherein in the alkali treatment modification process, the concentration of the alkali in the alkali liquor is 8-12M, and the mass ratio of the raw material porous carbon to the alkali liquor is 1: (1.5-2.2).
7. The purification method according to claim 5, wherein in the acid treatment modification process, the concentration of the acid in the acid solution is 3-5M, and the mass ratio of the alkali-modified porous carbon to the acid solution is 1: (1.5-2.2).
8. The purification method according to any one of claims 1 to 7, comprising the following steps performed in sequence:
providing an adsorption device flow: providing an adsorption device which is filled with the porous carbon and has the interior in a negative pressure state;
cooling process: refrigerating the adsorption device;
purging flow: filling helium into the adsorption device to be in a normal pressure state or a positive pressure state, balancing for a first preset time, and then vacuumizing to be in a negative pressure state;
the adsorption process comprises the following steps: filling the raw gas of the electronic special gas into the adsorption device, wherein the porous carbon adsorbs the electronic special gas and the impurity gas is in a free state;
and (3) an exhaust flow: discharging the impurity gas from the adsorption device;
a temperature return process; heating the adsorption device to desorb the electronic specialty gas from the porous carbon;
a gas production process: and outputting the desorbed electronic special gas from the adsorption device.
9. The purification method according to claim 8, wherein at least one of the following conditions (1) to (7) is satisfied;
(1) The process for providing the adsorption device comprises the following steps: filling the porous carbon into the adsorption device, vacuumizing until the air pressure reaches below 0.1mbar, filling helium gas until the air pressure reaches 1-3 bar, balancing for 3-5 min, and vacuumizing until the air pressure reaches below 0.1 mbar; wherein, the operations of filling helium, balancing and vacuumizing are repeated for 3 to 5 times;
(2) The cooling process comprises the following steps: refrigerating the environment of the adsorption device according to the standard of setting the temperature below-20 ℃ and keeping the temperature for 3-5 hr;
(3) In the purging process, helium is filled into the adsorption device until the air pressure reaches 1-3 bar, the first preset time is 3-5 min, and then the adsorption device is vacuumized until the air pressure reaches below 0.1 mbar; wherein, the purging process is repeated for 3-5 times between the cooling process and the adsorption process;
(4) In the adsorption process, the charging speed of the electronic special gas raw material gas is 15-20 lpm, and the air pressure in the adsorption device is below 1 bar; the adsorption process is finished after the adsorption is balanced for 3 to 5 hours until the reading of the pressure gauge is stable;
(5) The exhaust flow comprises the following steps: the adsorption device exhausts the gas outwards until the pressure reduction value reaches more than 0.1 bar;
(6) In the temperature return flow, the environment where the adsorption device is located is heated according to the standard of setting the temperature of 50-60 ℃ and continuing for 3-5 hr;
(7) In the gas production process, the gas analysis output time is 10-14 hr, and the electronic special gas is output from the adsorption device and is analyzed by a gas chromatograph to be qualified, and then the product is collected.
10. The purification method according to claim 8,
and adopting two groups of adsorption devices to work alternately, wherein when one group of adsorption devices starts the gas production process, the other group of adsorption devices starts to operate from the temperature reduction process to the temperature return process.
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