CN1561318A - Method of purifying tetrafluoromethane and utilization thereof - Google Patents
Method of purifying tetrafluoromethane and utilization thereof Download PDFInfo
- Publication number
- CN1561318A CN1561318A CN 01801119 CN01801119A CN1561318A CN 1561318 A CN1561318 A CN 1561318A CN 01801119 CN01801119 CN 01801119 CN 01801119 A CN01801119 A CN 01801119A CN 1561318 A CN1561318 A CN 1561318A
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- Prior art keywords
- tetrafluoromethane
- carbon
- impurity
- pore size
- zeolite
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- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims description 67
- 239000011148 porous material Substances 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- 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 33
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 38
- 235000011089 carbon dioxide Nutrition 0.000 claims description 28
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 21
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 17
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 claims description 8
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000002594 sorbent Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- -1 vinyl compound Chemical class 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004452 microanalysis Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/007—Preparation of halogenated hydrocarbons from carbon or from carbides and halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Tetrafluoromethane containing ethylene compounds, hydrocarbon compounds, carbon monoxide and/or carbon dioxide is contacted with zeolite having an average pore size of 3.4 to 11 ANGSTROM and an Si/Al ratio of 1.5 or less and/or a carbonaceous adsorbent having an average pore size of 3.4 to 11 ANGSTROM . Thus, high-purity tetrafluoromethane can be obtained which is advantageous in industry and provides good profitability.
Description
The cross reference of related application
The application is the application of submitting to according to 35U.S.C. the 111st (a) joint, requires to save according to 35U.S.C. the 111st (b) rights and interests of the applying date of the provisional application of submitting on July 9th, 2,000 60/230,704 according to 35U.S.C. the 119th (e) (1) joint.
Technical field
The present invention relates to a kind of purification tetrafluoromethane and (hereinafter can be called " FC-14 " or " CF
4") method and the application of the tetrafluoromethane of having purified.
Background technology
FC-14 is used as etching gas or clean air in the manufacturing of for example semiconducter device, therefore require its high purity product.
In order to produce FC-14, the whole bag of tricks has been proposed up to now.Known specifically have a for example following method:
(1) method that Refrigerant 12 and hydrogen fluoride are reacted in the presence of catalyzer;
(2) method that monochlorotrifluoromethane and hydrogen fluoride are reacted in the presence of catalyzer;
(3) method that trifluoromethane and fluorine gas are reacted;
(4) method that carbon and fluorine gas are reacted; With
(5) method of thermolysis tetrafluoroethylene.
Yet to be intermediate or the by product of the FC-14 that produced of reaction or the impurity that is derived from raw material form the mixture of azeotropic mixture or Azeotrope-like and its with target product FC-14 to the problem that these methods of producing FC-14 have separates and be the devil.In order to address this problem, for example proposed to contain trifluoromethane (CHF with zeolite or carbon-bearing adsorbent processing
3) as the FC-14 (referring to Japanese Patent 2,924,660) of impurity.
Disclosure of the Invention
Yet, still be not suitable for up to now suitability for industrialized production, can purify contains vinyl compound, hydrocarbon compound, carbon monoxide and/or the carbonic acid gas FC-14 as impurity, make it to have good benefit, contained the method for the high purity FC-14 of these impurity simultaneously hardly.
The present invention produces under above situation, and the purpose of this invention is to provide a kind of method of purification, and wherein FC-14 contacts with sorbent material and removes above-mentioned impurity by absorption, and can carry out suitability for industrialized production and obtain high purity FC-14 with good benefit.
In order to address the above problem, the inventor has carried out extensive studies, found that in the method for production high purity FC-14, when contain vinyl compound, hydrocarbon compound, carbon monoxide and/or carbonic acid gas as the FC-14 of impurity with comprise sorbent material with specific mean pore size and zeolite of specific Si/Al ratio and/or carbon-bearing adsorbent (molecular-sieve carbon (Molecular Sieving Carbon)) when contacting with specific mean pore size, can optionally adsorb and remove impurity and can obtain impure hardly high purity FC-14.The present invention is based on this discovery is accomplished.
Therefore, the invention provides as the method for the described purification tetrafluoromethane in following (1)-(15) and the application of the tetrafluoromethane of having purified.
(1) a kind of method of the tetrafluoromethane of purifying, comprise make contain one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas as the tetrafluoromethane of impurity and mean pore size be 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite and/or the mean pore size carbon-bearing adsorbent that is the 3.4-11 dust contact to reduce the amount of described impurity.
(2) method described in top (1), the tetrafluoromethane that wherein contains described impurity contacts in liquid phase with described zeolite and/or described carbon-bearing adsorbent.
(3) method described in top (1) or (2), wherein said zeolite is be selected from MS-4A, MS-5A, MS-10X and MS-13X at least a.
(4) method described in top (1) or (2), wherein said carbon-bearing adsorbent is molecular-sieve carbon 4A and/or molecular-sieve carbon 5A.
(5) as each described method in top (1)-(4), wherein one or more vinyl compounds are selected from ethene, vinyl fluoride, difluoroethylene and tetrafluoroethylene.
(6) method described in top (5), wherein one or more vinyl compounds are ethene and/or tetrafluoroethylene.
(7) as each described method in top (1)-(4), wherein one or more hydrocarbon compounds are selected from methane, ethane and propane.
(8) method described in top (7), wherein one or more hydrocarbon compounds are methane and/or ethane.
(9), wherein one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and the total content of carbonic acid gas in described tetrafluoromethane are reduced to 3ppm or lower as each described method in top (1)-(8).
(10), wherein contain the direct fluorination process production of tetrafluoromethane of one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas by trifluoromethane and fluorine gas are reacted as impurity as each described method in top (1)-(9).
(11), wherein contain the direct fluorination process production of tetrafluoromethane of one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas by carbon and fluorine gas are reacted as impurity as each described method in top (1)-(9).
(12) a kind of purity is 99.9997 quality % or higher tetrafluoromethane product, by obtaining according to purifying as each described method in top (1)-(11).
(13) a kind of etching gas comprises the tetrafluoromethane product described in top (12).
(14) a kind of clean air comprises the tetrafluoromethane product described in top (12).
In brief, the invention provides " a kind of method of the tetrafluoromethane of purifying; comprise making and contain one or more vinyl compounds; one or more hydrocarbon compounds; carbon monoxide and/or carbonic acid gas as the tetrafluoromethane of impurity and mean pore size be 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite and/or the mean pore size carbon-bearing adsorbent that is the 3.4-11 dust contact to reduce the amount of described impurity ", " a kind of purity that obtains by purifying according to the method described above is 99.9997 quality % or higher tetrafluoromethane product " and " a kind of etching gas and clean air that comprises above-mentioned tetrafluoromethane product ".
Implement best mode of the present invention
In order to produce FC-14, for example known a kind of method that makes trifluoromethane and fluorine gas reaction, a kind of carbon and the method for fluorine gas reaction and a kind of method of thermolysis tetrafluoroethylene of making.When using these methods, owing to existing impurity such as organic trace impurity, trace oxygen, trace water to grade in the raw material, gained FC-14 contains one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas as impurity.
Contained vinyl compound can be that one or more are selected from ethene (CH
2=CH
2), a vinyl fluoride (CH
2=CHF), difluoroethylene (CH
2=CF
2) and tetrafluoroethylene (CF
2=CF
2) compound.
Contained hydrocarbon compound can be that one or more are selected from methane (CH
4), ethane (C
2H
6) and propane (C
3H
8) compound.
Target product FC-14 and the boiling point of these impurity under normal pressure are shown in following table 1.
Table 1
| Compound name | Chemical formula | Boiling point (℃) |
| Carbon monoxide | ???CO | ???-191.5 |
| Methane | ???CH 4 | ???-161.5 |
| ???FC-14 | ???CF 4 | ???-128 |
| Ethene | ???CH 2＝CH 2 | ???-103.7 |
| Ethane | ???CH 3CH 3 | ???-89 |
| Difluoroethylene | ???CH 2＝CF 2 | ???-83 |
| Carbonic acid gas | ???CO 2 | ???-78.5 |
| Tetrafluoroethylene | ???CF 2＝CF 2 | ???-76.3 |
| One vinyl fluoride | ???CH 2＝CHF | ???-72 |
| Propane | ???CH 2CH 2CH 3 | ???-42.1 |
Because the mixture of target product FC-14 and these impurity formation Azeotrope-like or just as shown in table 1, their boiling point is approaching, so these impurity are very difficult to separate by distillation procedure.In order addressing this problem, in the distillation procedure of routine, reduce foreign matter content as much as possible with progression that increases distillation tower or the number that increases distillation tower, but this to be also uneconomical, and almost can not to be contained the high purity FC-14 of these impurity hardly.
In the present invention, for selective adsorption and remove these impurity among the FC-14, use mean pore size as 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite and/or mean pore size as the carbon-bearing adsorbent (molecular-sieve carbon) of 3.4-11 dust as sorbent material.In order to measure mean pore size, can utilize the gas adsorption method of using Ar gas.
Therefore, described sorbent material for (1) mean pore size be 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite, carbon-bearing adsorbent (molecular-sieve carbon) that (2) mean pore size is the 3.4-11 dust or (3) by with mean pore size be the carbon-bearing adsorbent of 3.4-11 dust add mean pore size be 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite in the sorbent material that obtains.Si/Al ratio used herein is an atomic ratio.
Can be unsaturated compound such as ethene, a vinyl fluoride, difluoroethylene and tetrafluoroethylene by the object lesson that uses impurity among the FC-14 that these sorbent materials remove, hydrocarbon compound such as methane, ethane and propane, and oxygenatedchemicals such as carbon monoxide and carbonic acid gas.As impurity preferably ethene, tetrafluoroethylene, methane, ethane, carbon monoxide and carbonic acid gas, more preferably ethene and ethane.
Molecular dimension difference between target product FC-14 and these impurity is little, thus among the FC-14 these impurity selective adsorption and remove almost and can not only reach by the difference on the molecular dimension.In the present invention, by considering the polarity and the aperture of sorbent material, use following three types sorbent material to adsorb and remove the sorbent material of these impurity as alternative.
First kind of sorbent material is that mean pore size is that 3.4-11 dust and Si/Al ratio are 1.5 or littler zeolite.Its object lesson comprises MS-4A.The mean pore size of MS-4A is that about 3.5 dusts and Si/Al ratio are 1.0.By using this zeolite to carry out adsorption operations, can reduce the content of ethene, tetrafluoroethylene, methane, ethane, carbon monoxide and carbonic acid gas as impurity.The kind that depends on zeolite, even foreign matter content can be reduced to 5ppm or lower, thus can obtain high purity FC-14.
If use mean pore size to be lower than 3.4 dusts, for example the aperture is about the zeolite of 3.2 dusts, can not guarantee the reduction of foreign matter content, even the Si/Al ratio is 1.5 or littler.
Even the Si/Al ratio is 1.5 or littler, if the mean pore size of zeolite can not be guaranteed the reduction of foreign matter content greater than 11 dusts.
In addition, even mean pore size is the 3.4-11 dust,, can not guarantee the reduction of foreign matter content if the Si/Al ratio of zeolite surpasses 1.5.
Second kind of sorbent material is that mean pore size is the carbon-bearing adsorbent (molecular-sieve carbon) of 3.4-11 dust.For example mean pore size is that the carbon-bearing adsorbent of about 4 dusts also can be reduced to foreign matter content 5ppm or lower as above-mentioned zeolite, thereby can obtain high purity FC-14.
Yet, if the mean pore size of carbon-bearing adsorbent surpasses 11 dusts, can not guarantee the reduction of foreign matter content, for example, almost can not guarantee the reduction of foreign matter content if use the mean pore size that is used and shows strong adsorption activity usually to be about the gac of 35 dusts.
The third sorbent material for by with mean pore size be the carbon-bearing adsorbent (second kind of sorbent material) of 3.4-11 dust add (sneaking into) mean pore size be 3.4-11 dust and Si/Al ratio be preferably 1.5 or littler zeolite (first kind of sorbent material) in the sorbent material that obtains.The kind that depends on this sorbent material can be reduced to foreign matter content even for 3ppm or lower, thereby can obtain more highly purified FC-14.The reason that obtains this result is considered to because zeolite particularly has excellent adsorption to carbon monoxide, carbonic acid gas etc., and carbon-bearing adsorbent particularly has excellent adsorption to unsaturated compound etc., and when these two kinds of sorbent materials are used in combination, brought by this effect that causes that is used in combination.
Above-mentioned zeolite and carbon-bearing adsorbent can use separately, but two or more sorbent materials also can be used in combination with required ratio.When using the third sorbent material, the ratio of mixture between zeolite and the carbon-bearing adsorbent can change according to the concentration of impurity.
Not limited especially as vinyl compound, hydrocarbon compound, carbon monoxide and/or concentration of carbon dioxide that impurity is contained among the FC-14, but this concentration is preferably 0.1 quality % or lower, 0.05 quality % or lower more preferably.
If sneak into the impurity beyond the above-mentioned impurity among the target product FC-14, for example such as FC-116 (CF
3CF
3) and FC-218 (C
3F
8) and so on perfluorochemical, these perfluorochemicals can separate and remove by carrying out distillation procedure before or after with the step of above-mentioned sorbent treatment.
In the method for the FC-14 that purifies according to the present invention, make method that the FC-14 that contains impurity contacts with sorbent material and unrestricted, for example can make impure FC-14 contact in gas phase with sorbent material, contact or in liquid phase, contact by solution-air.Wherein, the method that impure FC-14 and sorbent material are contacted in liquid phase is effectively with preferred.
For impure FC-14 is contacted in liquid phase with sorbent material, can use known method such as batch system or continous way system, but can use a kind of two unitary methods of fixed-bed type adsorption tower that for example provide usually industrial, and when a unit reaches its saturated absorption limit, use another unit and first module is regenerated.
When impure FC-14 contacted with sorbent material, treatment temp, treatment capacity and processing pressure were not restricted especially, but the preferred low temperature of treatment temp, suitable is-50 ℃ to+50 ℃.Under the liquid phase situation, just enough as long as processing pressure can be kept liquid phase, and under the gas phase situation, processing pressure is not restricted especially.
As mentioned above, the method for purification of the application of the invention, the vinyl compound, hydrocarbon compound, carbon monoxide and/or the carbonic acid gas that are contained among the FC-14 can and be removed by active adsorption, thereby can obtain high purity FC-14.The purity of gained FC-14 is 99.9997 quality % or higher, and for purity assay is 99.9997 quality % or higher FC-14 product, can use (1) to adopt the vapor-phase chromatography (GC) of TCD method, FID method (comprising the precut method separately) or ECD method, or the analytical instrument of (2) such as gas chromatography mass spectrometer (GC-MS).
Gained high purity FC-14 can be used as the etching gas in the etching step in the method for producing semiconducter device.In addition, high purity FC-14 can be used as the clean air in the cleaning in the method for producing semiconducter device.In the production method of semiconducter device such as LSI and TFT, use CVD method, sputtering method or vapor deposition method form thin or thick film and this film are etched with the formation circuit pattern.In the equipment that is used to form described thin or thick film, clean the unnecessary settling that accumulates on this equipment inwall, the anchor clamps etc. to remove, because unnecessary settling causes producing particle and must remove every now and then to produce high-quality film.
In by the etching of using FC-14, etching can be carried out under various dry etching conditions such as plasma etching and microwave etching, and FC-14 can pass through with suitable proportion and rare gas element such as He, N
2Mix with Ar or with such as HCl, O
2And H
2Gas mix and use.
Below by reference example and Comparative Examples the present invention is further specified, but the present invention is not limited to these embodiment.
The raw material embodiment 1 of FC-14
Carbon and fluorine gas are reacted in the presence of diluent gas, remove unreacted fluorine gas and purify by fractionation according to conventional methods and be rich in the product gas of FC-14.By the gc analysis product gas, gained FC-14 has the composition shown in the following table 2 as a result then.
Table 2
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9688 |
| Carbon monoxide | ????CO | ????0.0006 |
| Carbonic acid gas | ????CO 2 | ????0.0056 |
| Methane | ????CH 4 | ????0.0012 |
| Ethene | ????CH 2＝CH 2 | ????0.0112 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0028 |
| Ethane | ????CH 3CH 3 | ????0.0098 |
The raw material embodiment 2 of FC-14
Make methylene fluoride (CH
2F
2) react in the presence of diluent gas with fluorine gas, the gas with reaction imports hydrogen fluoride and the slight unreacted fluorine gas of measuring to remove generation in the alkaline cleaning tower then.Be rich in the product gas of FC-14 and passed through gc analysis by the fractionation purification according to currently known methods, gained FC-14 has the composition shown in the following table 3 as a result.
Table 3
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9722 |
| Carbon monoxide | ????CO | ????0.0005 |
| Carbonic acid gas | ????CO 2 | ????0.0025 |
| Methane | ????CH 4 | ????0.0004 |
| One vinyl fluoride | ????CH 2＝CHF | ????0.0056 |
| Difluoroethylene | ????CH 2＝CF 2 | ????0.0038 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0108 |
| Trifluoromethane | ????CHF 3 | ????0.0042 |
Embodiment 1
With 20g zeolite (molecular sieve 4A, produce by Union Showa K.K., mean pore size: 3.5 dusts, Si/Al ratio: 1) be filled in the 200ml stainless steel cylinder and vacuum-drying, the FC-14 that adds about 70g raw material embodiment 1 then in this cylinder of cooling is at the same content that often stirs that temperature is remained in-20 ℃.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 4.
Table 4
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9992 |
| Carbon monoxide | ????CO | ????＜0.0001 |
| Carbonic acid gas | ????CO 2 | ????＜0.0001 |
| Methane | ????CH 4 | ????＜0.0001 |
| Ethene | ????CH 2＝CH 2 | ????＜0.0001 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0003 |
| Ethane | ????CH 3CH 3 | ????0.0001 |
As seen from Table 4, by use mean pore size be 3.5 dusts and Si/Al ratio be 1 zeolite as sorbent material, the impurity level and the foreign matter content that can reduce among the FC-14 can be reduced to 10ppm or lower.
Embodiment 2
With 20g zeolite (molecular sieve 13X, produce by Union Showa K.K., mean pore size: 10 dusts, Si/Al ratio: 1.23) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 1 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 5.
Table 5
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9991 |
| Carbon monoxide | ????CO | ????＜0.0001 |
| Carbonic acid gas | ????CO 2 | ????＜0.0001 |
| Methane | ????CH 4 | ????＜0.0001 |
| Ethene | ????CH 2＝CH 2 | ????0.0003 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0002 |
| Ethane | ????CH 3CH 3 | ????0.0001 |
As seen from Table 5, by use mean pore size be 10 dusts and Si/Al ratio be 1.23 zeolite as sorbent material, the impurity level and the foreign matter content that can reduce among the FC-14 can be reduced to 10ppm or lower.
Embodiment 3
With 20g carbon-bearing adsorbent (molecular-sieve carbon, produce by Takeda Yakuhin Kogyo K.K., mean pore size: 4 dusts) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 2 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 6.
Table 6
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9992 |
| Carbon monoxide | ????CO | ????0.0001 |
| Carbonic acid gas | ????CO 2 | ????0.0002 |
| Methane | ????CH 4 | ????0.0001 |
| One vinyl fluoride | ????CH 2＝CHF | ????＜0.0001 |
| Difluoroethylene | ????CH 2＝CF 2 | ????＜0.0001 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????＜0.0001 |
| Trifluoromethane | ????CHF 3 | ????0.0001 |
As seen from Table 6, by use mean pore size be the carbon-bearing adsorbent (molecular-sieve carbon) of 4 dusts as sorbent material, the impurity level and the foreign matter content that can reduce among the FC-14 can be reduced to 10ppm or lower.
Embodiment 4
Will with 15g carbon-bearing adsorbent (molecular-sieve carbon, produce by Takeda Yakuhin Kogyo K.K., mean pore size: blended 15g zeolite (molecular sieve 4A 4 dusts), produce by Union Showa K.K., mean pore size: 3.5 dusts, Si/Al ratio: 1) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 1 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 7.
Table 7
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9994 |
| Carbon monoxide | ????CO | ????＜0.0001 |
| Carbonic acid gas | ????CO 2 | ????＜0.0001 |
| Methane | ????CH 4 | ????＜0.0001 |
| Ethene | ????CH 2＝CH 2 | ????＜0.0001 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????＜0.0001 |
| Ethane | ????CH 3CH 3 | ????＜0.0001 |
In order to determine the content of trace impurity, use TCD method, FID method (comprising the precut method) or ECD method to carry out microanalysis by vapor-phase chromatography or by carrying out microanalysis such as the analytical instrument of gas chromatography mass spectrometer (GC/MS), and by income value calculating purity.The result is as shown in table 8.
Table 8
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9998 |
| Carbon monoxide | ????CO | ????＜0.4ppm |
| Carbonic acid gas | ????CO 2 | ????＜0.4ppm |
| Methane | ????CH 4 | ????＜0.3ppm |
| Ethene | ????CH 2＝CH 2 | ????＜0.1ppm |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????＜0.2ppm |
| Ethane | ????CH 3CH 3 | ????＜0.2ppm |
As seen from Table 8, the purity of gained FC-14 is 99.9997 quality % or higher.
Comparative Examples 1
With 20g zeolite (molecular sieve XH-9, produce by Union Showa K.K., mean pore size: 3.2 dusts, Si/Al ratio: 1) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 1 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 9.
Table 9
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9698 |
| Carbon monoxide | ????CO | ????0.0004 |
| Carbonic acid gas | ????CO 2 | ????0.0051 |
| Methane | ????CH 4 | ????0.0012 |
| Ethene | ????CH 2＝CH 2 | ????0.0111 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0027 |
| Ethane | ????CH 3CH 3 | ????0.0097 |
As seen from Table 9, even the Si/Al ratio is 1, but if the mean pore size of zeolite less than 3.4 dusts, the content of impurity does not almost reduce.
Comparative Examples 2
With 20g zeolite (H-ZSM-5, produce by N.E.Chemcat K.K., mean pore size: 6 dusts, Si/Al ratio: 75) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 1 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 10.
Table 10
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9733 |
| Carbon monoxide | ????CO | ????0.0003 |
| Carbonic acid gas | ????CO 2 | ????0.0047 |
| Methane | ????CH 4 | ????0.0009 |
| Ethene | ????CH 2＝CH 2 | ????0.0098 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0021 |
| Ethane | ????CH 3CH 3 | ????0.0089 |
As seen from Table 10, even mean pore size is 6 dusts, but if the Si/Al ratio of zeolite surpasses 1.5, the content of impurity almost can not be reduced.
Comparative Examples 3
With 20g carbon-bearing adsorbent (gac, particulate state SHIROSAGI KL, produce by TakedaYakuhin Kygyo K.K., mean pore size: 35 dusts) be filled in the 200ml stainless steel cylinder and vacuum-drying, in this cylinder of cooling, add the FC-14 of about 70g raw material embodiment 2 then, under room temperature (about 18 ℃), stir content frequently.After about 8 hours, by the gc analysis liquid phase part.Analytical results is shown in the following table 11.
Table 11
| Compound name | Chemical formula | Purity (quality %) |
| ????FC-14 | ????CF 4 | ????99.9795 |
| Carbon monoxide | ????CO | ????0.0004 |
| Carbonic acid gas | ????CO 2 | ????0.0021 |
| Methane | ????CH 4 | ????0.0003 |
| Ethene | ????CH 2＝CH 2 | ????0.0038 |
| Difluoroethylene | ????CH 2＝CF 2 | ????0.0026 |
| Tetrafluoroethylene | ????CF 2＝CF 2 | ????0.0079 |
| Trifluoromethane | ????CHF 3 | ????0.0034 |
As seen from Table 11, if use mean pore size to surpass the carbon-bearing adsorbent of 11 dusts, the content of impurity can not be reduced.
Industrial applicability
According to the present invention, can reduce the contained amount that is very difficult to up to now impurity, particularly vinyl compound, hydrocarbon compound, carbon monoxide and/or the carbon dioxide removed in the tetrafluoromethane. High-purity tetrafluoromethane after the purification can be used as etching gas or clean air.
Claims (14)
1. the method for the tetrafluoromethane of purifying, comprise make contain one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas as the tetrafluoromethane of impurity and mean pore size be 3.4-11 dust and Si/Al ratio be 1.5 or littler zeolite and/or the mean pore size carbon-bearing adsorbent that is the 3.4-11 dust contact to reduce the amount of described impurity.
2. the method for claim 1, the tetrafluoromethane that wherein contains described impurity contacts in liquid phase with described zeolite and/or described carbon-bearing adsorbent.
3. method as claimed in claim 1 or 2, wherein said zeolite are to be selected from least a among MS-4A, MS-5A, MS-10X and the MS-13X.
4 methods as claimed in claim 1 or 2, wherein said carbon-bearing adsorbent are molecular-sieve carbon 4A and/or molecular-sieve carbon 5A.
5. as each described method among the claim 1-4, wherein one or more vinyl compounds are selected from ethene, vinyl fluoride, difluoroethylene and tetrafluoroethylene.
6. method as claimed in claim 5, wherein one or more vinyl compounds are ethene and/or tetrafluoroethylene.
7. as each described method among the claim 1-4, wherein one or more hydrocarbon compounds are selected from methane, ethane and propane.
8. method as claimed in claim 7, wherein one or more hydrocarbon compounds are methane and/or ethane.
9. as each described method among the claim 1-8, wherein one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and the total content of carbonic acid gas in described tetrafluoromethane are reduced to 3ppm or lower.
10. as each described method among the claim 1-9, wherein contain the direct fluorination process production of tetrafluoromethane of one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas by trifluoromethane and fluorine gas are reacted as impurity.
11., wherein contain the direct fluorination process production of tetrafluoromethane of one or more vinyl compounds, one or more hydrocarbon compounds, carbon monoxide and/or carbonic acid gas by carbon and fluorine gas are reacted as impurity as each described method among the claim 1-9.
12. a purity is 99.9997 quality % or higher tetrafluoromethane product, by obtaining according to purifying as each described method among the claim 1-11.
13. an etching gas comprises tetrafluoromethane product as claimed in claim 12.
14. a clean air comprises tetrafluoromethane product as claimed in claim 12.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP128681/2000 | 2000-04-28 | ||
| JP2000128681A JP4471448B2 (en) | 2000-04-28 | 2000-04-28 | Tetrafluoromethane purification method and use thereof |
| JP128681/00 | 2000-04-28 | ||
| US23070400P | 2000-09-07 | 2000-09-07 | |
| US60/230,704 | 2000-09-07 |
Publications (2)
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| CN1561318A true CN1561318A (en) | 2005-01-05 |
| CN1268592C CN1268592C (en) | 2006-08-09 |
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| CN 01801119 Expired - Lifetime CN1268592C (en) | 2000-04-28 | 2001-04-26 | Method of purifying tetrafluoromethane and utilization thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1268592C (en) |
| AU (1) | AU5261701A (en) |
| HK (1) | HK1072594A1 (en) |
| RU (1) | RU2215730C2 (en) |
| WO (1) | WO2001083412A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399126A (en) * | 2011-12-19 | 2012-04-04 | 天津市泰源工业气体有限公司 | Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption |
| CN103664502A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Octafluoropropane purifying method |
| CN103664501A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Hexafluoroethane purification method |
| CN106345264A (en) * | 2016-07-19 | 2017-01-25 | 浙江博瑞电子科技有限公司 | Method for purifying organic fluorine gas by using novel impurity decomposing agent |
| CN113784776A (en) * | 2019-08-06 | 2021-12-10 | 昭和电工株式会社 | Gas processing method and gas processing apparatus |
| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | A kind of separation method of CH3F and C3H8 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005226A1 (en) * | 2002-07-02 | 2004-01-15 | Showa Denko K. K. | Process for purifying pentafluoroethane, process for producing the same, and use thereof |
| GB0303972D0 (en) * | 2003-02-20 | 2003-03-26 | Ineos Fluor Holdings Ltd | Process |
| CN100455555C (en) * | 2003-11-10 | 2009-01-28 | 昭和电工株式会社 | Purification method of, 1, 1-difluoroethane |
| US7696392B2 (en) | 2003-11-10 | 2010-04-13 | Showa Denko K.K. | Purification method of 1,1-difluoroethane |
| US7597744B2 (en) * | 2006-07-12 | 2009-10-06 | Honeywell International Inc. | Use of molecular sieves for the removal of HFC-23 from fluorocarbon products |
| EP3693353A1 (en) * | 2019-02-11 | 2020-08-12 | Solvay Sa | A process for the purification of fluorinated olefins |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3026359A (en) * | 1960-03-16 | 1962-03-20 | Du Pont | Process for preparing polyfluoroalkanes of high purity |
| US5417742A (en) * | 1993-12-03 | 1995-05-23 | The Boc Group, Inc. | Removal of perfluorocarbons from gas streams |
| JP2924660B2 (en) * | 1994-09-08 | 1999-07-26 | 昭和電工株式会社 | Purification method of tetrafluoromethane |
-
2001
- 2001-04-26 AU AU52617/01A patent/AU5261701A/en not_active Abandoned
- 2001-04-26 CN CN 01801119 patent/CN1268592C/en not_active Expired - Lifetime
- 2001-04-26 RU RU2002101934A patent/RU2215730C2/en not_active IP Right Cessation
- 2001-04-26 WO PCT/JP2001/003664 patent/WO2001083412A2/en active Application Filing
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399126A (en) * | 2011-12-19 | 2012-04-04 | 天津市泰源工业气体有限公司 | Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption |
| CN103664502A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Octafluoropropane purifying method |
| CN103664501A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Hexafluoroethane purification method |
| CN103664501B (en) * | 2012-09-07 | 2015-09-23 | 佛山市华特气体有限公司 | A kind of purification process of hexafluoroethane |
| CN106345264A (en) * | 2016-07-19 | 2017-01-25 | 浙江博瑞电子科技有限公司 | Method for purifying organic fluorine gas by using novel impurity decomposing agent |
| CN113784776A (en) * | 2019-08-06 | 2021-12-10 | 昭和电工株式会社 | Gas processing method and gas processing apparatus |
| CN113784776B (en) * | 2019-08-06 | 2024-03-19 | 株式会社力森诺科 | Gas treatment method and gas treatment apparatus |
| US12121847B2 (en) | 2019-08-06 | 2024-10-22 | Resonac Corporation | Gas treatment method and gas treatment device |
| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | A kind of separation method of CH3F and C3H8 |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1072594A1 (en) | 2005-09-02 |
| WO2001083412A2 (en) | 2001-11-08 |
| CN1268592C (en) | 2006-08-09 |
| AU5261701A (en) | 2001-11-12 |
| RU2215730C2 (en) | 2003-11-10 |
| WO2001083412A3 (en) | 2002-04-25 |
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