CN103910600A - Method for preparing ultrapure fluoromethane - Google Patents
Method for preparing ultrapure fluoromethane Download PDFInfo
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- CN103910600A CN103910600A CN201310004972.3A CN201310004972A CN103910600A CN 103910600 A CN103910600 A CN 103910600A CN 201310004972 A CN201310004972 A CN 201310004972A CN 103910600 A CN103910600 A CN 103910600A
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- fluoromethane
- molecular sieve
- type molecular
- preparation
- superelevation
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Abstract
The invention provides a method for preparing ultrapure fluoromethane through an adsorption process. Impurities in crude fluoromethane are removed by adopting A-type molecular sieve and/or active carbon with the particle size of 1.5-3.0mm, and the A-type molecular sieve and active carbon are activated before use. Highly pure fluoromethane with the purity of above 99.99 even 99.9999% can be obtained through the preparation method, and the prepared ultrapure fluoromethane can be used in the semiconductor/electron industry as an etching gas.
Description
Technical field
The invention belongs to gas purification technical field, relate to the preparation method of the single fluoromethane of a kind of superelevation.
Background technology
One fluoromethane, chemical formula is CH
3f, code name R41 or HFC-41, be a kind of nontoxic, colourless, odorless, flammable liquefied gas in steel cylinder that is stored in.One fluoromethane is used in the processing procedure of semi-conductor and electronic product, can dissociate fluorion at next fluoromethane of radio-frequency field, the optionally film of etch silicon compound, i.e. reactive ion etching (reactive-ion etching).One fluoromethane etching gas is very strict to purity requirement, often needs to be greater than 99.99%, and even 99.999%.
The preparation method of one fluoromethane mainly contains two kinds, respectively taking methylol and methyl chloride as raw material.
Japanese Patent No.4-7330 discloses the method for HFC-41 of preparation a kind of, and wherein methylol and hydrogen fluoride use fluorination catalyst (chromium fluoride) to carry out gas-phase reaction at the temperature of 100～500 DEG C, see reaction formula (1):
CH
3OH+HF→CH
3F+H
2O (1)
In US Patent No. 4139568, also disclose methylol and hydrogen fluoride and at the temperature of 250400 DEG C, used fluorination catalyst generation gas-phase reaction, thereby prepared the method for HFC-41.But, the method produce problem be the deteriorated of fluorination catalyst and due to production water byproduct etching reactor.
Japanese Patent No.60-13726 discloses the method for the another kind of HFC-41 of preparation, wherein methyl chloride (CH
3cl) and HF at the temperature of 100～400 DEG C, use fluorination catalyst chromium fluoride to carry out gas-phase reaction, see reaction formula (2):
CH
3Cl+HF→CH
3F+HCl (2)
But because this reaction is the as above balanced reaction shown in surface chemistry equation (2), the problem of the method is to improve catalytic activity, and cause owing to forming the approaching HFC-41 of boiling point and the azeotropic mixture of hydrogenchloride the problem that is difficult to separate.
Chinese patent CN101023051A, for the HFC-41 preparation method taking methyl chloride as raw material, proposes the Methods For Purification HFC-41 absorbing with rectifying and alkali.After reaction, mixture is through rectifying separation, and tower top is fluoromethane and hydrogenchloride, is methyl chloride and hydrogen fluoride at the bottom of tower, and at the bottom of tower, component reuse is to reaction process, and tower top component absorbs and removes hydrogenchloride through alkali again, thereby obtains more than 99.9% HFC-41 product.Patent WO 2005/009933 A1 and WO 2006/030677 A1 clear and electrician company adopt rectification method separate fluorine methane and hydrogenchloride, and tower top is the HFC-41 after purifying, and is the azeotropic mixture of fluoromethane and hydrogenchloride at the bottom of tower.Hydrogenchloride can be reduced to below 1ppm.
In the preparation process of HFC-41, thick product is except HCl, HF, CH
3outside Cl impurity, also there is other by product being produced by cracking, as CH
4, C
2h
4, C
2h
6, C
3h
6, C
3h
8deng.For obtaining ultra-pure HFC-41 product, must remove these impurity to very low concentrations scope.
Summary of the invention
The object of the invention is to supply feasible, the applicable suitability for industrialized production of a kind of technological line, efficient adsorption to remove CH
4, C
2h
4, C
2h
6, C
3h
6, C
3h
8deng the preparation method of the single fluoromethane of superelevation of impurity.
For reaching goal of the invention, the invention provides following technical scheme:
The preparation method of the single fluoromethane of a kind of superelevation, adopt the gac that A type molecular sieve and/or particle diameter are 1.5～3.0mm to remove the impurity in a fluoromethane crude product, described A type molecular sieve and gac be activated processing before use, and activation temperature is 120～300 DEG C, and soak time is 2～3 hours.
The sorbent material that the present invention adopts can be A type molecular sieve and/or gac.Because the critical diameter of impurity in a fluoromethane crude product is all less than
so described A type molecular sieve is one or both in 4A type molecular sieve and 5A type molecular sieve preferably, gac is preferably coal mass active carbon.The use form of A type molecular sieve and gac is preferably particle.Sorbent material of the present invention is best activated processing before use, preferred activation treatment mode can be to activate in retort furnace, also can rare gas element in reaction tubes exist under high-temperature activation, soak time is 2～3 hours, wherein the activation temperature of A type molecular sieve is preferably 180～300 DEG C, the activation temperature of gac is preferably 120～180 DEG C, and rare gas element is preferably nitrogen.Sorbent material of the present invention can obtain by the mode of buying.
The fluoromethane crude product that the present invention uses contains the main organic impurity such as methane, ethene, ethane, propylene, propane, and sorbent material provided by the invention can be removed these organic impuritys effectively.
For obtaining good implementation result, after changing gas phase into, the fluoromethane crude product that the present invention uses enters gas-solid adsorption bed and A type molecular sieve and/or gac Continuous Contact imurity-removal.One fluoromethane crude product can contact with sorbent material by carrier gas conveying, and described carrier gas is rare gas element, preferred nitrogen.The input speed of one fluoromethane crude product is preferably 0.1～5.5g/min.Adsorption temp is preferably-30～40 DEG C.
Method provided by the invention has following distinguishing feature compared to existing technology:
(1) can obtain the even single fluoromethane product of more than 99.9999% superelevation of purity 99.999%;
(2) organic impuritys such as methane in can disposable removal one fluoromethane crude product, ethene, ethane, propylene, propane, adsorption rate is higher, is applicable to scale operation;
(3) sorbent material is nontoxic, environmentally friendly, and non-secondary pollution is easily realized operate continuously.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that within the scope of claims, may comprise.
Embodiment 1
First with pallet, a certain amount of 4A type molecular sieve is put into retort furnace, be heated to 300 DEG C of activation, keep soak time to take out after 3 hours.The 4A type molecular sieve taking after 300g activation is positioned in 1L stainless steel steel cylinder, sealing, vacuumize, then toward adding 400g mono-fluoromethane crude product in 1L steel cylinder, (foreign matter content is: methane 10ppm, ethene 3ppm, ethane 1ppm, propylene 2ppm, propane 103ppm), at room temperature start absorption, until adsorption equilibrium.After adsorption equilibrium, result is as shown in table 1.
Embodiment 2
First with pallet, a certain amount of 5A type molecular sieve is put into retort furnace, be heated to 300 DEG C of activation, keep soak time to take out after 3 hours.The 5A type molecular sieve taking after 300g activation is positioned in 1L stainless steel steel cylinder, and sealing, vacuumizes, and then in 1L steel cylinder, adds 400g mono-fluoromethane crude product (foreign matter content is with embodiment 1), at room temperature starts absorption, until adsorption equilibrium.After adsorption equilibrium, result is as shown in table 1.
Embodiment 3
First with pallet, a certain amount of gac is put into baking oven, be heated to 180 DEG C of activation, keep soak time to take out after 3 hours.The gac taking after 300g activation is positioned in 1L stainless steel steel cylinder, and sealing, vacuumizes, and then in 1L steel cylinder, adds 400g mono-fluoromethane crude product (foreign matter content is with embodiment 1), at room temperature starts absorption, until adsorption equilibrium.After adsorption equilibrium, result is as shown in table 1.
Table 1
| Embodiment | Sorbent material | Methane | Ethene | Ethane | Propylene | Propane | HFC-41 |
| 1 | 4A type molecular sieve | ≤1ppm | 3ppm | 1ppm | 1ppm | 4ppm(8h) | 99.999% |
| 2 | 5A type molecular sieve | ≤1ppm | 2ppm | 1ppm | 3ppm(8h) | 2ppm(8h) | 99.999% |
| 3 | Gac | ≤1ppm | 2ppm | 1ppm | 1ppm | 1ppm | 99.9994% |
Embodiment 4
Taking 130g gac I (particle diameter is 1.5mm) is filled in the stainless steel gas-solid adsorption column that internal diameter is 25mm, the high 90cm of being, first by adsorption tube N
2under 180 DEG C, 1atm, purge 3h, then continue logical nitrogen and be cooled to room temperature, vacuumize.Then at room temperature, pressure is under 0.05～0.5MPa (gauge pressure), adds a fluoromethane crude product (foreign matter content is with embodiment 1) with the input speed of 5.5g/min from absorption fixed bed top, starts absorption, until adsorption equilibrium.Gas after absorption 13h with the wherein content of each component of gas chromatograph analysis, the results are shown in Table 2 after condensation is collected.
Embodiment 5
Taking 130g gac II (particle diameter is 2.5～3.0mm) is filled in the stainless steel gas-solid adsorption column that internal diameter is 25mm, the high 90cm of being, first by adsorption tube N
2under 180 DEG C, 1atm, purge 3h, then continue logical nitrogen and be cooled to room temperature, vacuumize.Then at room temperature, pressure is under 0.05～0.5MPa (gauge pressure), adds a fluoromethane crude product (foreign matter content is with embodiment 1) with the input speed of 5.5g/min from absorption fixed bed top, starts absorption, until adsorption equilibrium.Gas after absorption 16h with the wherein content of each component of gas chromatograph analysis, the results are shown in Table 2 after condensation is collected.
Embodiment 6
Taking 300g 4A molecular sieve filled is in 25mm, the high stainless steel gas-solid adsorption column for 90cm, first by adsorption tube N at internal diameter
2under 300 DEG C, 1atm, purge 3h, then continue logical nitrogen and be cooled to room temperature, vacuumize.Then at room temperature, pressure is under 0.05～0.5MPa (gauge pressure), adds a fluoromethane crude product (foreign matter content is with embodiment 1) with the input speed of 5.5g/min from absorption fixed bed top, starts absorption, until adsorption equilibrium.Gas after absorption 9.5h with the wherein content of each component of gas chromatograph analysis, the results are shown in Table 2 after condensation is collected.
Table 2
| Embodiment | Sorbent material | Methane | Ethene | Ethane | Propylene | Propane | HFC-41 |
| 4 | Gac I | ≤1ppm | ≤1ppm | ≤1ppm | ≤1ppm | 1ppm | ≥99.999% |
| 5 | Gac II | ≤1ppm | ≤1ppm | ≤1ppm | ≤1ppm | ≤1ppm | ≥99.9995% |
| 6 | 4A molecular sieve | ≤1ppm | ≤1ppm | ≤1ppm | ≤1ppm | 1ppm | ≥99.999% |
Claims (9)
1. the preparation method of the single fluoromethane of superelevation, it is characterized in that adopting the gac that A type molecular sieve and/or particle diameter are 1.5～3.0mm to remove the impurity in a fluoromethane crude product, described A type molecular sieve and gac be activated processing before use, activation temperature is 120～300 DEG C, and soak time is 2～3 hours.
2. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that described A type molecular sieve is selected from the one, two or three in 3A type molecular sieve, 4A type molecular sieve and 5A type molecular sieve.
3. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that described gac is coal mass active carbon.
4. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that the use form of described A type molecular sieve and gac is particle.
5. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that described A type molecular sieve and gac activate in retort furnace or in reaction tubes under rare gas element exists high-temperature activation, the activation temperature of A type molecular sieve is 180～300 DEG C, and the activation temperature of gac is 120～180 DEG C.
6. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that the impurity in a described fluoromethane crude product is methane, ethene, ethane, propylene and propane.
7. according to the preparation method of the single fluoromethane of superelevation claimed in claim 1, it is characterized in that a described fluoromethane crude product enters gas-solid adsorption bed and A type molecular sieve and/or gac Continuous Contact imurity-removal after gasification.
8. according to the preparation method of the single fluoromethane of superelevation claimed in claim 7, it is characterized in that described adsorption temp is-30～40 DEG C.
9. according to the preparation method of the single fluoromethane of superelevation claimed in claim 7, it is characterized in that a described fluoromethane crude product input speed is 0.1～5.5g/min.
Priority Applications (1)
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|---|---|---|---|
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363407A (en) * | 2014-08-11 | 2016-03-02 | 浙江蓝天环保高科技股份有限公司 | Modified adsorbent and applications of modified adsorbent in ultra-high purity methyl fluoride preparation |
| CN105646138A (en) * | 2014-11-26 | 2016-06-08 | 天津市科密欧化学试剂有限公司 | Preparation method of chromatographic-grade carbon tetrachloride |
| CN105712351A (en) * | 2016-04-18 | 2016-06-29 | 张玲 | Method for adsorption purification of silicane |
| US20200172456A1 (en) * | 2015-06-03 | 2020-06-04 | Daikin Industries, Ltd. | Composition including fluoromethane and method for producing same |
| CN112898114A (en) * | 2020-09-30 | 2021-06-04 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of monofluoromethane |
| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | Separation method of CH3F and C3H8 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363407A (en) * | 2014-08-11 | 2016-03-02 | 浙江蓝天环保高科技股份有限公司 | Modified adsorbent and applications of modified adsorbent in ultra-high purity methyl fluoride preparation |
| CN105363407B (en) * | 2014-08-11 | 2018-02-02 | 浙江蓝天环保高科技股份有限公司 | A kind of adsorbent of modification and its application in the preparation of a ultra-pure fluoromethane |
| CN105646138A (en) * | 2014-11-26 | 2016-06-08 | 天津市科密欧化学试剂有限公司 | Preparation method of chromatographic-grade carbon tetrachloride |
| US20200172456A1 (en) * | 2015-06-03 | 2020-06-04 | Daikin Industries, Ltd. | Composition including fluoromethane and method for producing same |
| CN105712351A (en) * | 2016-04-18 | 2016-06-29 | 张玲 | Method for adsorption purification of silicane |
| CN112898114A (en) * | 2020-09-30 | 2021-06-04 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of monofluoromethane |
| CN114249628A (en) * | 2021-12-31 | 2022-03-29 | 华南理工大学 | Separation method of CH3F and C3H8 |
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Application publication date: 20140709 |