CN102399126A - Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption - Google Patents
Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption Download PDFInfo
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- CN102399126A CN102399126A CN2011104250680A CN201110425068A CN102399126A CN 102399126 A CN102399126 A CN 102399126A CN 2011104250680 A CN2011104250680 A CN 2011104250680A CN 201110425068 A CN201110425068 A CN 201110425068A CN 102399126 A CN102399126 A CN 102399126A
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- tetrafluoromethane
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Abstract
The invention discloses a method for preparing high purity tetrafluoromethane through combination of rectification and adsorption. The method is mainly characterized in that: equipment for generating tetrafluoromethane continuously supplies the tetrafluoromethane, and fluorochloromethane and potassium bifluoride are subjected to gas-phase reaction to form the tetrafluoromethane. In the method for preparing the high purity tetrafluoromethane, a raw material preparation system, a tetrafluoromethane gas preparation system and a liquefying and gasifying system for the tetrafluoromethane purified through combination of rectification and adsorption. The method has the advantages that: the product has high yield and high purity (99.0-99.9 percent), has a few impurities which are easy to separate; and besides the product, other harmful and toxic byproducts are absent, the operation is convenient, and the method is an ideal technology for preparing the high purity tetrafluoromethane.
Description
Technical field
The present invention relates to a kind of alkanes Chemicals, particularly a kind of rectifying and adsorption combined mode prepare the Technology of high-purity tetrafluoromethane method, are suitable for the synthetic tetrafluoromethane of chemical industry
Background technology
tetrafluoro-methane is incombustible colourless, tasteless high pressure liquefied gas.Tetrafluoro-methane is the maximum plasma etch gases of consumption in the present microelectronics industry; In the electron device surface cleaning; The production of solar cell; Laser technology, gas phase insulation, cryogenic refrigeration, leak check agent, control cosmic rocket attitude, the aspects such as stain remover during printed wiring is produced are also used in a large number.Because its chemicalstability, tetrafluoro-methane can be used for Metal smelting, for example: copper, stainless steel, carbon steel, aluminium, Monel etc.; Also can be used for plastic industry; As: viton, X 050, also can be widely used in silicon, silicon-dioxide, silicon nitride, the etching of thin-film materials such as phosphorosilicate glass and tungsten is in the electron device surface cleaning.Original technology can not continuous production, the equipment fluctuation of service, and energy consumption is high, and product purity is low
Summary of the invention
problem to be solved by this invention is that overcome the deficiency of prior art, prior art can not be produced high-purity tetrafluoromethane, and present technique provides the high-purity tetrafluoromethane method of a kind of preparation Technology.This technology not only technology is reasonable, and preparation is simple, and is that the tetrafluoromethane purity of producing is brought up to 5N (99.999%), and has solved problem of environmental pollution.
The technical scheme that the present invention adopts is:
A kind of method that adopts rectifying and adsorption combined mode to produce high-purity tetrafluoromethane is characterized in that, at catalyzer CrO
2
F
2
Fluidized-bed, supply with thick tetrafluoromethane (300-350 kilogram/hour) continuously by the equipment that tetrafluoromethane takes place, carry out gas-phase reaction with fluorochloromethane and hydrogen fluoride and prepare tetrafluoromethane, through the high-purity tetrafluoromethane of multistage reacted;
Wherein the 1st section reaction is to be filled with CrO
2
F
2
Make CF in the fluidized-bed reactor of catalyzer
3
Cl and HF reaction, 200-600 ℃ of reaction down, or CrF
3
3H
2
O is at O
2
Exist to heat down in 350-750 ℃ down and make; CF3Cl is controlled at 1:2-8 with the amount of substance ratio of HF, and gas space velocity is 10-150h
-1
, temperature of reaction is 380-420 ℃, the gas of the 1st section generation gets into the 2nd section reaction after washing, alkali cleaning, drying;
In the 2nd section reaction, feed HF again, make CF
3
Cl is controlled at 1:0.3-5 with the amount of substance ratio of HF, and gas space velocity is at 10 ~ 300h
-1
, temperature of reaction is constant; Can make unreacted CF in this way
3
The Cl x is controlled at 15 * 10
-6
Below, product has higher purity;
In rectifying, adsorb, select to adsorb the sorbent material of removing these impurity, be about to distillation and make up, make total impurities be lower than 1 * 10 with absorption
-6
, produce high-purity tetrafluoromethane of 99.999%.
More detailed the disclosing of
the present invention adopts rectifying and adsorption combined mode to produce the Technology of high-purity tetrafluoromethane method; Mainly be to supply with thick tetrafluoromethane continuously by the equipment that tetrafluoromethane takes place; Carry out gas-phase reaction with fluorochloromethane and hydrogen fluoride (HF) and prepare tetrafluoromethane; Since fluorochloromethane fluoridize corresponding methane difficulty, therefore reaction is many carries out having under the condition of catalyzer, catalyzer uses the compound that contains Cr usually.Technology through the high-purity tetrafluoromethane of multistage reacted.The 1st section reaction is in the fluidized-bed reactor that is filled with the CrO2F2 catalyzer, to make CF3Cl and HF reaction, and reaction formula is following:
CF
3
Cl?+?HF
CF
4
?+?HCl
Catalyst system therefor can pass through Cr (III) oxyhydroxide and HF reacts down at 200-600 ℃, or CrF
3
3H
2
O is at O
2
Exist to heat down in 350-750 ℃ down and make.CF
3
Cl is controlled at 1 with the amount of substance ratio of HF: (2-8), gas space velocity is 10 ~ 150h
-1
, temperature of reaction is 380-420 ℃.The gas of the 1st section generation gets into the 2nd section reaction after washing, alkali cleaning, drying.
In the 2nd section reaction, feed HF again, make CF3Cl and the amount of substance ratio of HF be controlled at 1: (0.3-5), gas space velocity is at 10 ~ 300h
-1
, temperature of reaction is constant.Can make unreacted CF3Cl x be controlled at 15 * 10 in this way
-6
Below, product has higher purity.According to the foreign matter content of rough tetrafluoromethane, will contain low boiling point component and (C such as H2, N2, O2, Ar, CO, CH4
2
H
5
) 2O, CH
3
Cl, C
2
H
5
High boiling point compositions such as Cl, B4H10, B5H9, B5H11 are particularly near BF
3
The rough BF3 of impurity such as the CO2 that is difficult to fractionation by distillation of boiling point, C2H6 adsorbs in rectifying, selects to adsorb the sorbent material of removing these impurity, is about to distillation and makes up with absorption, makes total impurities be lower than 1 * 10
-6
, produce high-purity tetrafluoromethane of 99.999%.
by raw material preparation system → tetrafluoromethane gas preparation system, → liquefaction of rectifying and adsorption combined purifying tetrafluoromethane, carburetion system constitutes the high-purity tetrafluoromethane method technology of preparation.Its advantage is that product yield is high, purity high (99.0% ~ 99.9%), and the few and separate easily of impurity except that product itself, does not have other harmful, deleterious by products, operates more conveniently yet, is the desirable technique that high-purity tetrafluoromethane prepares.
The advantage that preparation method of the present invention had is:
(1) present method can continous-stable the purification tetrafluoro-methane, solved the drawback that can not stablize purification of original batch fractionating.
(2) integrated continuous rectification can better utilised cold and heat, makes production cost lower.
Steady quality behind
(3) continuous production can large-scale industrial production.
Description of drawings
Fig. 1 produces the technical process of high-pure carbon tetrafluoride for the absorption-low temperature rectification method
Wherein
1, the 2-adsorber; The 3-low-temperature fractionating tower; The 4-surge tank; The 5-molding machine; The 6-condensing surface
The 7-cryogenic heat exchanger; 8-ethene surge tank; The 9-vacuum pump; The 10-compressor.
Embodiment:
The present invention is explained below in conjunction with embodiment in
; The scheme of embodiment described here; Do not limit the present invention; One of skill in the art can make improvements and change according to spirit of the present invention, and described these improvement and variation all should be regarded as within the scope of the invention, and scope of the present invention and essence are limited claim.
Embodiment 1
At the fluidized-bed of catalyzer CrO2F2, supply with thick tetrafluoromethane (300 kilograms/hour) continuously by the equipment that tetrafluoromethane takes place, carry out gas-phase reaction with fluorochloromethane and hydrogen fluoride and prepare tetrafluoromethane, through the high-purity tetrafluoromethane of multistage reacted;
Wherein the 1st section reaction is in the fluidized-bed reactor that is filled with the CrO2F2 catalyzer, to make CF3Cl and HF reaction, and 200 ℃ of reactions down, or CrF33H2O heats under 350 ℃ under O2 and makes; CF
3
Cl is controlled at 1:2 with the amount of substance ratio of HF, and gas space velocity is 10-150h
-1
, temperature of reaction is 380 ℃, the gas of the 1st section generation gets into the 2nd section reaction after washing, alkali cleaning, drying;
In the 2nd section reaction, feed HF again, make CF
3
Cl is controlled at 1:0.3 with the amount of substance ratio of HF, and gas space velocity is at 10 ~ 300h
-1
, temperature of reaction is constant; Can make unreacted CF in this way
3
The Cl x is controlled at 15 * 10
-6
Below, product has higher purity; In rectifying, adsorb, select to adsorb the sorbent material of removing these impurity, be about to distillation and make up, make total impurities be lower than 1 * 10 with absorption
-6
, produce high-purity tetrafluoromethane of 99.999%.
At catalyzer CrO
2
F
2
Fluidized-bed, supply with thick tetrafluoromethane (350 kilograms/hour) continuously by the equipment that tetrafluoromethane takes place, carry out gas-phase reaction with fluorochloromethane and hydrogen fluoride and prepare tetrafluoromethane, through the high-purity tetrafluoromethane of multistage reacted;
Wherein the 1st section reaction is to be filled with CrO
2
F
2
Make CF in the fluidized-bed reactor of catalyzer
3
Cl and HF reaction, 600 ℃ of reactions down, or CrF
3
3H
2
O is at O
2
Exist to heat down in 750 ℃ down and make; CF
3
Cl is controlled at 1:8 with the amount of substance ratio of HF, and gas space velocity is 10-150h
-1
, temperature of reaction is 420 ℃, the gas of the 1st section generation gets into the 2nd section reaction after washing, alkali cleaning, drying;
In the 2nd section reaction, feed HF again, make CF
3
Cl is controlled at 1:5 with the amount of substance ratio of HF, and gas space velocity is at 10 ~ 300h
-1
, temperature of reaction is constant; Can make unreacted CF in this way
3
The Cl x is controlled at 15 * 10
-6
Below, product has higher purity; In rectifying, adsorb, select to adsorb the sorbent material of removing these impurity, be about to distillation and make up, make total impurities be lower than 1 * 10 with absorption
-6
, produce high-purity tetrafluoromethane of 99.999%
Claims (1)
1. method that adopts rectifying and adsorption combined mode to produce high-purity tetrafluoromethane; It is characterized in that; Fluidized-bed at catalyzer CrO2F2; By the equipment 300-350 kilogram that tetrafluoromethane takes place/hour supply with thick tetrafluoromethane continuously, carry out gas-phase reaction with fluorochloromethane and hydrogen fluoride and prepare tetrafluoromethane, through the high-purity tetrafluoromethane of multistage reacted;
Wherein the 1st section reaction is to be filled with CrO
2F
2Make CF in the fluidized-bed reactor of catalyzer
3Cl and HF reaction, 200-600 ℃ of reaction down, or CrF
33H
2O is at O
2Exist to heat down in 350-750 ℃ down and make; CF
3Cl is controlled at 1:2-8 with the amount of substance ratio of HF, and gas space velocity is 10-150h
-1, temperature of reaction is 380-420 ℃, the gas of the 1st section generation gets into the 2nd section reaction after washing, alkali cleaning, drying;
In the 2nd section reaction, feed HF again, make CF
3Cl is controlled at 1:0.3-5 with the amount of substance ratio of HF, and gas space velocity is at 10 ~ 300h
-1, temperature of reaction is constant; Can make unreacted CF in this way
3The Cl x is controlled at 15 * 10
-6Below, product has higher purity;
In rectifying, adsorb, select to adsorb the sorbent material of removing these impurity, be about to distillation and make up, make total impurities be lower than 1 * 10 with absorption
-6, produce high-purity tetrafluoromethane of 99.999%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104250680A CN102399126A (en) | 2011-12-19 | 2011-12-19 | Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption |
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|---|---|---|---|
| CN2011104250680A CN102399126A (en) | 2011-12-19 | 2011-12-19 | Method for preparing high purity tetrafluoromethane through combination of rectification and adsorption |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664502A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Octafluoropropane purifying method |
| CN103951543A (en) * | 2014-04-18 | 2014-07-30 | 佛山市华特气体有限公司 | Device and method for purifying trifluoromethane |
| CN108529589A (en) * | 2018-06-21 | 2018-09-14 | 山东重山光电材料股份有限公司 | A kind of method of industrialized production fluorinated carbon material |
| CN111099957A (en) * | 2019-12-26 | 2020-05-05 | 福建德尔科技有限公司 | Purification system and method for electronic-grade carbon tetrafluoride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264530A (en) * | 1979-02-26 | 1981-04-28 | Daikin Kogyo Co., Ltd. | Process for preparing high purity tetrafluoromethane |
| EP0690147A1 (en) * | 1994-07-01 | 1996-01-03 | Haldor Topsoe A/S | Process for the electrochemical fluorination of a hydrocarbon substratum |
| CN1561318A (en) * | 2000-04-28 | 2005-01-05 | 昭和电工株式会社 | Method of purifying tetrafluoromethane and utilization thereof |
| CN101541673A (en) * | 2006-05-31 | 2009-09-23 | 纳幕尔杜邦公司 | Process for purifying perfluorinated products |
-
2011
- 2011-12-19 CN CN2011104250680A patent/CN102399126A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264530A (en) * | 1979-02-26 | 1981-04-28 | Daikin Kogyo Co., Ltd. | Process for preparing high purity tetrafluoromethane |
| EP0690147A1 (en) * | 1994-07-01 | 1996-01-03 | Haldor Topsoe A/S | Process for the electrochemical fluorination of a hydrocarbon substratum |
| CN1561318A (en) * | 2000-04-28 | 2005-01-05 | 昭和电工株式会社 | Method of purifying tetrafluoromethane and utilization thereof |
| CN101541673A (en) * | 2006-05-31 | 2009-09-23 | 纳幕尔杜邦公司 | Process for purifying perfluorinated products |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664502A (en) * | 2012-09-07 | 2014-03-26 | 佛山市华特气体有限公司 | Octafluoropropane purifying method |
| CN103664502B (en) * | 2012-09-07 | 2015-09-23 | 佛山市华特气体有限公司 | A kind of octafluoropropane purification process |
| CN103951543A (en) * | 2014-04-18 | 2014-07-30 | 佛山市华特气体有限公司 | Device and method for purifying trifluoromethane |
| CN103951543B (en) * | 2014-04-18 | 2016-04-20 | 广东华特气体股份有限公司 | A kind of trifluoromethane purification devices and purification process |
| CN108529589A (en) * | 2018-06-21 | 2018-09-14 | 山东重山光电材料股份有限公司 | A kind of method of industrialized production fluorinated carbon material |
| CN108529589B (en) * | 2018-06-21 | 2024-04-26 | 山东重山光电材料股份有限公司 | Industrial production method of fluorocarbon material |
| CN111099957A (en) * | 2019-12-26 | 2020-05-05 | 福建德尔科技有限公司 | Purification system and method for electronic-grade carbon tetrafluoride |
| CN111099957B (en) * | 2019-12-26 | 2021-04-13 | 福建德尔科技有限公司 | Purification system and method for electronic-grade carbon tetrafluoride |
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Application publication date: 20120404 |