CN1076333C - Process for producing hexafluoroethane - Google Patents
Process for producing hexafluoroethane Download PDFInfo
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- CN1076333C CN1076333C CN97102133A CN97102133A CN1076333C CN 1076333 C CN1076333 C CN 1076333C CN 97102133 A CN97102133 A CN 97102133A CN 97102133 A CN97102133 A CN 97102133A CN 1076333 C CN1076333 C CN 1076333C
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- Prior art keywords
- reaction
- gas
- tetrafluoroethane
- fluorine
- hydrofluorocarbons
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-
- 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
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing hexafluoroethane which comprises reacting a hydrofluorocarbon containing two carbon atoms in the molecule with fluorine gas at an elevated temperature in a vapor phase in the presence of a diluent gas.
Description
The present invention relates to produce the method for hexafluoroethane, comprise making the hydrofluorocarbons that contains two carbon atoms in the molecule and fluorine gas in vapour phase, under the higher temperature, in the presence of diluent gas, react.
Hexafluoroethane (hereinafter is designated as " FC-116 " or " CF
3CF
3") is used to for example semi-conductive dry etching.
About the production of FC-16, several different methods has been proposed so far.The example of this class currently known methods comprises that (1) is raw-material electrochemical fluorination method with ethane and/or ethene; (2) with tetrafluoroethylene or another kind of starting material pyrolytic method; (3) comprise and make fluorizated methods such as acetylene, ethene and/or ethane with metal fluoride; (4) comprise and make fluorizated methods such as dichloro tetrafluoro ethane, a chloropentafluoroethane with hydrogen fluoride; (5) make the direct fluorination method of ethane etc. and fluorine gas reaction.
The shortcoming of aforesaid method (1) is many side reactions and the separation of the product that responds and the problem of purifying to occur.
Method (2) not only must be used high temperature of reaction, and yield is also low.Method (3) exists from the problem of the aspects such as consumption of the regeneration of the fluorine gas of metal pentafluoride deposits yields, fluorine gas, though the control of reaction heat improves.In using hydrofluoric method (4), it is low that reaction produces a large amount of hydrochloric acid by-product and necessary employing high temperature and yield.
The known embodiment of method (5) reaction comprises that (a) makes fluorine gas and ethane (C with injection reactor
2H
6) react to obtain tetrafluoromethane and C
2F
6Method (J.Amer.Chem.Soc., 77,3307 (1955), J.Amer.Chem.Soc., 82,5827 (1960)), wherein be diluent gas with nitrogen; (b) with the reactor that has a porousness alumina tube with fluorine gas with C-H fluorizated method (EP-31,519 (1981)); (c) with the reactor (two-tube reactor) that has a porous metal pipe with fluorine gas in the presence of diluent gas with straight chain hydrocarbon fluorizated method, diluent gas is SF
6, CF
4, C
2F
6Or C
3F
8(EP-33,210 (1981)).
Other known method with fluorine gas reaction comprises that (e) makes the method (United States Patent (USP) 5,406,008 (1995)) of fluorine gas and saturated or unsaturated hydrocarbons or partially fluorinated hydrocarbon reaction generation hydrofluorocarbons; With the method (JP-A-2-207052) (" JP-A " is meant unexamined disclosed Japanese patent application) of producing fluorinated olefin from alkene and the carbon that is adsorbed with fluorine gas.
The shortcoming of the above-mentioned direct fluorizated method of use fluorine gas is owing to used reactive extremely strong fluorine gas, has as the organic compound of substrate and the danger of fluorine gas blast, and also has the danger of corrosion etc.In addition, comprise in addition owing to producing heat and the C-C key is decomposed and polymeric danger and the fear that produces rapid reaction or blast owing to the generation and the deposition of carbon etc.For example, for the synthetic perfluoro-carbon of direct fluorination method the time, straight chain hydrocarbon compound and fluorine gas reaction react the super amount heat of simultaneous, shown in reaction scheme (1) and (2).
(ΔH＝-690 kcal/mol)
(ΔH＝-479 kcal/mol)
With ethane is that every mole of ethane of the reaction shown in the raw-material reaction scheme (1) needs 6 moles of fluorine, and is that the every mole of methane of the reaction shown in the raw-material reaction scheme (2) needs 4 moles of fluorine with methane.
Thereby the amount of reaction heat is directly proportional with the mole number of used fluorine; The amount of the big more then reaction heat of the consumption of fluorine is big more.The increase of reaction heat causes the strong division of C-C, blast etc. easily, and causes the reduction of yield, thus the generation problem relevant with operation with industrial production.Being suppressed at the routine techniques that reaction heat takes place suddenly in the direct fluorination method comprises: with rare gas element (for example nitrogen or helium) dilution fluorine; Being dissolved in the organic compound substrate to fluorine is in the inert solvent, with the preparation low concentration solution; With in low temperature range, react.Be reflected at vapour phase and carry out for making, the device that the someone has proposed a kind of design is injection reactor for example, makes fluorine contact bit by bit with organic compound as substrate.
Finished the present invention for overcoming the problems referred to above with the realization above-mentioned purpose.Therefore, one of purpose of the present invention provide a kind of with organic compound substrate and fluorine gas by direct fluorination method safety, the method for suitability for industrialized production FC-116 effectively and at low cost.
In the following description, other purpose of the present invention and effect become apparent.
The invention provides the method for producing hexafluoroethane, comprise making the hydrofluorocarbons (HFC) that contains two carbon atoms in the molecule and fluorine gas in vapour phase, under the higher temperature, in the presence of diluent gas, react.
Diluent gas preferably includes at least a in tetrafluoromethane, hexafluoroethane, octafluoropropane and the hydrogen fluoride, preferably be rich in hydrogen fluoride (its hydrogen fluoride content be preferably the diluent gas total amount 50% or higher).
Organic compound as substrate is the hydrofluorocarbons (HFC) that contains two carbon atoms in molecule, and is the compound that contains three or more fluorine atoms in molecule.This substrate preferably 1,1,1,2-Tetrafluoroethane (CF
3CH
2F), 1,1,2,2-Tetrafluoroethane (CHF
2CHF
2) and/or pentafluoride ethane, preferred 1,1,1,2-Tetrafluoroethane (CF
3CH
2F).
When implementing reaction, the concentration of hydrofluorocarbons at the reactor inlet place that contains two carbon atoms in molecule preferably is adjusted in and is no more than 6% (mole).For 1,1,1, the 2-Tetrafluoroethane, its concentration at the reactor inlet place preferably is adjusted to and is no more than 4% (mole).
Be reflected under the higher temperature and carry out, be preferably in 250-500 ℃ the temperature range and carry out.React under the pressure that is preferably in 0-3MPa and carry out.
Below explain in detail the method for production FC-116 of the present invention.
Organic compound as raw material is the hydrofluorocarbons that contains two carbon atoms in molecule in the present invention, and it can use formula (3) expression.
C
2H
yF
z (3)
In formula (3), x and y are the integers that satisfies 1≤x≤5 and 1≤y≤5, and precondition is x+y=6.The example of this compounds has a fluoroethane (C
2H
5F), 1,2-C2H4F2 C2H4F2 (CH
2FCH
2F), 1,1-C2H4F2 C2H4F2 (CHF
2CH
3), 1,1,1-Halothane (CF
3CH
3), 1,1,2-Halothane (CHF
2CH
2F), 1,1,1,2-Tetrafluoroethane (CF
3CH
2F), 1,1,2,2-Tetrafluoroethane (CHF
2CHF
2) and pentafluoride ethane (CF
3CHF
2).These raw materials can use or mix its two or more use separately.
As mentioned above, the reaction of organic compound and fluorine gas is accompanied by super amount heat, and the amount of reaction heat is directly proportional with the mole number of fluorine, and promptly the amount of fluorine is big more, and the amount of reaction heat is big more.Therefore, should be few more by the H atom number that the F atom replaces, then the consumption of easy more control of reaction heat and expensive fluorine is also more little.Thereby in above-mentioned hydrofluorocarbons, starting material are the compounds that contain three or more fluorine atoms in the molecule preferably.The compound that preferably has four or more a plurality of fluorine atoms, especially 1,1,1,2-Tetrafluoroethane, 1,1,2,2-Tetrafluoroethane and/or pentafluoride ethane.
1,1,1,2-Tetrafluoroethane and pentafluoride ethane are the cfc (CFC) of suitability for industrialized production and the surrogate of hydrofluorocarbons (HCFC).Thereby all be easy to get, the purity of its commercially available prod is not less than 99.9%.When producing FC-116 with these compounds and fluorine gas, reaction heat is shown in reaction scheme (4) and (5).
(ΔH＝-231 kcal/mol)
(ΔH＝-119 kcal/mol)
Therefore, with 1,1,1,2-Tetrafluoroethane and pentafluoride ethane do raw-material advantage be the amount of reaction heat can be low to moderate when hydrocarbon polymer and fluorine gas prepare FC-116 reaction heat 1/3 to 1/6.
With 1,1,1,2-Tetrafluoroethane and pentafluoride ethane be relatively the time, and be preferred 1,1,1, the 2-Tetrafluoroethane.One of reason is that the activity of 2-Tetrafluoroethane is bigger when the starting material 1,1,1.Another important reasons is relevant with the purity of the commercially available prod of present industrial these two kinds of compounds.Specifically, 1,1,1,2-Tetrafluoroethane commercially available prod purity be not less than 99.9%, wherein contained impurity mainly is 1,1,2,2-tetrafluoroethane isomers and comprise chlorine compound hardly.
On the contrary, a pentafluoride ethane and a chloropentafluoroethane (CF
3CClF
2) form azeotropic mixture, make the pentafluoride ethane product of process distillation and other purification process contain the chloropentafluoroethane of hundreds of to several thousand ppm.It is undesirable this chlorine compound occurring in reaction, because it can produce by products such as chloro-fluoride, muriate.Therefore, 1,1,1, the 2-Tetrafluoroethane is particularly useful.
Under the existence that is reflected at diluent gas of above-mentioned hydrofluorocarbons and fluorine gas, under higher temperature, carry out.
Though, for example use the rare gas element of nitrogen, helium or argon and so on to make diluent gas usually, consider and rare gas element must be separated with target compound and be purified that it does not always have superiority aspect cost.In an embodiment preferred of the present invention, used to comprise at least the gas of one of Tetrafluoroethane (boiling point :-127.9 ℃), hexafluoroethane (boiling point :-78.5 ℃), octafluoropropane (boiling point :-37.7 ℃) and hydrogen fluoride (boiling point: 20 ℃) and make diluent gas.These diluted compounds not only have the effect that suppresses burning, blast etc., and also being favourable aspect the cost of energy of separation and purifying, because they have the boiling point than helium (boiling point :-268.9 ℃) and other carrier gas height.Preferred especially the use is rich in hydrofluoric diluent gas (its hydrogen fluoride content preferably be not less than diluent gas total amount 50%).
For example, 1 mole 1,1,1,2-Tetrafluoroethane and 2 moles of fluorine reactions produce 1 mole of FC-116 and 2 moles of hydrogen fluoride, shown in reaction scheme (4).Because the boiling point of target compound (being FC-116) and by product (being hydrogen fluoride) differs about 100 ℃, the simple method by for example partial condensation and so on just can obtain to be rich in hydrofluoric gas.Using this gas is economical as diluent gas.Perhaps, can newly add hydrogen fluoride and make diluent gas.In the direct oxidation method that uses fluorine gas, in above-mentioned long reaction, owing to for example division of C-C key produces carbon formation, deposition etc.Though carbon formation, deposition etc. may cause the danger with fluorine gas reaction suddenly or blast, being to use hydrogen fluoride gas to make diluent gas is being effective aspect formation that suppresses carbon or the deposition.A speech is meant " contained main component is a hydrogen fluoride " " to be rich in hydrogen fluoride ".
The reaction of reaction substrate and fluorine gas is to carry out in the presence of diluent gas.Before in introducing reactor, with diluent gas one of reaction substrate and fluorine gas or both are diluted usually.From the angle of safety, the most handy diluent gas is diluted to enough low concentration with reaction substrate and fluorine gas.
Temperature of reaction is one of the condition that should consider, is that above-mentioned hydrofluorocarbons and fluorine gas reacts in the presence of for example above-mentioned diluent gas effectively so that make starting material.The optimum range of temperature of reaction depends on duration of contact and the raw-material kind of hydrofluorocarbons.For example, for 1,1,1, the reaction of 2-Tetrafluoroethane and fluorine is in the presence of diluent gas, with what long duration of contact, carried out (15 seconds), the temperature of reaction during the reaction beginning is about 50 ℃, is reflected at about 250 ℃ temperature and is issued to about 100% transformation efficiency.Adopt higher temperature of reaction, temperature is preferably in 200-550 ℃ the temperature range.
Be lower than 250 ℃ temperature of reaction since the transformation efficiency of hydrofluorocarbons low be disadvantageous.The temperature of reaction that surpasses 500 ℃ is disadvantageous, and for example the generation of the division of C-C key, polymerization etc. can cause the reduction of yield and problem such as reactor corrosion and energy consumption increase is arranged.
Although to having no particular limits duration of contact, usually in the scope of second of 0.1-120 for example.Yet, generally be preferably 1-30 second duration of contact, preferred 3-30 second, owing to require to use bigger reactor long duration of contact, thereby be uneconomic.Preferably with reaction substrate and fluorine gas thorough mixing.
As mentioned above, in the direct fluorination method of using fluorine gas, organic compound substrate (organic compound that particularly contains hydrogen) may explode or burn when being exposed in the fluorine, because fluorine is reactive extremely strong.
In reaction of the present invention,, importantly should avoid the blast of hydrofluorocarbons and fluorine owing to used the hydrofluorocarbons that contains hydrogen to make the organic compound substrate.For avoiding blast, the composition of mixed gas should be regulated makes it outside explosive range.The inventor shows that for the result of study of the explosive range of the mixture of hydrofluorocarbons and fluorine gas the lower limit of the explosive range of pentafluoride ethane is that concentration is about 6% (mole), 1,1,1, the 2-Tetrafluoroethane be that concentration is about 4%.Hydrofluorocarbons of the present invention should be adjusted in its corresponding safety range in the concentration at reactor inlet place.
Send into the fluorine gas of each reaction system and the preferred 0.5-5.0 of mol ratio of hydrofluorocarbons, more preferably 1.0-3.0.If the molar ratio of the fluorine gas of sending into is lower than 0.5, then reaction can not be carried out effectively.It is uneconomic that its molar ratio surpasses 5.0, because sent into excessive fluorine gas, and this for example needs the device with its recovery.
In the process of implementing reaction, from avoiding the dangerous viewpoint such as blast, reaction pressure also is important.In general, pressure is high more, and explosive range is wide more.Therefore, reaction is preferably under the lower pressure to be carried out, preferably in the scope of 0-3MPa.
Reactor is preferably made by the material that corrosive gases is had patience.Examples of material comprises nickel, invar and Hastelloy.
Be embodiments of the invention below, only limit to this but should not be construed as the present invention.
At first the starting material that use in the following reaction are described below: (1,1,1, the 2-Tetrafluoroethane)
Used Ecoloace 134a (trade(brand)name), it is at present as CFC-12 (CClF
2) the substitute supply.Its purity is not less than 99.99%, contains 1,1,2 of about 20ppm, the 2-tetrafluoroethane isomers.Do not detect chlorine compound impurity.(pentafluoride ethane)
Used Ecoloace 125 (trade(brand)name), it is at present as HCFC-22 (CHClF
2) the substitute supply.Its purity is not less than 99.95%, contains 1,1,1,2-Tetrafluoroethane, 1,1,1-Halothane and chlorine compound (i.e. a chloropentafluoroethane and 1-chloro-1,2,2,2-Tetrafluoroethane) impurity.
Embodiment 1
With internal diameter is that 20.6 millimeters, length are 500 millimeters Inconel 600 reactor (electric heating types; Reactor process fluorine gas is 600 ℃ of following inertization) be heated to 280 ℃, the speed with 30 NL/h is introduced nitrogen dilution gas in reactor simultaneously.Subsequently, with the speed of 50 NL/h the hydrogen fluoride diluent gas is introduced wherein.The mobile of diluent gas is divided into two strands, adds 1,1,1 with the speed of 1.8NL/h to one of them, the 2-Tetrafluoroethane is made hydrofluorocarbons.Then, react by fluorine gas being added in the diluent gas that another stock goes out with the speed of 3.9 NL/h.
1,1,1, the concentration of 2-Tetrafluoroethane at the reactor inlet place is 2.1% (mole), and temperature of reaction is 280 ℃.
After three hours, with the gaseous mixture of potassium hydroxide aqueous solution and the acquisition of potassium iodide aqueous solution processing reaction, to remove hydrogen fluoride and unreacted fluorine gas.With the composition (% (volume)) of gas chromatographic analysis gained gas, the result is as follows:
CF
4 0.56％
C
2F
6 84.59％
CF
3CHF
2 14.45％
CF
3CH
2The F trace
Other compound 0.40%
Embodiment 2 to 5
Under the condition identical, react, only the temperature of reaction difference with embodiment 1.The results are shown in the table 1 of used temperature of reaction and acquisition.
Table 1
| Embodiment | Temperature of reaction (℃) | Form (vol%) | ||||
| FC-14 | FC-116 | HFC- 125 | HFC- 134a | Other composition | ||
| 2 | 200 | 0.49 | 65.16 | 28.85 | 5.20 | 0.3 |
| 3 | 350 | 0.78 | 90.52 | 8.02 | - | 0.68 |
| 4 | 450 | 1.28 | 95.17 | 2.66 | - | 0.89 |
| 5 | 550 | 4.68 | 92.55 | 0.89 | - | 1.88 |
In table, FC-14 is meant CF
4, FC-116 is meant CF3CF
3, HFC-125 is meant CF
3CHF
2, HFC-134 is meant CF
3CH
2F.
" other composition " in the table 1 mainly comprises carbonic acid gas.Yet, in the time of 550 ℃, observe C
3F
8Generation.The result shows that the yield of target compound FC-116 is lower at low temperatures, and under 550 ℃ high temperature, the selectivity of target compound is low, and observes C
3The generation of perfluorochemical, it is to be produced by the acceleration division of C-C key and polymerization.
Embodiment 6-8
Use the reactor identical with embodiment 1, react in the mode identical with embodiment 1, different is as the pentafluoride ethane of hydrofluorocarbons and fluorine gas respectively with the speed charging of 3.6NL/h and 3.9NL/h, hydrogen fluoride and nitrogen as diluent gas are introduced with the speed of 50NL/h and 30NL/h respectively, and change temperature of reaction.Used temperature of reaction and gained the results are shown in the table 2.
Table 2
| Embodiment | Temperature of reaction (℃) | Form (vol%) | ||||
| FC-14 | FC-116 | HFC- 125 | The Cl compound | Other composition | ||
| 6 | 200 | 0.21 | 6.70 | 92.17 | 0.48 | 0.44 |
| 7 | 300 | 0.48 | 85.21 | 13.07 | 0.47 | 0.77 |
| 8 | 400 | 0.72 | 98.18 | - | 0.22 | 0.88 |
" other composition " in the table 2 mainly comprises carbonic acid gas, and " Cl compound " mainly comprises a chloropentafluoroethane and 1-chloro-1,2,2,2-Tetrafluoroethane.
Though the result shows pentafluoride ethane the reactivity of fluorine gas is not so good as 1,1,1 that the height of 2-Tetrafluoroethane (in low temperature range) provides good FC-116 yield.Yet, in embodiment 8, detect chlorine and chloro-fluoride.
Embodiment 9
Use the reactor identical with embodiment 1, react in the mode identical with embodiment 1, different is as 1 of hydrofluorocarbons, 1,1, with the speed charging of 2.2NL/h and 4.8NL/h, hydrogen fluoride and Tetrafluoroethane are introduced with the speed of 60NL/h and 20NL/h respectively, and temperature of reaction becomes 480 ℃ respectively for 2-Tetrafluoroethane and fluorine gas.Gained result (% (volume)) is as follows:
CF
4 1.46％
C
2F
6 95.98％
CF
3CHF
2 1.78％
CF
3CH
2F -
Other compound 0.78%
Reaction was carried out 30 days under these conditions continuously, in the time of the 30th day, collected gas at reactor outlet, analyzed and formed.The result of Huo Deing and much at one top like this.Then, termination reaction, to room temperature, the while is to wherein introducing nitrogen with reactor cooling.Check the reactor internal surface with endoscope (endoscope).The result does not observe the deposition of carbon and other material.
The method according to this invention can be by making the hydrofluorocarbons that contains two carbon atoms in the molecule and fluorine gas in vapour phase, react in the presence of diluent gas, with high yield, industrialization ground and produce FC-116 safely.
Although the contrast specific embodiments has described the present invention in detail, those skilled in the art are apparent, can make multiple variation and modification under the situation that does not deviate from the spirit and scope of the invention.
Claims (9)
1. produce the method for hexafluoroethane, comprise making the hydrofluorocarbons that contains two carbon atoms in the molecule and fluorine gas in vapour phase, be 250-500 ℃, in the presence of diluent gas, react in temperature.
2. the described method of claim 1, wherein diluent gas is the gas that comprises one of tetrafluoromethane, hexafluoroethane, octafluoropropane and hydrogen fluoride at least.
3. the described method of claim 1, wherein diluent gas is rich in hydrogen fluoride.
4. the described method of claim 1, the hydrofluorocarbons that wherein contains two carbon atoms in the molecule is the hydrofluorocarbons that contains three or more fluorine atoms.
5. the described method of claim 1, the hydrofluorocarbons that wherein contains two carbon atoms in the molecule is 1,1,1,2-Tetrafluoroethane, 1,1,2, at least a in 2-Tetrafluoroethane and the pentafluoride ethane.
6. the described method of claim 5, the hydrofluorocarbons that wherein contains two carbon atoms in the molecule is 1,1,1, the 2-Tetrafluoroethane.
7. the described method of claim 1 wherein is adjusted in the hydrofluorocarbons that contains two carbon atoms in the molecule concentration at the reactor inlet place in reaction, it is no more than by 6% of mole.
8. the described method of claim 7, wherein 1,1,1, the concentration of 2-Tetrafluoroethane at the reactor inlet place is no more than by 4% of mole.
9. the described method of claim 1, wherein reaction is what to carry out under the reaction pressure of 0-3MPa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5032396A JP2947158B2 (en) | 1996-03-07 | 1996-03-07 | Production of hexafluoroethane |
| JP50323/1996 | 1996-03-07 | ||
| JP50323/96 | 1996-03-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1165803A CN1165803A (en) | 1997-11-26 |
| CN1076333C true CN1076333C (en) | 2001-12-19 |
Family
ID=12855706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97102133A Expired - Fee Related CN1076333C (en) | 1996-03-07 | 1997-01-15 | Process for producing hexafluoroethane |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100283711B1 (en) |
| CN (1) | CN1076333C (en) |
| SG (1) | SG48501A1 (en) |
| TW (1) | TW409114B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6958596B2 (en) * | 2019-07-01 | 2021-11-02 | ダイキン工業株式会社 | Alkane manufacturing method |
| CN111484389A (en) * | 2020-04-16 | 2020-08-04 | 山东重山光电材料股份有限公司 | Production process for co-producing high-purity electronic grade hydrogen fluoride and carbon fluoride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0031519A1 (en) * | 1979-12-26 | 1981-07-08 | Allied Corporation | Preparation of fluorinated organic compounds with elemental fluorine and fused alumina reactor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02131438A (en) * | 1988-11-11 | 1990-05-21 | Asahi Glass Co Ltd | Production of hexafluoroethane |
-
1996
- 1996-12-12 SG SG1996011695A patent/SG48501A1/en unknown
- 1996-12-18 KR KR1019960067179A patent/KR100283711B1/en not_active IP Right Cessation
- 1996-12-23 TW TW085115908A patent/TW409114B/en not_active IP Right Cessation
-
1997
- 1997-01-15 CN CN97102133A patent/CN1076333C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0031519A1 (en) * | 1979-12-26 | 1981-07-08 | Allied Corporation | Preparation of fluorinated organic compounds with elemental fluorine and fused alumina reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970065491A (en) | 1997-10-13 |
| TW409114B (en) | 2000-10-21 |
| KR100283711B1 (en) | 2001-03-02 |
| SG48501A1 (en) | 1998-04-17 |
| CN1165803A (en) | 1997-11-26 |
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