CN1090162C - Method for production of perfluorocarbon - Google Patents
Method for production of perfluorocarbon Download PDFInfo
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- CN1090162C CN1090162C CN97102131A CN97102131A CN1090162C CN 1090162 C CN1090162 C CN 1090162C CN 97102131 A CN97102131 A CN 97102131A CN 97102131 A CN97102131 A CN 97102131A CN 1090162 C CN1090162 C CN 1090162C
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- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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Abstract
A process by which perfluorocarbons can be industrially produced safely and efficiently from organic compounds and fluorine gas. A process wherein a hydrofluorocarbon is reacted with fluorine gas in a vapor phase to produce a gas which is to be used as a diluent gas. To economically and efficiently obtain perfluorocarbon with industrial safety by using a gas formed by vapor-phase reaction between a hydrofluorocarbon and fluorine gas as a diluent. In the first reaction zone, a hydrofluorocarbon and fluorine gas are brought into contact with each other at an elevated temperature, preferably at 200-550 deg.C and the produced gas is introduced into the second reaction zone as a diluent. In the second reaction zone, another hydrofluorocarbon different from that in the first zone, when necessary, fluorine gas are fed and they are brought into contact with each other at the temperature as stated above. At least a part of the produced gas in the second zone is preferably used as a diluent in the first reaction zone. The reaction pressure is preferably 0-5Mpa. The perfluorocarbon produced preferably comprises 2 or more kinds selected from tetrafluoromethane, hexafluoroethane or octafluoropropane.
Description
The present invention relates to by making hydrofluorocarbons and fluorine gas in vapour phase, react the method for producing perfluoro-carbon, more particularly, the present invention relates to a kind of like this method of producing perfluoro-carbon: this method comprises makes hydrofluorocarbons and fluorine gas in vapour phase, in first reaction zone, contacting under the higher temperature of reaction, introducing in second reaction zone as diluent gas the gained gaseous reaction mixture and the hydrofluorocarbons (in case of necessity with fluorine gas) that will be different from first reaction zone reaction is sent into second reaction zone so that hydrofluorocarbons contacts in higher temperature of reaction with gaseous reaction mixture.In semi-conductor industry, be used as for example etching reagent and washing composition for the gasiform perfluoro-carbon at normal temperatures, and be used as for example refrigerant for liquid perfluoro-carbon at normal temperatures.Therefore, perfluoro-carbon has the range of application of broad and is industrial useful compound.
About the production of perfluoro-carbon, several different methods has been proposed up to now.For example for the perfluoro-carbon that has a carbon atom---tetrafluoromethane (hereinafter being designated as ＂ FC-14 ＂ or ＂ CF ＂), the example of prior art comprises makes monochlorotrifluoromethane (CClF
3) method (JP-B-62-10211 that in the presence of catalyzer, reacts with HF; ＂ JP-B ＂ is meant the Japanese patent application of having examined); Comprise and make Refrigerant 12 (CCl
2F
2) method (JP-B-42-3004) of in the presence of catalyzer, reacting with HF; Comprise and make tetracol phenixin (CCl
4) with the method (JP-B-43-10601) of HF reaction; Comprise and make trifluoromethane (CHF
3) and F
2The method (BG-1116920 (1986)) of reaction; Comprise and make carbon (C) and F
2At BrF
3Or IF
5Method (the JP-A-62-10211 of middle reaction; ＂ JP-A ＂ is meant unexamined Japanese patent application); Make tetrafluoroethylene (CF with comprising
2=CF
2) and CO
2Pyrolytic method (United States Patent (USP) 4,365,102 (1982)) at high temperature.
For the perfluoro-carbon that has two carbon atoms---hexafluoroethane (hereinafter is designated as ＂ FC-116 ＂ or ＂ CF
3CF
3＂), the example of currently known methods comprises that with ethane and/or ethene be raw-material electrochemical fluorination method; With tetrafluoroethylene or another kind of starting material pyrolytic method; Comprise and make fluorizated methods such as acetylene, ethene and/or ethane with metal fluoride; Comprise and make fluorizated methods such as dichloro tetrafluoro ethane, a chloropentafluoroethane with hydrogen fluoride; With the direct fluorination method that makes ethane etc. with the fluorine gas reaction.
In addition, for the perfluoro-carbon that has three carbon atoms---octafluoropropane (hereinafter is designated as ＂ FC-218 ＂ or ＂ C
3F
8＂), known method comprises the direct fluorination method (EP-31,519 (1981)) that makes fluorine gas and propane reaction.
Use the example of the direct fluorination method of fluorine gas to comprise that (a) makes fluorine gas and ethane reaction to obtain the method (J.Amer.Chem.Soc., 77,3307 (1955), J.Amer.Chem.Soc., 82,5827 (1960)) of FC-14 and FC-116 with injection reactor; (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 (d) 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) of producing fluorinated olefin from alkene and the carbon that is adsorbed with fluorine gas.
The shortcoming of using the direct fluorination method of 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 (C) 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 (2) and (3).
(ΔH＝-479Kcal/mol)
(ΔH＝-690Kcal/mol)
Above-mentioned reaction scheme shows that a c h bond produces the reaction heat of about-110Kcal/mol when being replaced by a C-F key.In the direct fluorination method of propane and fluorine gas direct reaction, Δ H is approximately-880Kcal/mol.
With methane is that the every mole of methane of the reaction shown in the raw-material reaction scheme (2) needs 4 moles of fluorine, and is that every mole of ethane of the reaction shown in the raw-material reaction scheme (3) needs 6 moles of fluorine with ethane.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.The conventional method that reaction heat takes place suddenly in the direct fluorination method that is suppressed at comprises: with rare gas element (for example nitrogen or helium) dilution fluorine; Being dissolved in the organic compound substrate to fluorine in advance 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 perfluoro-carbon 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 perfluoro-carbon, comprise make hydrofluorocarbons and fluorine gas in vapour phase, in first reaction zone, contacting the step of acquisition gaseous reaction mixture under the higher temperature of reaction; With with gaseous reaction mixture as diluent gas introduce in second reaction zone with its in this district under higher temperature of reaction (in case of necessity with fluorine gas) send into the step that the hydrofluorocarbons of second reaction zone contacts, the hydrofluorocarbons of sending into second reaction zone is with different at the hydrofluorocarbons of first reaction zone.In the present invention, the gaseous reaction mixture circulation that preferably obtains at second reaction zone to major general's part also is used as the diluent gas of first reaction zone.
Fig. 1 is the schema of one embodiment of the invention.
The example of available diluent gas comprises: tetrafluoromethane, perfluoroethane, octafluoropropane and hydrogen fluoride. Wherein preferred tetrafluoromethane, perfluoroethane and hydrogen fluoride. More preferably be rich in hydrofluoric gas (its hydrogen fluoride content be preferably the diluent gas total amount 50% or higher).
When implementing reaction, preferably be incorporated in the corresponding reaction zone as raw-material hydrofluorocarbons, so that each hydrogen fluoride concentration that records in the reaction zone porch is no more than 8% (mole). Reaction is carried out under higher temperature; The reaction temperature of the first reaction zone and/or second reaction zone is preferably 200-550 ℃. In addition, the reaction pressure of the first reaction zone and/or second reaction zone is preferably 0-5MPa.
Reaction obtains two or more perfluocarbons. The example comprises FC-14, FC-116 and FC-218. Preferred FC-14 and FC-116.
The hydrofluorocarbons of sending into as starting material is two or more general formula C
xH
yF
z(wherein, x, y and z are the integers that satisfies 1≤x≤3,1≤y≤4 and 1≤z≤7, and precondition is when x is 1, y+z=4; When x is 2, y+z=6; When x is 3, y+z=8) Dai Biao hydrofluorocarbons.Hydrofluorocarbons preferably is selected from a fluoromethane (CH
3F), methylene fluoride (CH
2F
2), trifluoromethane (CHF
3), Halothane (C
2H
3F
3), Tetrafluoroethane (C
2H
2F
4), pentafluoride ethane (C
2HF
5), pentafluoropropane (C
3H
3F
5), HFC-236fa (C
3H
2F
6) and heptafluoro-propane (C
3H
2F
7) perfluoro-carbon.A wherein preferred fluoromethane, methylene fluoride, trifluoromethane, Halothane, Tetrafluoroethane and pentafluoride ethane.Preferred especially methylene fluoride, trifluoromethane, Tetrafluoroethane and pentafluoride ethane.
The mass action of chlorine compound impurity is no more than 2% (mole) in the hydrofluorocarbons of sending into as starting material.
Describe the method for production perfluoro-carbon of the present invention below in detail.
The method of production perfluoro-carbon of the present invention comprises makes hydrofluorocarbons and fluorine gas in vapour phase, contacting in first reaction zone under the higher temperature of reaction, and the gaseous reaction mixture (perfluoro-carbon and/or hydrogen fluoride) that obtains is sent into second reaction zone as diluent gas; Send into second reaction zone so that hydrofluorocarbons contacts in higher temperature of reaction with gaseous reaction mixture with the hydrofluorocarbons (in case of necessity with fluorine gas) that will be different from the reaction of first reaction zone.Preferred gaseous reaction mixture (perfluoro-carbon and/or the hydrogen fluoride) circulation that obtains at second reaction zone to major general part and as the diluent gas of first reaction zone, thus can overcome problem that conventional direct fluorination method produces and can be safely, effectively, the useful perfluoro-carbon of suitability for industrialized production at low cost.
One of feature of the present invention is diluent gas.
For the situation by making the reaction of hydrofluorocarbons and fluorine gas produce perfluoro-carbon, reaction scheme and reaction heat route available (4) to (7) are represented.
(ΔH＝-259Kcal/mol)
(ΔH＝-120Kcal/mol)
(ΔH＝-231Kcal/mol)
(ΔH＝-119Kcal/mol)
Although use the rare gas element such as nitrogen, helium or argon gas to make diluent gas usually, owing to must from these rare gas elementes, isolate the target perfluoro-carbon with steps such as distillation, purifying, always this method does not have advantage aspect cost.Favourable economically used diluent gas is the gas reaction mixture that produces, and it comprises tetrafluoromethane, hexafluoroethane, octafluoropropane and hydrogen fluoride, preferably comprises tetrafluoromethane, hexafluoroethane and hydrogen fluoride, and preferably is rich in hydrogen fluoride.
In the present invention, hydrogen fluoride (boiling point: 20 ℃) produces as by product, for example shown in the route (4) to (7).For example for being the situation of material organic compound with the methylene fluoride, per 2 moles of hydrogen fluoride produce 1 mole of FC-14.For the situation of pentafluoride ethane, per 1 moles of hydrogen fluoride produces 1 mole of FC-116.Because the target compound boiling point is that the difference of FC-14 (boiling point :-127.9 ℃) or FC-116 (boiling point :-78.5 ℃) and by product (being hydrogen fluoride) boiling point is about 100 ℃, thereby can pass through distillation/purification step separating fluorine hydride easily.Those compounds are owing to the boiling point that has than helium (boiling point :-286.9 ℃) and other carrier gas height, so be favourable aspect separation and the distillatory cost of energy.
In addition, use that to make diluent gas without the gaseous reaction mixture (perfluoro-carbon and hydrofluoric mixture) of any processing be favourable aspect the cost.Although can in distillation/purification step, reclaim hydrogen fluoride and as diluent gas and circulation, the hydrogen fluoride of recovery is generally used for other application.In the direct fluorination method of using fluorine gas, in aforesaid long reaction process, the division of C-C key, polymerization etc. cause the appearance of carbon generation, deposition etc.Though carbon generation, deposition etc. may cause a series of and trigger reaction or blast fluorine gas, are rich in generation and decomposition that hydrofluoric diluent gas can suppress carbon effectively." be rich in hydrogen fluoride " and be meant " containing hydrogen fluoride " as main component.
Hydrofluorocarbons (reaction substrate) is to carry out in the presence of diluent gas with the reaction of fluorine 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.
In the present invention, reaction is preferably in each hydrofluorocarbons reaction substrate concentration adjustment is no more than at reactor inlet under the condition of 8% (mole) and carries out.As mentioned above, in the direct fluorination process that uses fluorine gas, organic compound substrate (compound that particularly contains hydrogen) is exposed to the danger that has burning or blast under 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 use the hydrofluorocarbons that contains hydrogen to make the organic compound substrate.For avoiding blast, mixed gas should be regulated, so that make composition outside explosive range.The inventor finds that to the result of study of the explosive range of the mixture of hydrofluorocarbons and fluorine gas following being limited to of the explosive range of these hydrofluorocarbons is no more than 8% (mole), although they change to some extent according to the kind of hydrofluorocarbons.Based on this, can assaying reaction in the safety range of organic compound entrance concentration.
Temperature of reaction is one of the condition that should consider, so that react effectively.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, for first reaction zone and second reaction zone, temperature is preferably in 200-550 ℃ the temperature range.
Be lower than 200 ℃ temperature of reaction since the transformation efficiency of hydrofluorocarbons low be disadvantageous.The temperature of reaction that surpasses 550 ℃ 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.
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.There is no particular restriction to send into the method for fluorine gas.For example, can adopt and send into first reaction zone and unreacted remaining fluorine gas is used for second reaction zone fluorine gas is excessive.Yet, in general preferably fluorine gas is sent into and is both sent into first reaction zone and also send into second reaction zone from the viewpoint of safety.
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 and carries out.Specifically, the reaction pressure of first reaction zone and second reaction zone is preferably in the scope of 0-5MPa, 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.
As mentioned above, the direct fluorination method of organic compound substrate and fluorine gas reaction is accompanied by super amount heat, and the amount of reaction heat is directly proportional with the mole number of used fluorine gas, and promptly the fluorine amount is big more, and the heat of generation is big more.Therefore, the number of the c h bond that is replaced by the C-F key is few more, and the control of reaction heat is also easy more, and the consumption of expensive fluorine is also few more, and promptly cost is low more.
Another feature of the present invention is substrate.As mentioned above, not that contain in a large number should be by the straight chain hydrocarbon of the displaced c h bond of C-F key as the organic compound of substrate in the present invention, but partially fluorinated hydrofluorocarbons (HFC).---wherein contain on a small quantity should by the displaced c h bond of C-F key---control of reaction heat be easy owing to used such substrate.Send into two or more hydrofluorocarbons in the present invention to produce two or more perfluoro-carbons.The example of available hydrofluorocarbons is represented with following formula (8):
C
xH
yF
z(8) (wherein, x, y and z are the integers that satisfies 1≤x≤3,1≤y≤4 and 1≤z≤7, and precondition is when x is 1, y+z=4; When x is 2, y+z=6; When x is 3, y+z=8).
Substrate preferably is selected to contain and is no more than three and should specifically be selected from a fluoromethane, methylene fluoride, trifluoromethane, Halothane, Tetrafluoroethane, pentafluoride ethane, pentafluoropropane, HFC-236fa and heptafluoro-propane by the hydrofluorocarbons of the displaced c h bond of C-F key.From the equal angles that is easy to get, a preferred fluoromethane, methylene fluoride, trifluoromethane, Halothane, Tetrafluoroethane and pentafluoride ethane.Particularly preferably be contain be no more than two should be by the hydrofluorocarbons of the displaced c h bond of C-F key, especially methylene fluoride, trifluoromethane, Halothane, Tetrafluoroethane and pentafluoride ethane.These hydrofluorocarbons of these industrial productions all are for example as the surrogate of Chlorofluorocarbons (CFCs) (CFC) or Hydrochlorofluorocarbons (HCFC) with as refrigerant.The purity of its commercially available prod is not less than 99.9%, and this is gratifying.
Thereby, 1/2 to 1/6 of the amount (route (2) and (3)) of reaction heat advantage when the amount (route (4) is to (7)) of using for example above-named hydrofluorocarbons to have reaction heat only is usefulness straight chain hydrocarbon compound and fluorine gas production perfluoro-carbon.
These hydrofluorocarbons can use separately or use with the form of its mixture.Can make two or more target compound perfluoro-carbons from hydrofluorocarbons.Preferred perfluoro-carbon is Tetrafluoroethane, hexafluoroethane and/or octafluoropropane, more preferably tetrafluoromethane and hexafluoroethane.
Preferably do not contain chlorine compound as raw-material hydrofluorocarbons.From the angle of reactor material and distillation procedure, comprising of chlorine compound is undesirable, generates chlorine and chloro-fluoride because they can react.The concentration of the chlorine compound in each hydrofluorocarbons is preferably lower than 2% (mole), preferably is no more than 1% (mole), especially preferably is no more than 0.1% (mole).
Of the present invention another be characterised in that provide since above-mentioned feature and aspect cost, security and efficient all improved method.This method comprises makes hydrofluorocarbons and fluorine gas in vapour phase, contacting in first reaction zone under the higher temperature of reaction, produces first perfluoro-carbon and hydrogen fluoride; Part or all introduces second reaction zone as diluent gas with it; To be different from the hydrofluorocarbons of sending into first reaction zone and send into second reaction zone (sending into fluorine gas in case of necessity), and hydrofluorocarbons be contacted under higher temperature of reaction with diluent gas, thereby produce second perfluoro-carbon and hydrogen fluoride; Be partially or totally recycled to first reaction zone and/or second reaction zone uses as diluent gas.
For example, will be as 1,1,1 of hydrofluorocarbons, 2-Tetrafluoroethane and fluorine gas and be rich in the hydrogen fluoride diluent gas and send into and in the first reaction zone vapour phase, generate FC-116 perfluoro-carbon and hydrogen fluoride in first reaction zone under the comparatively high temps.Partial reaction device exit gas can directly be used as diluent gas, perhaps exit gas can be sent to distilation steps.Yet, usually exit gas is sent into second reactor.In the ingress of second reactor, with hydrofluorocarbons not of the same race for example methylene fluoride mix with the exit gas of discharging (also having fluorine gas in case of necessity) from first reaction zone.Compound is sent in second reactor with higher reaction temperatures to generate perfluoro-carbon FC-14 and hydrogen fluoride.
The exit gas of discharging from second reaction zone is to comprise as the FC-116 of perfluoro-carbon and FC-14 and as the hydrogen fluoride mixture bigger than perfluoro-carbon amount of by product.Mixture circulation to the first reaction zone that part is obtained as the exit gas of discharging from second reaction zone and/or second reaction zone also directly are used as diluent gas with it.Residuum is separated into perfluoro-carbon and hydrogen fluoride in distillation and purification step.
With compare from the ordinary method of a kind of perfluoro-carbon of a kind of hydrogen fluoride production, above-mentioned advantage of producing the method for the present invention of two or more perfluoro-carbons from two or more hydrofluorocarbons for example is that the equipment of distilation steps can be simplified and can reach lower cost of energy.
Though reaction zone can preferably use two or more reactors from the simplification and the security consideration of operation usually by a reactor is separately formed.Reactor is not to be exactly series arrangement side by side usually, but usually preferred series arrangement.
For example methylene fluoride and trifluoromethane can produce for example FC-14 of a kind of perfluorochemical from two or more hydrofluorocarbons.Also can all send into a kind of hydrofluorocarbons in second and first reaction zone, methylene fluoride for example is leniently to react.
In the present invention, the ratio of two kinds of feed hydrogen fluorocarbonss charging can change, thereby changes the ratio of two kinds of perfluoro-carbons will being produced by them.Also can use three or more reaction zones, to produce three kinds or more kinds of perfluoro-carbon simultaneously.
As mentioned above, according to method of the present invention, can be safely, effectively, suitability for industrialized production perfluoro-carbon at low cost.
Be embodiments of the invention below, only limit to this but should not be construed as the present invention
At first be described below: (methylene fluoride) being used as raw-material hydrofluorocarbons in the following reaction
Used methylene fluoride (CH
2F
2) Ecoloace 32 (trade(brand)name, Japanese Showa DenkoK.K. makes), it is at present as HCFC-22 (CHClF
2) the substitute supply.
Its purity is not less than 99.99%, contains 1,1,1-Halothane (CF
3CH
3) and a fluoromethane (CH
3F) impurity.Wherein almost detect less than chlorine compound impurity.(trifluoromethane)
Used trifluoromethane (CHF
3) Ecoloace 23 (trade(brand)name, Japanese Showa DenkoK.K. makes), it is at present as the refrigerant supply.Its purity is not less than 99.95%, contains to comprise monochlorodifluoromethane (CHClF
2) and monochlorotrifluoromethane (CClF
3) impurity.(1,1,1, the 2-Tetrafluoroethane)
Used 1,1,1,2-Tetrafluoroethane (CF
3CH
2F) Ecoloace 134a (trade(brand)name, Japanese Showa Denko K.K. makes), it is at present as CFC-12 (CClF
2) the substitute supply.Its purity is not less than 99.99%, contains 1,1,2, the 2-tetrafluoroethane isomers.Do not detect chlorine compound impurity.(pentafluoride ethane)
Used pentafluoride ethane (CF
3CHF
2) Ecoloace 125 (trade(brand)name, Japanese ShowaDenko K.K. makes), it is at present as HCFC-22 (CHClF
2) the substitute supply.Its purity is not less than 99.95%, contains CF
3CH
2F, CF
3CH
3An and chlorine compound (i.e. chloropentafluoroethane (CF
3CClF
2) and 1-chloro-1,2,2,2-Tetrafluoroethane (CHClFCF
3)) impurity.
Embodiment 1
Fig. 1 is the schema of one of embodiment of perfluoro-carbon production method of the present invention.Above-mentioned trifluoromethane is mixed with fluorine gas (11) and diluent gas (19) as hydrofluorocarbons (12), mixed gas (13) is introduced in first reaction zone (1).In first reaction zone, reagent is reacted under the following conditions: reaction pressure is 0.15MPa, and temperature of reaction is 400 ℃, F
2/ trifluoromethane mol ratio is 1.51, and the trifluoromethane entrance concentration is 2.1% (mole).Thereby, obtain the exit gas (14) of discharging from first reaction zone.
With this exit gas and 1,1,2, the 2-Tetrafluoroethane mixes as fresh hydrogen fluorocarbons (16) and fluorine gas (15).This mixed gas (17) is introduced in second reaction zone (2).In second reaction zone, reagent is reacted under the following conditions: reaction pressure is 0.15MPa, and temperature of reaction is 370 ℃, F
2/ 1,1,1,2-Tetrafluoroethane mol ratio is 2.06,1,1,1, and the entrance concentration of 2-Tetrafluoroethane is 1.35% (mole).Thereby the exit gas (18) that acquisition is discharged from second reaction zone.With this exit gas be divided into diluent gas (19) wait to introduce in the distillation/purification step (3) and gas (20).Gained the results are shown in the table 1, and the label shown in the wherein epimere is corresponding to label given among Fig. 1.
Embodiment 2
Produce perfluoro-carbon with the technical process identical with embodiment 1, its process is as follows.With the pentafluoride ethane is that hydrofluorocarbons (12) mixes with fluorine gas (11) and diluent gas (19), and mixed gas (13) is introduced in first reaction zone (1).In first reaction zone, reagent is reacted under the following conditions: reaction pressure is 0.15MPa, and temperature of reaction is 370 ℃, F
2/ five fluoromethane mol ratios are 1.47, and the pentafluoride ethane entrance concentration is 32% (mole).Thereby, obtain the exit gas (14) of discharging from first reaction zone.
This exit gas is mixed with methylene fluoride and fluorine gas (15) as fresh hydrogen fluorocarbons (16).This mixed gas (17) is introduced in second reaction zone (2).In second reaction zone, reagent is reacted under the following conditions: reaction pressure is 0.15MPa, and temperature of reaction is 350 ℃, F
2/ methylene fluoride mol ratio is 2.01, and the entrance concentration of methylene fluoride is 2.05% (mole).Thereby the exit gas (18) that acquisition is discharged from second reaction zone.This exit gas is divided into diluent gas (19) and waits to introduce gas (20) in the distillation/purification step (3).Gained the results are shown in the table 2.
Table 1
(embodiment 1)
| Composition | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| F 2 | 1.003 | - | 1.012 | 0.367 | 0.585 | - | 0.952 | 0.010 | 0.009 | 0.001 |
| HFC-134a | - | - | 0.004 | - | - | 0.462 | 0.462 | 0.004 | 0.004 | - |
| HFC-23 | - | 0.665 | 0.668 | 0.047 | - | - | 0.047 | 0.003 | 0.003 | - |
| HF | - | - | 17.288 | 17.933 | - | - | 17.933 | 18.873 | 17.288 | 1.585 |
| HFC-125 | - | - | 0.030 | 0.015 | - | - | 0.015 | 0.033 | 0.030 | 0.003 |
| FC-116 | - | - | 4.983 | 5.002 | - | - | 5.002 | 5.440 | 4.983 | 0.457 |
| FC-14 | - | - | 7.295 | 7.916 | - | - | 7.916 | 7.964 | 7.295 | 0.669 |
| Other | 0.010 | 0.001 | 0.031 | 0.031 | 0.007 | - | 0.038 | 0.038 | 0.020 | 0.018 |
| Amount to | 1.013 | 0.666 | 31.489 | 31.489 | 0.592 | 0.462 | 32.365 | 32.365 | 29.632 | 2.733 |
The unit of each composition is Kmol/hr in the table.In table, HFC-134a is 1,1,1, and 2-Tetrafluoroethane, HFC-23 are trifluoromethanes, and HFC-125 is a pentafluoride ethane.
Table 2
(embodiment 2)
| Composition | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
| F 2 | 1.505 | - | 1.514 | 0.516 | 0.878 | - | 1.394 | 0.015 | 0.009 | 0.006 |
| HFC-125 | - | 0.9980 | 1.028 | 0.045 | - | - | 0.045 | 0.034 | 0.030 | 0.004 |
| HFC-32 | - | - | - | - | - | 0.693 | 0.693 | - | - | - |
| HF | - | - | 17.288 | 18.286 | - | - | 18.286 | 19.665 | 17.288 | 2.377 |
| HFC-23 | - | - | 0.030 | 0.015 | - | - | 0.015 | 0.033 | 0.030 | 0.003 |
| FC-116 | - | - | 4.983 | 5.966 | - | - | 5.966 | 5.977 | 4.983 | 0.994 |
| FC-14 | - | - | 7.295 | 7.310 | - | - | 7.310 | 7.985 | 7.295 | 0.690 |
| Other | 0.014 | 0.002 | 0.036 | 0.036 | 0.007 | - | 0.043 | 0.043 | 0.020 | 0.023 |
| Amount to | 1.519 | 1.000 | 32.174 | 32.174 | 0.885 | 0.693 | 33.752 | 33.752 | 29.655 | 4.097 |
The unit of each composition is Kmol/hr in the table.In table, HFC-125 is a pentafluoride ethane, and HFC-32 is a methylene fluoride, and HFC-23 is a trifluoromethane.
According to the present invention, can provide a kind of can be safely, effectively, the method for suitability for industrialized production perfluoro-carbon at low cost.
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 (12)
1. produce the method for perfluoro-carbon, comprise making by general formula C
xH
yF
zThe hydrofluorocarbons of representative and fluorine gas contact in first reaction zone with 200-550 ℃ temperature of reaction in vapour phase, to obtain the step of gaseous reaction mixture; With gaseous reaction mixture is introduced in second reaction zone as diluent gas and with its in this district in 200-550 ℃ temperature of reaction with send into second reaction zone by general formula C
xH
yF
zThe step of the hydrofluorocarbons contact of representative can comprise the step of sending into fluorine gas if necessary, and the hydrofluorocarbons of sending into second reaction zone is different with the hydrofluorocarbons that reacts at first reaction zone, at general formula C
xH
yF
zIn x, y and z are the integers that satisfies 1≤x≤3,1≤y≤4,1≤z≤7, its condition is y+z=4 when x is 1, when x is 2, y+z=6, y+z=8 when x is 3.
2. the described method of claim 1, wherein the gaseous reaction mixture that obtains at least partially in second reaction zone is used as the diluent gas of first reaction zone.
3. the described method of claim 1, wherein the diluent gas of first reaction zone and/or second reaction zone contains at least a in tetrafluoromethane, hexafluoroethane, octafluoropropane and the hydrogen fluoride.
4. the described method of claim 1, wherein diluent gas contains the hydrogen fluoride as a kind of main component.
5. the described method of claim 1, wherein the concentration of the hydrofluorocarbons that records in the inlet of first reaction zone and/or second reaction zone is no more than 8% (mole).
6. the described method of claim 1, wherein the reaction pressure of first reaction zone and/or second reaction zone is 0-5MPa.
7. the described method of claim 1 wherein produces two or more perfluoro-carbons.
8. the described method of claim 7, wherein having two kinds in the perfluoro-carbon that is produced at least is to be selected from tetrafluoromethane, hexafluoroethane and octafluoropropane.
9. the described method of claim 8, wherein the perfluoro-carbon that is produced is tetrafluoromethane and hexafluoroethane.
10. the described method of claim 1, wherein said hydrofluorocarbons is by at least two kinds of hydrofluorocarbons selecting in a fluoromethane, methylene fluoride, trifluoromethane, Halothane, Tetrafluoroethane, pentafluoride ethane, pentafluoropropane, hexafluoroethane and the heptafluoro-propane.
11. the described method of claim 10, wherein said hydrofluorocarbons are by at least two kinds of hydrofluorocarbons selecting in methylene fluoride, trifluoromethane, Tetrafluoroethane and the pentafluoride ethane.
12. the described method of claim 1, wherein in applied hydrofluorocarbons, the concentration of chlorine compound impurity is no more than 2% (mole).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8070294A JP3067633B2 (en) | 1996-03-26 | 1996-03-26 | Method for producing perfluorocarbon |
| JP70294/96 | 1996-03-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1161952A CN1161952A (en) | 1997-10-15 |
| CN1090162C true CN1090162C (en) | 2002-09-04 |
Family
ID=13427310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97102131A Expired - Fee Related CN1090162C (en) | 1996-03-26 | 1997-01-15 | Method for production of perfluorocarbon |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP3067633B2 (en) |
| KR (1) | KR100294570B1 (en) |
| CN (1) | CN1090162C (en) |
| DE (1) | DE19654719C2 (en) |
| GB (1) | GB2311522B (en) |
| SG (1) | SG99836A1 (en) |
| TW (1) | TW509666B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780691A (en) * | 1996-12-23 | 1998-07-14 | Allied Signal Inc. | Process for producing 1,1,1,2,3,3,3,-heptafluoroprane |
| KR100353491B1 (en) * | 2000-02-22 | 2002-09-19 | 울산화학주식회사 | Manufacturing method for perfluoroethane |
| WO2001098240A2 (en) * | 2000-06-21 | 2001-12-27 | Showa Denko K.K. | Process for producing hexafluoroethane and use thereof |
| WO2002018305A2 (en) | 2000-08-30 | 2002-03-07 | Showa Denko K. K. | Production and use of octafluoropropane |
| JP4539793B2 (en) * | 2000-08-30 | 2010-09-08 | 昭和電工株式会社 | Octafluoropropane production method and use thereof |
| TWI288025B (en) | 2000-09-14 | 2007-10-11 | Showa Denko Kk | Adsorbent for purifying perfluorocarbon, process for producing same, high purity octafluoropropane and octafluorocyclobutane, and use thereof |
| JP4703865B2 (en) * | 2001-02-23 | 2011-06-15 | 昭和電工株式会社 | Method for producing perfluorocarbons and use thereof |
| WO2002066408A2 (en) * | 2001-02-23 | 2002-08-29 | Showa Denko K.K. | Process for producing perfluorocarbons and use thereof |
| KR100447804B1 (en) * | 2001-07-09 | 2004-09-08 | 울산화학주식회사 | Manufacturing method of high purity perfluoroprpane |
| CN103772136B (en) * | 2012-10-24 | 2016-02-10 | 中化蓝天集团有限公司 | The production technique of hexafluoroethane |
| KR102657143B1 (en) * | 2016-08-31 | 2024-04-11 | 최은서 | A Storage Device Of Vinyl Roll For Portable |
| CN109867586A (en) * | 2017-12-04 | 2019-06-11 | 浙江省化工研究院有限公司 | A kind of method of fluoroform resourcable transformation production carbon tetrafluoride |
| CN111566077B (en) * | 2018-01-17 | 2023-03-24 | 昭和电工株式会社 | Method for producing tetrafluoromethane |
| WO2019142627A1 (en) * | 2018-01-19 | 2019-07-25 | 昭和電工株式会社 | Method of producing tetrafluoromethane |
| CN108114273B (en) * | 2018-02-02 | 2020-12-22 | 南京大学 | Perfluorocarbon albumin nanoparticles and preparation method and application thereof |
| CN113195443A (en) | 2018-12-19 | 2021-07-30 | 大金工业株式会社 | Process for producing fluoroethane and process for producing fluoroolefin |
| CN113195442A (en) | 2018-12-19 | 2021-07-30 | 大金工业株式会社 | Process for producing fluoroethane and process for producing fluoroolefin |
| JP6966712B2 (en) | 2019-01-25 | 2021-11-17 | ダイキン工業株式会社 | Method for producing fluoroethane and method for producing fluoroolefin |
| 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 |
| CN112614997B (en) * | 2020-12-18 | 2022-07-01 | 中国民航大学 | Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material |
| CN112778077A (en) * | 2021-01-18 | 2021-05-11 | 福建德尔科技有限公司 | Micro-reactor based electronic stage C2F6Preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4733715A (en) * | 1986-03-20 | 1988-03-29 | Hitachi Carbide Tools, Ltd. | Cemented carbide sleeve for casting apparatus |
| US4929317A (en) * | 1986-12-01 | 1990-05-29 | Tokuyama Soda Kabushiki Kaisha | Process for preparation of perfluoro organic compounds |
-
1996
- 1996-03-26 JP JP8070294A patent/JP3067633B2/en not_active Expired - Lifetime
- 1996-12-12 SG SG9611696A patent/SG99836A1/en unknown
- 1996-12-16 GB GB9626079A patent/GB2311522B/en not_active Expired - Fee Related
- 1996-12-18 KR KR1019960067181A patent/KR100294570B1/en not_active IP Right Cessation
- 1996-12-23 TW TW085115907A patent/TW509666B/en active
- 1996-12-30 DE DE19654719A patent/DE19654719C2/en not_active Expired - Fee Related
-
1997
- 1997-01-15 CN CN97102131A patent/CN1090162C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4733715A (en) * | 1986-03-20 | 1988-03-29 | Hitachi Carbide Tools, Ltd. | Cemented carbide sleeve for casting apparatus |
| US4929317A (en) * | 1986-12-01 | 1990-05-29 | Tokuyama Soda Kabushiki Kaisha | Process for preparation of perfluoro organic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970065493A (en) | 1997-10-13 |
| CN1161952A (en) | 1997-10-15 |
| TW509666B (en) | 2002-11-11 |
| GB9626079D0 (en) | 1997-02-05 |
| GB2311522A (en) | 1997-10-01 |
| DE19654719A1 (en) | 1997-10-02 |
| JPH09255598A (en) | 1997-09-30 |
| GB2311522B (en) | 1999-09-29 |
| JP3067633B2 (en) | 2000-07-17 |
| DE19654719C2 (en) | 2000-09-28 |
| SG99836A1 (en) | 2003-11-27 |
| KR100294570B1 (en) | 2001-09-17 |
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