CA1117144A - Manufacture of halogenated hydrocarbons - Google Patents
Manufacture of halogenated hydrocarbonsInfo
- Publication number
- CA1117144A CA1117144A CA000303896A CA303896A CA1117144A CA 1117144 A CA1117144 A CA 1117144A CA 000303896 A CA000303896 A CA 000303896A CA 303896 A CA303896 A CA 303896A CA 1117144 A CA1117144 A CA 1117144A
- Authority
- CA
- Canada
- Prior art keywords
- dichloro
- tetrafluoroethane
- hydrogen
- fluorine
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A B S T R A C T
A new route to tetrafluoroethane consists of the reaction of 1,1-dichloro 1,2,2,2-tetrafluoroethane and/
or 1,2-dichloro-1,1,2,2-tetrafluoroethane with hydrogen in the vapour phase in the presence of an hydrogenation catalyst, preferably a palladium catalyst.
A new route to tetrafluoroethane consists of the reaction of 1,1-dichloro 1,2,2,2-tetrafluoroethane and/
or 1,2-dichloro-1,1,2,2-tetrafluoroethane with hydrogen in the vapour phase in the presence of an hydrogenation catalyst, preferably a palladium catalyst.
Description
This invention relates to a process for the manufacture of tetrafluoroethane.
According to the present invention we provide a process for the manufacture of tetrafluoroethane having the formula :: 5 CHF2CHF2 or CF3CH2F characterised in that a ~ haloethane having four or five fluorine atoms of : formula CF2 X CFYZ where X is fluorine or chlorine and when X is fluorlne, Y is chlorine or fluorine and when Y
is chlorine Z is chlorine, fluorine or hydrogen and ~: 10 when Y is fluorine Z is hydrogen and when X is chlorine Y is fluorine and Z is either chlorine or hydrogen is : reacted with hydrogen at elevated temperature in the presence of a hydrogenation catalyst.
3~:
The or~anic starting materials of the present invention consist of :-1,2-dichloro-1,1,2,2-tetrafluoroethane (CClF2 CClF2) l,l-dichloro 1,2,2,2-tetrafluoroethane (CC12F CF3) 1-chloro-1,1,2,2,2-pentafluoroethane (CClF2 CF3) l-chloro-1,2,2,2-tetrafluoroethane (CHClFCF3)
According to the present invention we provide a process for the manufacture of tetrafluoroethane having the formula :: 5 CHF2CHF2 or CF3CH2F characterised in that a ~ haloethane having four or five fluorine atoms of : formula CF2 X CFYZ where X is fluorine or chlorine and when X is fluorlne, Y is chlorine or fluorine and when Y
is chlorine Z is chlorine, fluorine or hydrogen and ~: 10 when Y is fluorine Z is hydrogen and when X is chlorine Y is fluorine and Z is either chlorine or hydrogen is : reacted with hydrogen at elevated temperature in the presence of a hydrogenation catalyst.
3~:
The or~anic starting materials of the present invention consist of :-1,2-dichloro-1,1,2,2-tetrafluoroethane (CClF2 CClF2) l,l-dichloro 1,2,2,2-tetrafluoroethane (CC12F CF3) 1-chloro-1,1,2,2,2-pentafluoroethane (CClF2 CF3) l-chloro-1,2,2,2-tetrafluoroethane (CHClFCF3)
2-chloro-1,1,2,2-tetrafluoroethane (CHF2 CClF2) 1,1,2,2,2-pentafluoroethane (CHF2 CF3) Mixtures of said organic starting materials may be employed. Two very suitable starting materials are 1,2-dichloro-1,1,2,2-tetrafluoroethane (the sym isomer of dichloro-tetrafluoroethane, CClF2CClF2) and 1,1-dichloro-1,2,2,2-tetrafluoroethane (the asym isomer of dichloro-tetrafluoroethane, CC12FCF3). 1,2-dichloro-1,1,2,2-tetrafluoroethane containing a small proportion (e.g. up to 10% by wt) of 1,1-dichloro-1,2,2,2-tetrafluoro-ethane) as produced commercially may be used as organic starting materials. Alternatively mixtures of said dichloro-tetrafluoroethanes in any proportions may be employed.
3~
Hydro~enation catalysts are in themselves known.
In the present process there is removal of two chlorine atoms or a chlorine and/or a fluorine atom feom the haloethane starting material and substitution oE hydrogen therefor. Examples of hydrogenation catalysts include nickel or metals of Group VIIIa of the Periodic Table or oxides or salts thereof.
In use a compound of such a metal is reduced at least in part to the metal. One very useful metal which can be employed in the process of the present invention is palladium. The metal may be carried on a suitable support, for example, alumina or activated carbon.
The proportion of hydrogen to organic feed is capable of considerable variation. Usually at least the stoichiometric amount of hydrogen is employed to remove the halogen atom or atoms. Considerably greater than said stoichiometric amounts for example
Hydro~enation catalysts are in themselves known.
In the present process there is removal of two chlorine atoms or a chlorine and/or a fluorine atom feom the haloethane starting material and substitution oE hydrogen therefor. Examples of hydrogenation catalysts include nickel or metals of Group VIIIa of the Periodic Table or oxides or salts thereof.
In use a compound of such a metal is reduced at least in part to the metal. One very useful metal which can be employed in the process of the present invention is palladium. The metal may be carried on a suitable support, for example, alumina or activated carbon.
The proportion of hydrogen to organic feed is capable of considerable variation. Usually at least the stoichiometric amount of hydrogen is employed to remove the halogen atom or atoms. Considerably greater than said stoichiometric amounts for example
4 or more moles of hydrogen may be employed per total mole of starting material. When the organic starting materials consists of essentially pure 1,2-dichloro-1,1,2,2-tetrafluoroethane (CClF2CClF2) or l,l-dichloro-1,2,2,2-tetrafluoroethane (CCl2FCF3~ it is preferred to employ at least two moles of hydrogen (the stoichiometric amount) per mole of organic starting material. When a mixture of CClF2CClF2 and CC12FCF3 is employed as organic feed there may be employed at least the stoichiometric amount of hydrogen per mole of CC12FCF3. This can mean that there is sometimes less tha:n the stoichiometric amount of hydrogen with respect. to total mole fluorochloroethane feed. Thus with a mixture containing 3 moles CClF2CClF2 and 1 mole CC12FCF3 there may be employed 2 to 3 moles of hydrogen per mole CClF2CF3 and this corresponds to a molar ratio of hydrogen to total mole fluorochloroethane feed of 0.5:1 to 0.75:1 respectively. Similarly when there is employed an equimolar mixture of CClF2CClF2 and CC12FCF3 there may be employed 2 to 3 moles of hydrogen per mole CC12FCF3 and thus corresponds to a molar ratio of hydrogen to total mole fluorochloro-ethane feed of 1:1 to 1.5:1. On the other hand with a mixture of 3 moles CF2ClCF2Cl and 1 mole CC12FCF3 there may be employed 3 moles H2 per total mole of total fluoroethane and this corresponds to 12 moles H2 per mole C12FCF3.
~- Atmospheric or superatmospheric pressures may be employed.
~ -' ' , 6.
The reactiorl temperature is suitably carried out ~n the vapour phase at a temperature which is at least 200C
and not greater than 450C. Preferably the reaction temperature is in the range 225C to 40~ac.
Contact times are usually in the ~ange 5 to 60 seconds especially 5 to 30 seconds when the reaction is carried out in the vapour phase.
The tetraEluoroethane product obtained depends to a considerable extent on the choice of starting material.
When the organic starting material is 1,l~dic~loro-1,2,2j2-tetrafluoroethane, l,1,1,2-tetrafluoroethane (asym tetra-fluoroethane; CF3CH2F) is obtained almost to the exclusion of 1,1,2,2-tetrafluoroethane tsym tetrafluoro-e~hane, CHF2.CHF2). When the organic stàrting material is 1,2-dichloro-1,1,2,2-tetra~luoroethane the reactian , ~ product usually comprises a mixture o the twa isomers of tetrafluoroethane. As the proportion of l,l-dichloro-1,Z,2¦2-tetrafluoroethane with respect to 1,2-dichloro-1,1,2,2-tetrafluoroethane is increased in a mixture thereof increased amounts of the asymmetrical isomer CF3CH2F is formed. Also an alumina support is especially useful for the manufacture of CF3CH2F while an activated carbon support is especially useful~in the manufacture of a mixture of CF3CH2F and CHF2FHF2.
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In the present process hydrogen and organic by-prod~cts, for example, 2-chloro-1,1,1,2-tetrafluoro-ethane may be recycled to the process. The desired products of the present invention may be separated by conventional means e.g. by fractional distillation.
Unreacted 1,2-dichloro-1,1,2,2-tetrafluoroethanè may if desired be tapped off and used as a refrigerant.
The present process has the advantages that the desirable l,1,1,2-tetraEluoroethane, 1,1,2,2-tetrafluoroethane or mixtures thereo~ in variousproportions can be obtained by a simple and convenient method. Desired products can be obtained in high degree of purity with good conversions of the fluoro-chloroethane starting material.
The following Examples illustrate the invention:-Into a heat-resistant glass tube 30 cms long and 2.5 cms internal diameter, surrounded by an electric furnace, were centrally placed 40 mls o~ a particulate catalyst consisting of palladium supported on charcoal~ This catalyst was intimately mixed with 40 mls glass helices to prevent clogging of the catalyst. The palladium was present in the proportion
~- Atmospheric or superatmospheric pressures may be employed.
~ -' ' , 6.
The reactiorl temperature is suitably carried out ~n the vapour phase at a temperature which is at least 200C
and not greater than 450C. Preferably the reaction temperature is in the range 225C to 40~ac.
Contact times are usually in the ~ange 5 to 60 seconds especially 5 to 30 seconds when the reaction is carried out in the vapour phase.
The tetraEluoroethane product obtained depends to a considerable extent on the choice of starting material.
When the organic starting material is 1,l~dic~loro-1,2,2j2-tetrafluoroethane, l,1,1,2-tetrafluoroethane (asym tetra-fluoroethane; CF3CH2F) is obtained almost to the exclusion of 1,1,2,2-tetrafluoroethane tsym tetrafluoro-e~hane, CHF2.CHF2). When the organic stàrting material is 1,2-dichloro-1,1,2,2-tetra~luoroethane the reactian , ~ product usually comprises a mixture o the twa isomers of tetrafluoroethane. As the proportion of l,l-dichloro-1,Z,2¦2-tetrafluoroethane with respect to 1,2-dichloro-1,1,2,2-tetrafluoroethane is increased in a mixture thereof increased amounts of the asymmetrical isomer CF3CH2F is formed. Also an alumina support is especially useful for the manufacture of CF3CH2F while an activated carbon support is especially useful~in the manufacture of a mixture of CF3CH2F and CHF2FHF2.
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7.
In the present process hydrogen and organic by-prod~cts, for example, 2-chloro-1,1,1,2-tetrafluoro-ethane may be recycled to the process. The desired products of the present invention may be separated by conventional means e.g. by fractional distillation.
Unreacted 1,2-dichloro-1,1,2,2-tetrafluoroethanè may if desired be tapped off and used as a refrigerant.
The present process has the advantages that the desirable l,1,1,2-tetraEluoroethane, 1,1,2,2-tetrafluoroethane or mixtures thereo~ in variousproportions can be obtained by a simple and convenient method. Desired products can be obtained in high degree of purity with good conversions of the fluoro-chloroethane starting material.
The following Examples illustrate the invention:-Into a heat-resistant glass tube 30 cms long and 2.5 cms internal diameter, surrounded by an electric furnace, were centrally placed 40 mls o~ a particulate catalyst consisting of palladium supported on charcoal~ This catalyst was intimately mixed with 40 mls glass helices to prevent clogging of the catalyst. The palladium was present in the proportion
5% by weight with reference to the charcoal.
' , ~' ' ', ~1~17 a.
Hydro~en and dichlorotetrafluoroethane (96.5~ hy weight, 1,2-dichloro-1,1,2,2-tetra1uoroethane; 3.5~
by weight, l,l-dichloro-1,2,2,2-tetrafluoroethane) at a molar ratio of 2:1 were passed through the heated tube, the catalyst bed being maintained at various reaction temperatures. The flow rates of organic material and hydrogen were 50 cc/min and 100 cc/min, respectively. The % v/v of organic materials in the exit gas was determined by gas liauid chromatography.
The other reaction conditions and composition of the organic products were as shown in Table 1.
TABLE I
.. . ._ Temperature C
Product % v/v I ~ . ' 1---_ Contact time (secs.) e 17.916.3 15.614.6 . . _____e-- _ __ __ CF3 CH2F 6.1 9.2 9.811.4 CHF2 CHF2 4.4 8.911.7 CHF CClF /
CHC~FCF32 3.620.1 21.321.4 :: .__ - . .... __ CClF CClF2i .
CCl2~Cp3 ~ 89.264.8 57.3 146.2 CF3CH3 0.6 1.5 1 2.2 3.3 Othe~- 0 5 5 9 The procedure of Example 1 was essentially repeated but with a molar ratio of H2:organic . starting material of 3:1. The flow rates of organic material and hydrogen were 50 cc/min and 150 cc/min, respectively. The other reaction conditions and composition of the organic products were as shown in Table II.
TABLE II
_ . _I
Temperature C
Product ~ v/v 240 1 255 1 300 ~ 325 Contact time (secs.) _ 12 8 12.-4 ~~ 11 4 ll.o CF3.cH2F 11.3 9.9 9.7 8.1 : CHF2CHF2 7.4 17.6 29.6 35.9 .. ___ ..
:1 : CHF CClF2/
~1 CHC~FCF3 - 40.548.9 40.1 39.5 CClF .CClF2/
: CC12FCF3 . 39.421.4 17.3 10.8 :~ CF3.CH3 1.4 11.8 1 2.1 3.1 ._ ~ - ~ !
I Others I ¦ 0.3 1.2 l 2.6 :
:~
10 .
.
The general proceclure of Example 2 was repeated but with l,l-clichloro-1,2,2,2-tetrafluoroethane as organic starting material. The other reaction conditions and composition of the organic products were as indicated in Table III.
TABLE III
. . . _ Temperature C
Product %v/v .. _ . 285 310 Contact time (secs.) .
: 1205 12.0 _ CF3.CH2F 71.7 72.0 - . ~ ........ . ___ CHF2.CHF2 0.9 ¦ 0.3 C~ClFCF /
:~ CF2ClCF32H 8.1 6.1 :~ .. .
lS ~ CClb2'C~1~2 11.
. CF3.CH3 1 8.3 1509 The general procedure of Example 2 was repeated but with a mixture of 1,2-dichloro-1,1,2,2~tetra-fluoroethane, (72% by weight) and l,l-dichloro-S 1,2,2,2-tetrachloroethane (28~ by weight) as organic starting material. The molar ratio of N2:the mixed organic starting material WclS 3:1. The flow rates of hydrogen and organic starting material were 150 cc/min and 50 cc/min, respectively. The reaction temperature was 300C. The contact time was 12 seconds.
The composition of the organic product was as given in Table IV.
TABLE IV
Product ~ v/v ;~ 15 CF3.CH2F l 37.6 .. _ ~._ CHF2CH~2 14.9 2CClF2/C~ClFCF3 26.8 CF3.CH3 13.0 . .
2 2/cFcl2cF3 7.7 , _ : ' ~
:
12.
ÆXAMPLE 5 The general procedure o~ Example 4 was repeated except that the flow rate of hydrogen and the mixed organic starting material and h~drogen was 100 cc/min and 33 cc/min, respectively, and the contact time was 18 seconds.
The composition of the organic product was as given in Table V.
TABLE V
I Product % v/v _ _ . CF3 CH2F 46.2 ~ .
CHF2CHF2 8.0 CHF CClF2/
CHC~FCF3 26 _ F3 CH3 ~8.2 .~ .
: : CClF2 CClF2/
2CF3 11.3 , . . .__ . ___ The general procedure of Example 5 was repeated ~:: except that the f~low rates:of hydrogen and organic starting material were 90 cc/mln and 30 cc/min, respectively, the contact time was l9 seconds and the reaction temperature was 350C.
' , ~
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:~
11~17~g~4 13.
The composition o~ the organic product was as given in Table VI.
TABLE VI
Product % v/v CF3 CH2F 41.~ ¦
.
CHF2 CHF2 16.3 .. _ , _ CHF CClF2/
CHC~FCF3 24.8 : . 3 3 11.8 ¦ CClF2 CClF2/ 5.3 , CFC12CF3 ~ ~ .
The general procedure of Example 2 was~repeated but with 2-chloro-1,1,1,2-tetrafluoroethane as starting material. The other reaction conditions and composition of the organic product were as indicated ; 15 in Table VII.
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TABLE VII
, Temperature C
Product % v/v ~
Contact time (secs.)l CF3 CH2F 82.0 94.1 95.8 CHF2 CHF2 0.8 0.8 0 CF3 CH3 1.4 2.9 3.3 .
CHClFCF3 15.7 2.3 0 C~F4 0 0.9 The apparatus comprised a heat-resistant glass tube 30 cms long and 2.5 cms internal diameter surrounded by an electric furnace. Two part.culate catalysts were employed which consisted of palladium (2% w/w and 5~ w/w) ~ supported on alumina.
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,' ~ . ~ ' 15.
Hydrogen and a mixture of 1,2-dichloro-1,1,2,2 tetrafluoroethane ~72~ by weight) and l,l-dichloro-1,2,2,2-tetrafluoroethane (28% by weight) were passed over the catalyst under various reaction conditions as disclosed in Table VIII. The molar ratios of hydrogen with respect to total dichlorotetrafluoroethane starting material for Runs 1,2 and 3 were O.S:l, 0.5:1 of 0.75:1, respectively. The flow rates of H2 and CC12FCF3 for these Runs were 50 and 25 cc/min, 50 and 25 cc/min, and 63 cc/min and 21 cc/min, respectively.
Thé % v/v of organic materials in the exit gas was determined by gas liquid chromatography.
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TA~LE VI I I
j Run 1 ¦Run 2 I Run 3 ff . . . I
Temperature C f 3~)0 ~ 2g5 1 300 Product Contact timfef ( secs) ~ v/v . 10.6 1 10.3 I 16.3 ~ Pf~ in catalyst (w/w) Molar Ratio H2: CFC12CF3 .
.. , CF3CH2F 20 18 . 8 24 . 9 ._. .. . : .
CHF2CHF2 _ . .. ~ .
I ~ ICHC1FCF /
~ CHF2CC1~2 2.6 0.4 ~ 0.3 ~. I ~------jCF3CH3 ~ 0.4 0.5 ¦0. 3 - ~_ - __ _ .
j 15 CFC12CF3 62.5 171.9 I64.4 ~: f . __ I , I ~1: Other fluoro~
chlor water C
;: compounds 2 j 10.9 5 . 7 f8 .0 - . . . ~ , ,, .
.
.
.
n~ 9L 4 17.
The apparatus comprised a vertical 'Inconel' tube ('Inconel' is a Registered Trade Mark) of 7.5 cms internal diameter. The tube was packed to a height of 90 cm with a catalyst in the form of spheres (3 mm diameter) consisting of 2% w/w Pd supported on alumina.
: Hydrogen and a mixture of l,2-dichloro-1,1,2,2-tetrafluoroethane (50% by weight) and l,l-dichloro-l,2,2,2-tetrafluoroethane (50% by weight) were passed upwardly through the static catalyst under various process conditions as disclosed in Table IX. The molar ratios of hydrogen with respect to total dichlorotetrafluoroethane starting material for Runs 1,2 and 3 were l.45:1, 1.6:l and l.6:l, respectively.
The flow rates of H2: CFC12CF3 for these runs were 3.14 1 and 0.98 l/min, 3.81 l and l.lS l/min and 3.8 l and 1.15 1/min, respectively.
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TABLE IX
. . _ _ . . _ . . i , . _ ~ . _ _ . _ ! I Run 1 I Run 2 ~ Run 2 ~ --- I
, Temperature C
Product ~ ¦
v/v ~ ..... _ 250 1 275 ~ 330 _ . .
Contact time (secs) . ,~ .. _I
Molar ratio H2:CFCl2CF3 ,. _ .
3.2:1 1 3.2:1 3.3:1 ... ... _ 1 .. . _ CF3CH2F 46.l ~ 35.5 26.8 :.. _.. _ =_.___ _ __ - !
CHF2CHF2 _ _ ~ . __ CHClFCF /
CHF2CC1~2 3.4 5.4 2.0 ~ __ .
: : CF3CH3 l.6 1.9 1.2 _ ~............ ...... ............... ... .... .
CClF2CClF2/
:~ CFCl2CF3 45.8 54.6 69 .__~
:~ Other fluoro- I I
chloro C ' ¦
~: : 15 compound~ 0.5 1 0.5 0.4 1,1,1,2-tetrafluoroethane was recovered from the crude reaction product by distillation in a glass apparatus : consisting of a boiler, surmounted by a fractionation column having 40 theoretical plates, a reflux divlder and condenser. The apparatus was operated at atmospheric ' ~
19 .
pressure and after removal of lights boiling at - 40C to -27C said 1,1,1,2 tetrafluoroethane was eecovered as a top-product boiling at -26C.
The apparatus comprised a mild steel tube (5 cms diameter) packed through 300 cms of its length with a catalyst in the form of spheres (3 mm diameter) consisting of 2% w/w Pd supported on alumlna.
5 Kgs per hour of a mixture of 1,2-dichloro-1,1,2,2-tetrafluoroethane (50% by weight) and 1,1-dichloro-1,2,2,2-tetrafluoroethane (50% by weight) and 770 l/hour of hydrogen were passed upwardly through the static catalyst. The pressure was 5 Bars gauge. The temperature of the catalyst bed was maintained by a molten salt bath at 340C. The contact time was 51 seconds. The molar ratio of hydrogen with respect to total dichlorotetrafluoroethane starting material was 1.1:1, the molar ratio of hydrogen ; ~ with respect to 1,1-dichloro-1,2,2,2-tetrafluoroethane being 2.2:1.
The organic reaction product after washing with dilute caustic soda solution and drying over calcium chloride was condensed at -70C and comprised (v/v):
25% CF3CH2F
5% CF3CH3 5% CHClFCF3 65~ CF2ClCF2Cl/CF3CFC12 .
' , ~' ' ', ~1~17 a.
Hydro~en and dichlorotetrafluoroethane (96.5~ hy weight, 1,2-dichloro-1,1,2,2-tetra1uoroethane; 3.5~
by weight, l,l-dichloro-1,2,2,2-tetrafluoroethane) at a molar ratio of 2:1 were passed through the heated tube, the catalyst bed being maintained at various reaction temperatures. The flow rates of organic material and hydrogen were 50 cc/min and 100 cc/min, respectively. The % v/v of organic materials in the exit gas was determined by gas liauid chromatography.
The other reaction conditions and composition of the organic products were as shown in Table 1.
TABLE I
.. . ._ Temperature C
Product % v/v I ~ . ' 1---_ Contact time (secs.) e 17.916.3 15.614.6 . . _____e-- _ __ __ CF3 CH2F 6.1 9.2 9.811.4 CHF2 CHF2 4.4 8.911.7 CHF CClF /
CHC~FCF32 3.620.1 21.321.4 :: .__ - . .... __ CClF CClF2i .
CCl2~Cp3 ~ 89.264.8 57.3 146.2 CF3CH3 0.6 1.5 1 2.2 3.3 Othe~- 0 5 5 9 The procedure of Example 1 was essentially repeated but with a molar ratio of H2:organic . starting material of 3:1. The flow rates of organic material and hydrogen were 50 cc/min and 150 cc/min, respectively. The other reaction conditions and composition of the organic products were as shown in Table II.
TABLE II
_ . _I
Temperature C
Product ~ v/v 240 1 255 1 300 ~ 325 Contact time (secs.) _ 12 8 12.-4 ~~ 11 4 ll.o CF3.cH2F 11.3 9.9 9.7 8.1 : CHF2CHF2 7.4 17.6 29.6 35.9 .. ___ ..
:1 : CHF CClF2/
~1 CHC~FCF3 - 40.548.9 40.1 39.5 CClF .CClF2/
: CC12FCF3 . 39.421.4 17.3 10.8 :~ CF3.CH3 1.4 11.8 1 2.1 3.1 ._ ~ - ~ !
I Others I ¦ 0.3 1.2 l 2.6 :
:~
10 .
.
The general proceclure of Example 2 was repeated but with l,l-clichloro-1,2,2,2-tetrafluoroethane as organic starting material. The other reaction conditions and composition of the organic products were as indicated in Table III.
TABLE III
. . . _ Temperature C
Product %v/v .. _ . 285 310 Contact time (secs.) .
: 1205 12.0 _ CF3.CH2F 71.7 72.0 - . ~ ........ . ___ CHF2.CHF2 0.9 ¦ 0.3 C~ClFCF /
:~ CF2ClCF32H 8.1 6.1 :~ .. .
lS ~ CClb2'C~1~2 11.
. CF3.CH3 1 8.3 1509 The general procedure of Example 2 was repeated but with a mixture of 1,2-dichloro-1,1,2,2~tetra-fluoroethane, (72% by weight) and l,l-dichloro-S 1,2,2,2-tetrachloroethane (28~ by weight) as organic starting material. The molar ratio of N2:the mixed organic starting material WclS 3:1. The flow rates of hydrogen and organic starting material were 150 cc/min and 50 cc/min, respectively. The reaction temperature was 300C. The contact time was 12 seconds.
The composition of the organic product was as given in Table IV.
TABLE IV
Product ~ v/v ;~ 15 CF3.CH2F l 37.6 .. _ ~._ CHF2CH~2 14.9 2CClF2/C~ClFCF3 26.8 CF3.CH3 13.0 . .
2 2/cFcl2cF3 7.7 , _ : ' ~
:
12.
ÆXAMPLE 5 The general procedure o~ Example 4 was repeated except that the flow rate of hydrogen and the mixed organic starting material and h~drogen was 100 cc/min and 33 cc/min, respectively, and the contact time was 18 seconds.
The composition of the organic product was as given in Table V.
TABLE V
I Product % v/v _ _ . CF3 CH2F 46.2 ~ .
CHF2CHF2 8.0 CHF CClF2/
CHC~FCF3 26 _ F3 CH3 ~8.2 .~ .
: : CClF2 CClF2/
2CF3 11.3 , . . .__ . ___ The general procedure of Example 5 was repeated ~:: except that the f~low rates:of hydrogen and organic starting material were 90 cc/mln and 30 cc/min, respectively, the contact time was l9 seconds and the reaction temperature was 350C.
' , ~
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:~
11~17~g~4 13.
The composition o~ the organic product was as given in Table VI.
TABLE VI
Product % v/v CF3 CH2F 41.~ ¦
.
CHF2 CHF2 16.3 .. _ , _ CHF CClF2/
CHC~FCF3 24.8 : . 3 3 11.8 ¦ CClF2 CClF2/ 5.3 , CFC12CF3 ~ ~ .
The general procedure of Example 2 was~repeated but with 2-chloro-1,1,1,2-tetrafluoroethane as starting material. The other reaction conditions and composition of the organic product were as indicated ; 15 in Table VII.
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TABLE VII
, Temperature C
Product % v/v ~
Contact time (secs.)l CF3 CH2F 82.0 94.1 95.8 CHF2 CHF2 0.8 0.8 0 CF3 CH3 1.4 2.9 3.3 .
CHClFCF3 15.7 2.3 0 C~F4 0 0.9 The apparatus comprised a heat-resistant glass tube 30 cms long and 2.5 cms internal diameter surrounded by an electric furnace. Two part.culate catalysts were employed which consisted of palladium (2% w/w and 5~ w/w) ~ supported on alumina.
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: ~:
,' ~ . ~ ' 15.
Hydrogen and a mixture of 1,2-dichloro-1,1,2,2 tetrafluoroethane ~72~ by weight) and l,l-dichloro-1,2,2,2-tetrafluoroethane (28% by weight) were passed over the catalyst under various reaction conditions as disclosed in Table VIII. The molar ratios of hydrogen with respect to total dichlorotetrafluoroethane starting material for Runs 1,2 and 3 were O.S:l, 0.5:1 of 0.75:1, respectively. The flow rates of H2 and CC12FCF3 for these Runs were 50 and 25 cc/min, 50 and 25 cc/min, and 63 cc/min and 21 cc/min, respectively.
Thé % v/v of organic materials in the exit gas was determined by gas liquid chromatography.
.
.. ~ , , :
:
16 .
TA~LE VI I I
j Run 1 ¦Run 2 I Run 3 ff . . . I
Temperature C f 3~)0 ~ 2g5 1 300 Product Contact timfef ( secs) ~ v/v . 10.6 1 10.3 I 16.3 ~ Pf~ in catalyst (w/w) Molar Ratio H2: CFC12CF3 .
.. , CF3CH2F 20 18 . 8 24 . 9 ._. .. . : .
CHF2CHF2 _ . .. ~ .
I ~ ICHC1FCF /
~ CHF2CC1~2 2.6 0.4 ~ 0.3 ~. I ~------jCF3CH3 ~ 0.4 0.5 ¦0. 3 - ~_ - __ _ .
j 15 CFC12CF3 62.5 171.9 I64.4 ~: f . __ I , I ~1: Other fluoro~
chlor water C
;: compounds 2 j 10.9 5 . 7 f8 .0 - . . . ~ , ,, .
.
.
.
n~ 9L 4 17.
The apparatus comprised a vertical 'Inconel' tube ('Inconel' is a Registered Trade Mark) of 7.5 cms internal diameter. The tube was packed to a height of 90 cm with a catalyst in the form of spheres (3 mm diameter) consisting of 2% w/w Pd supported on alumina.
: Hydrogen and a mixture of l,2-dichloro-1,1,2,2-tetrafluoroethane (50% by weight) and l,l-dichloro-l,2,2,2-tetrafluoroethane (50% by weight) were passed upwardly through the static catalyst under various process conditions as disclosed in Table IX. The molar ratios of hydrogen with respect to total dichlorotetrafluoroethane starting material for Runs 1,2 and 3 were l.45:1, 1.6:l and l.6:l, respectively.
The flow rates of H2: CFC12CF3 for these runs were 3.14 1 and 0.98 l/min, 3.81 l and l.lS l/min and 3.8 l and 1.15 1/min, respectively.
' ~ ~
~:
.: .
TABLE IX
. . _ _ . . _ . . i , . _ ~ . _ _ . _ ! I Run 1 I Run 2 ~ Run 2 ~ --- I
, Temperature C
Product ~ ¦
v/v ~ ..... _ 250 1 275 ~ 330 _ . .
Contact time (secs) . ,~ .. _I
Molar ratio H2:CFCl2CF3 ,. _ .
3.2:1 1 3.2:1 3.3:1 ... ... _ 1 .. . _ CF3CH2F 46.l ~ 35.5 26.8 :.. _.. _ =_.___ _ __ - !
CHF2CHF2 _ _ ~ . __ CHClFCF /
CHF2CC1~2 3.4 5.4 2.0 ~ __ .
: : CF3CH3 l.6 1.9 1.2 _ ~............ ...... ............... ... .... .
CClF2CClF2/
:~ CFCl2CF3 45.8 54.6 69 .__~
:~ Other fluoro- I I
chloro C ' ¦
~: : 15 compound~ 0.5 1 0.5 0.4 1,1,1,2-tetrafluoroethane was recovered from the crude reaction product by distillation in a glass apparatus : consisting of a boiler, surmounted by a fractionation column having 40 theoretical plates, a reflux divlder and condenser. The apparatus was operated at atmospheric ' ~
19 .
pressure and after removal of lights boiling at - 40C to -27C said 1,1,1,2 tetrafluoroethane was eecovered as a top-product boiling at -26C.
The apparatus comprised a mild steel tube (5 cms diameter) packed through 300 cms of its length with a catalyst in the form of spheres (3 mm diameter) consisting of 2% w/w Pd supported on alumlna.
5 Kgs per hour of a mixture of 1,2-dichloro-1,1,2,2-tetrafluoroethane (50% by weight) and 1,1-dichloro-1,2,2,2-tetrafluoroethane (50% by weight) and 770 l/hour of hydrogen were passed upwardly through the static catalyst. The pressure was 5 Bars gauge. The temperature of the catalyst bed was maintained by a molten salt bath at 340C. The contact time was 51 seconds. The molar ratio of hydrogen with respect to total dichlorotetrafluoroethane starting material was 1.1:1, the molar ratio of hydrogen ; ~ with respect to 1,1-dichloro-1,2,2,2-tetrafluoroethane being 2.2:1.
The organic reaction product after washing with dilute caustic soda solution and drying over calcium chloride was condensed at -70C and comprised (v/v):
25% CF3CH2F
5% CF3CH3 5% CHClFCF3 65~ CF2ClCF2Cl/CF3CFC12 .
Claims (13)
What we claim is:-
1. A process for the manufacture of tetrafluoro-ethane having the formula CF3CH2F or CHF2CHF2 characterised in that a haloethane having four or five fluorine atoms of formula CF2XCFYZ where X is fluorine or chlorine and when X is fluorine, Y is chlorine or fluorine and when Y is chlorine Z is chlorine, fluorine or hydrogen and when Y is fluorine Z is hydrogen and when X is chlorine Y is fluorine and Z
is either chlorine or hydrogen is reacted with hydrogen at a temperature of at least 200°C and noy greater than 450°C in the presence of a hydrogenation.
catalyst.
is either chlorine or hydrogen is reacted with hydrogen at a temperature of at least 200°C and noy greater than 450°C in the presence of a hydrogenation.
catalyst.
2. A process as claimed in Claim 1 characterised in that the haloethane starting material is 1,2-dichloro-1,1,2,2-tetrafluoroethane.
3. A process as claimed in Claim 1 characterised in that the haloethane starting material is 1,1-dichloro-1,2,2,2-tetrafluoroethane.
4. A process as claimed in Claim 1 characterised in that the haloethane starting material is a mixture of 1,2-dichloro-1,1,2,2-tetrafluoro-ethane and 1,1-dichloro-1,2,2,2-tetrafluoroethane.
21.
21.
5. A process as claimed in Claim 4 characterised in that the molar ratio of 1,2-dichloro-1,1,2,2-tetrafluoroethane to 1,1-dichloro-1,2,2,2-tetra-fluoroethane is in the range 3:1 to 1:1.
6. A process as claimed in Claim 1, 2 or 3 characterised in that at least the stoichiometric amount of hydrogen is employed to remove the halogen atom or atoms.
7. A process as claimed in Claim 1, 2 ox 3 characterised in that there is employed up to four moles of hydrogen per total mole of haloethane.
8. A process as claimed in Claim 5 characterised in that the molar ratio of 1,2-dichloro-1,1,2,2-tetra-fluoroethane to 1,1-dichloro-1,2,2,2-tetrafluoroethane is 3:1 and in which there is employed 2 to 3 moles of hydrogen per mole of 1,1-dichloro-1,2,2,2-tetrafluoro-ethane corresponding to 0.5 to 0.75 moles hydrogen per total mole fluorochloroethane, respectively.
9. A process as claimed in Claim 5 characterised in that the molar ratio of 1,2-dichloro-1,1,2,2-tetrafluoroethane to 1,1-dichloro-1,2,2,2-tetrafluoro-ethane is essentially 1:1 and in which there is employed 2 to 3 moles of hydrogen per mole of 1,1-dichloro-1,2,2,2- tetrafluoroethane corresponding to 1 to 1.5 moles hydrogen per total mole fluorochloro-ethane, respectively.
22.
22.
10. A process as claimed in Claim 1 characterised in that the hydrogenation catalyst is palladium.
11. A process as claimed in Claim 10 characterised in that the palladium is carried on an activated carbon support.
12. A process as claimed in Claim 10 characterised in that the palladium is carried on an alumina support.
13. A process as claimed in Claim 1 characterised in that the reaction temperature is in the range 225°C to 400°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB21806/77A GB1578933A (en) | 1977-05-24 | 1977-05-24 | Manufacture of halogenated hydrocarbons |
| GB21806/77 | 1977-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117144A true CA1117144A (en) | 1982-01-26 |
Family
ID=10169139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000303896A Expired CA1117144A (en) | 1977-05-24 | 1978-05-23 | Manufacture of halogenated hydrocarbons |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS53147005A (en) |
| AR (1) | AR223815A1 (en) |
| AU (1) | AU515866B2 (en) |
| BE (1) | BE867285A (en) |
| BR (1) | BR7803299A (en) |
| CA (1) | CA1117144A (en) |
| DE (1) | DE2822471A1 (en) |
| ES (1) | ES470170A1 (en) |
| FR (1) | FR2391980A1 (en) |
| GB (1) | GB1578933A (en) |
| GR (1) | GR63074B (en) |
| IT (1) | IT1094775B (en) |
| MX (1) | MX149569A (en) |
| NL (1) | NL175991C (en) |
| ZA (1) | ZA782480B (en) |
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| US4319060A (en) * | 1980-12-08 | 1982-03-09 | Allied Chemical Corporation | Process for producing 1,2-dichloro-1,1,2,2-tetrafluoroethane substantially free of 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| GB8415201D0 (en) * | 1984-06-14 | 1984-07-18 | Ici Plc | Chemical process |
| IT1221776B (en) * | 1988-01-15 | 1990-07-12 | Ausimont Spa | PROCESS FOR THE PREPARATION OF 1,2 DIFLUOROETHANE AND 1,1,2 TRIFLUOROETHANE |
| US4873381A (en) * | 1988-05-20 | 1989-10-10 | E. I. Du Pont De Nemours And Company | Hydrodehalogenation of CF3 CHClF in the presence of supported Pd |
| US4996379A (en) * | 1988-05-30 | 1991-02-26 | Central Glass Company, Limited | Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| DE68912657T2 (en) * | 1988-06-21 | 1994-09-01 | Asahi Glass Co Ltd | Process for the preparation of 1,1,1,2-tetrafluoroethane. |
| JP2508807B2 (en) * | 1988-06-21 | 1996-06-19 | 旭硝子株式会社 | Method for producing R-134a |
| EP0366404B1 (en) * | 1988-10-25 | 1993-01-20 | E.I. Du Pont De Nemours And Company | Improved process for the preparation of 1,1,1,2-tetrafluoroethane |
| US5008476A (en) * | 1988-10-25 | 1991-04-16 | E. I. Du Pont De Nemours And Company | Process for the preparation of 1,1,1,2-tetrafluoroethane |
| US4902838A (en) * | 1988-12-28 | 1990-02-20 | E. I. Du Pont De Nemours And Company | Isomerization of saturated fluorohydrocarbons |
| FR2641780B1 (en) * | 1989-01-19 | 1991-04-19 | Atochem | SELECTIVE HYDROGENOLYSIS OF PERHALOGENATED ETHANE DERIVATIVES |
| DE69019090T2 (en) * | 1989-02-02 | 1996-01-25 | Asahi Glass Co. Ltd., Tokio/Tokyo | METHOD FOR PRODUCING A HYDROGEN-CONTAINING 2,2-DIFLUOROPROPANE. |
| US5068473A (en) * | 1989-02-03 | 1991-11-26 | E. I. Du Pont De Nemours And Company | Hydrogenolysis/dehydrohalogenation process |
| US5146018A (en) * | 1989-02-03 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Hydrogenolysis/dehydrohalogenation process |
| US4944890A (en) | 1989-05-23 | 1990-07-31 | E. I. Du Pont De Nemours And Company | Compositions and process of using in refrigeration |
| IT1230779B (en) * | 1989-07-12 | 1991-10-29 | Ausimont Srl | PROCEDURE FOR PREPARING 1,1,1,2 TETRAFLUOROETHANE. |
| US5364992A (en) * | 1989-10-10 | 1994-11-15 | E. I. Du Pont De Nemours And Company | Halocarbon hydrogenolysis |
| GB8927580D0 (en) * | 1989-12-06 | 1990-02-07 | Isc Chemicals Ltd | Improvements in or relating to the reduction of halogenated organic compounds |
| FR2655982B1 (en) * | 1989-12-15 | 1992-03-27 | Atochem | MANUFACTURE OF CHLOROFLUOROETHANES BY SELECTIVE HYDROGENOLYSIS OF PERHALOGENATED ETHANE DERIVATIVES. |
| US5057470A (en) * | 1990-05-22 | 1991-10-15 | E. I. Du Pont De Nemours And Company | Regeneration of noble metal catalysts used in hydrodehalogenation of halogen-substituted hydrocarbons containing fluorine and at least one other halogen |
| US5202510A (en) * | 1990-05-22 | 1993-04-13 | E. I. Du Pont De Nemours And Company | Activation of noble metal catalysts for use in hydrodehalogenation of halogen-substituted hydrocarbons containing fluorine and at least one other halogen |
| US5208396A (en) * | 1990-06-05 | 1993-05-04 | E. I. Du Pont De Nemours And Company | Production of saturated halohydrocarbons |
| US5097082A (en) * | 1990-06-05 | 1992-03-17 | E. I. Du Pont De Nemours And Company | Production of saturated halohydrocarbons |
| US5030372A (en) * | 1990-07-31 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Catalytic equilibration to improve the relative yield of selected halocarbons |
| US5621151A (en) * | 1990-10-09 | 1997-04-15 | E. I. Du Pont De Nemours And Company | Halocarbon hydrogenolysis |
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| BE1004608A3 (en) * | 1990-11-16 | 1992-12-22 | Solvay | Method for manufacturing of chloroform from carbon tetrachloride, catalyst composition and method for obtaining. |
| AU9134291A (en) | 1990-12-26 | 1992-08-17 | E.I. Du Pont De Nemours And Company | Catalytic hydrogenolysis |
| US5208397A (en) * | 1991-04-09 | 1993-05-04 | E. I. Du Pont De Nemours And Company | Hydrogenolysis of halocarbon mixtures |
| US5243108A (en) * | 1991-06-03 | 1993-09-07 | E. I. Du Pont De Nemours And Company | Aluminum fluoride catalyst compositions and use thereof in a chlorofluorination process for preparing 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| US5136113A (en) * | 1991-07-23 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenolysis |
| US5569797A (en) * | 1992-01-07 | 1996-10-29 | E. I. Du Pont De Nemours And Company | Method of removing olefinic impurities from hydrochlorofluorocarbons |
| US5286398A (en) * | 1992-02-13 | 1994-02-15 | E. I. Du Pont De Nemours And Company | End-capped polyalkylene oxide compositions with hydroxyl group functionality and use thereof for lubrication in refrigeration systems |
| US5302765A (en) * | 1992-05-29 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Catalytic process for producing CF3 CHClF |
| US5602288A (en) * | 1992-05-29 | 1997-02-11 | E. I. Du Pont De Nemours And Company | Catalytic process for producing CF3 CH2 F |
| US5463152A (en) * | 1994-12-08 | 1995-10-31 | E. I. Du Pont De Nemours And Company | Halofluorocarbon hydrogenolysis |
| US5744660A (en) * | 1992-06-10 | 1998-04-28 | Imperial Chemical Industries Plc | Products of tetrafluorothanes |
| US5447896A (en) * | 1992-06-23 | 1995-09-05 | E. I. Du Pont De Nemours And Company | Hydrodehalogenation catalysts and their preparation and use |
| EP0649398A1 (en) * | 1992-07-17 | 1995-04-26 | E.I. Du Pont De Nemours And Company | Separation of tetrafluoroethane isomers |
| US5600040A (en) * | 1992-07-17 | 1997-02-04 | E. I. Du Pont De Nemours And Company | Separation of tetrafluoroethane isomers |
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| US5395999A (en) * | 1992-11-06 | 1995-03-07 | E. I. Du Pont De Nemours And Company | Catalytic chlorofluorination process for producing CHClFCF3 and CHF2 CF3 |
| US5258561A (en) * | 1992-11-06 | 1993-11-02 | E. I. Du Pont De Nemours And Company | Catalytic chlorofluorination process for producing CF3 CHClF and CF3 CHF2 |
| EP0687660B2 (en) * | 1993-03-05 | 2006-05-17 | Daikin Industries, Limited | Process for producing 1,1,1,2,2-pentafluoroethane, process for producing 2,2-dichloro-1,1,1-trifluoroethane, and method of purifying 1,1,1,2,2-pentafluoroethane |
| US5866730A (en) * | 1993-04-02 | 1999-02-02 | E. I. Du Pont De Nemours And Company | Process for enriching 1,2-dichloro-1,1,2,2-tetrafluoroethane from a mixture of dichlorotetrafluoroethane isomers |
| US5300712A (en) * | 1993-05-27 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Homogeneous catalytic hydrodechlorination of chlorocarbons |
| US5326914A (en) * | 1993-05-27 | 1994-07-05 | E. I. Du Pont De Nemours And Company | Homogeneous catalytic hydrodechlorination of chlorocarbons |
| AU1912295A (en) * | 1994-03-11 | 1995-09-25 | E.I. Du Pont De Nemours And Company | Process for converting chlorodifluoromethane and/or dichlorodifluoromethane |
| US5723429A (en) * | 1994-03-11 | 1998-03-03 | E. I. Du Pont De Nemours And Company | Azeotropic or azeotrope-like compositions of tetrafluoroethane and chlorotetrafluoroethane |
| US5470442A (en) * | 1994-03-11 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Separating and removing impurities from tetrafluoroethanes by using extractive distillation |
| JP3491702B2 (en) * | 1994-07-29 | 2004-01-26 | ダイキン工業株式会社 | Method for purifying pentafluoroethane |
| WO1996016009A2 (en) * | 1994-11-23 | 1996-05-30 | E.I. Du Pont De Nemours And Company | Hydrofluorocarbon production using heat carriers in high temperature hydrogenolysis |
| US6291729B1 (en) | 1994-12-08 | 2001-09-18 | E. I. Du Pont De Nemours And Company | Halofluorocarbon hydrogenolysis |
| US5481051A (en) * | 1994-12-08 | 1996-01-02 | E. I. Du Pont De Nemours And Company | 2,2-dichlorohexafluoropropane hydrogenolysis |
| WO1996023752A1 (en) * | 1995-02-01 | 1996-08-08 | E.I. Du Pont De Nemours And Company | SEPARATING AND REMOVING IMPURITIES FROM 1,1,1-TRIFLUOROETHANE (HFC-143a) BY USING EXTRACTIVE DISTILLATION |
| US5750808A (en) * | 1995-07-11 | 1998-05-12 | E. I. Du Pont De Nemours And Company | Dehydrohalogenation processes |
| US7329786B2 (en) * | 2001-09-28 | 2008-02-12 | Great Lakes Chemical Corporation | Processes for producing CF3CFHCF3 |
| US7223351B2 (en) | 2003-04-17 | 2007-05-29 | Great Lakes Chemical Corporation | Fire extinguishing mixtures, methods and systems |
| MY161767A (en) | 2010-12-14 | 2017-05-15 | Du Pont | Combinations of e-1,3,3,3-tetrafluoropropene and at least one tetrafluoroethane and their use for heating |
| WO2012082941A1 (en) | 2010-12-14 | 2012-06-21 | E. I. Du Pont De Nemours And Company | Use of refrigerants comprising e-1,3,3,3-tetrafluoropropene and at least one tetrafluoroethane for cooling |
| TWI573971B (en) | 2011-01-31 | 2017-03-11 | 杜邦股份有限公司 | Producing heating using working fluids comprising z-1,1,1,4,4,4-hexafluoro-2-butene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1267427A (en) * | 1960-09-09 | 1961-07-21 | Ici Ltd | Manufacture of 2-bromo-2-chloro-1: 1: 1-trifluoroethane |
| FR1409109A (en) * | 1963-10-01 | 1965-08-20 | Allied Chem | Process for the production of tetrafluoroethylene by reduction of dichlorotetrafluoroetane |
| DE2060041C3 (en) * | 1970-12-05 | 1973-10-25 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Process for the production of fluorinated hydrocarbons |
-
1977
- 1977-05-24 GB GB21806/77A patent/GB1578933A/en not_active Expired
-
1978
- 1978-05-01 ZA ZA00782480A patent/ZA782480B/en unknown
- 1978-05-04 GR GR56139A patent/GR63074B/en unknown
- 1978-05-09 MX MX173395A patent/MX149569A/en unknown
- 1978-05-09 AU AU35909/78A patent/AU515866B2/en not_active Expired
- 1978-05-18 AR AR272236A patent/AR223815A1/en active
- 1978-05-19 IT IT23624/78A patent/IT1094775B/en active
- 1978-05-19 BE BE187878A patent/BE867285A/en not_active IP Right Cessation
- 1978-05-22 NL NLAANVRAGE7805499,A patent/NL175991C/en not_active IP Right Cessation
- 1978-05-23 FR FR7815223A patent/FR2391980A1/en active Granted
- 1978-05-23 CA CA000303896A patent/CA1117144A/en not_active Expired
- 1978-05-23 BR BR7803299A patent/BR7803299A/en unknown
- 1978-05-23 DE DE19782822471 patent/DE2822471A1/en active Granted
- 1978-05-24 JP JP6117178A patent/JPS53147005A/en active Granted
- 1978-05-24 ES ES470170A patent/ES470170A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2391980A1 (en) | 1978-12-22 |
| AU3590978A (en) | 1979-11-15 |
| NL7805499A (en) | 1978-11-28 |
| GB1578933A (en) | 1980-11-12 |
| FR2391980B1 (en) | 1982-12-03 |
| AR223815A1 (en) | 1981-09-30 |
| ZA782480B (en) | 1979-04-25 |
| JPS53147005A (en) | 1978-12-21 |
| DE2822471C2 (en) | 1987-12-17 |
| AU515866B2 (en) | 1981-05-07 |
| BE867285A (en) | 1978-11-20 |
| IT1094775B (en) | 1985-08-02 |
| NL175991B (en) | 1984-09-03 |
| BR7803299A (en) | 1979-01-02 |
| IT7823624A0 (en) | 1978-05-19 |
| DE2822471A1 (en) | 1978-12-07 |
| ES470170A1 (en) | 1980-12-16 |
| GR63074B (en) | 1979-08-08 |
| NL175991C (en) | 1985-02-01 |
| MX149569A (en) | 1983-11-25 |
| JPS5638131B2 (en) | 1981-09-04 |
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