GB1578933A - Manufacture of halogenated hydrocarbons - Google Patents

Manufacture of halogenated hydrocarbons Download PDF

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GB1578933A
GB1578933A GB2180677A GB2180677A GB1578933A GB 1578933 A GB1578933 A GB 1578933A GB 2180677 A GB2180677 A GB 2180677A GB 2180677 A GB2180677 A GB 2180677A GB 1578933 A GB1578933 A GB 1578933A
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tetrafluoroethane
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Imperial Chemical Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/23Preparation of halogenated hydrocarbons by dehalogenation

Description

(54) MANUFACTURE OF HALOGENATED HYDROCARBONS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SWIP 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: 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 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 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 elevated temperature in the presence of a hydrogenation catalyst.

The organic starting materials of the present invention consist of: 1 ,2-dichloro- 1,1 2,2-tetrafluoroethane (COIF2 COIF2) 1,1 -dichloro- 1 ,2,2,2-tetrafluoroethane (CCl2F CF3) I-chloro-l,l ,2,2,2-pentafluoroethane (COIF2 CF3) I -chloro- 1 ,2,2,2-tetrafluoroethane (CHClFCF3) 2-chloro- 1,1 ,2,2-tetrafluoroethane (CHF2 COIF2) 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 asym isomer of dichloro-tetrafluoroethane, CCIF2CCIF2) and 1,1 -dichloro- 1,2,2,2- tetrafluoroethane (the asym isomer of dichloro-tetrafluoroethane, CCl2FCF3). 1,2dichloro - 1,1,2,2-tetrafluoroethane containing a small proportion (e.g. up to 10% by wt) of l,l-dichloro - 1,2,2,2-tetrafluoroethane) as produced commercially may be used as organic starting materials. Alternatively mixtures of said dichlorotetrafluoroethanes in any proportions may be employed. In the present process there is removal of two chlorine atoms or a chlorine and/or a fluorine atom from the haloethane starting material and substitution of hydrogen therefore.

Hydrogenation catalysts are in themselves known. Examples of hydrogenation catalysts include nickel or metals of Group Villa 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 mole of starting material. When the organic starting materials consists of essentially pure 1,2-dichloro - 1,1,2,2-tetrafluoroethane (CCIF2CCIF2) or I,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 CClF3CClF2 and CCI2FCF3 is employed as organic feed there may be employed at least the stoichiometric amount of hydrogen per mole of CCI2FCF3.

This can mean that there is sometimes less than the stoichiometric amount of hydrogen with respect to total mole fluorochloroethane feed. Thus with a mixture containing 3 moles CClF3CClF3 and 1 mole CCI2FCF3 there may be employed 2 to 3 moles of hydrogen per mole CCIF2CF3 and this corresponds to a molar ratio of hydrogen to total mole fluorochloroethane feed of 0.55:1 to 0.75:1 respectively.

Similarly when there is employed an equimolar mixture of CCIF2CCIF2 and CCI2FCF3 there may be employed 2 to 3 moles of hydrogen per mole CCI2FCF3 and this corresponds to a molar ratio of hydrogen to total mole fluorochloroethane feed of 1:1 to 1.5:1. On the other hand with a mixture of 3 moles CF2CICF2CI and I mole CCI2FCF3 there may be employed 3 moles H2 per total mole of total fluoroethane and this corresponds to 12 moles H2 per mole CCI2FCF3.

Atmospheric or superatmospheric pressures may be employed.

The reaction is suitably carried out in the vapour phase at a temperature which is at least 200"C and not greater than 450"C. Preferably the reaction temperature is in the range 225"C to 400"C.

Contact times are usually in the range 5 to 60 seconds especially 5 to 30 seconds when the reaction is carried out in the vapour phase.

The tetrafluoroethane product obtained depends to a considerable extent on the choice of starting material. When the organic starting material is 2,2-dichloro 1,1,1 2-tetrafluoroethane, 1,1,1 ,2-tetrafluoroethane (asym tetrafluoroethane; CF3CH2F) is obtained almost to the exclusion of 1,1,2,2-tetrafluoroethane (sym tetrafluoroethane, CHF2.CHF2). When the organic starting material is 1,2 dichloro-1,1,2,2-tetrafluoroethane the reaction product usually comprises a mixture of the two isomers of tetrafluoroethane. As the proportion of 2,2-dichloro1,1,1 ,2-tetrafluoroethane with respect to 1,2-dichloro-l,l ,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 CHF2CHF2.

In the present process hydrogen and organic by-products, for example, 2 chloro-l,l,l,2-tetrafluoroethane 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-tetrafluoroethane may if desired be tapped off and used as a refrigerant.

The present process has the advantages that the desirable 1,1,1,2- tetrafluoroethane, 1,1,2,2-tetrafluoroethane or mixtures thereof in various proportions can be obtained by a simple and convenient method. Desired products can be obtained in high degree of purity with good conversions of the fluorochloroethane starting material.

The following Examples illustrate the invention: Example 1.

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 of 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.

Hydrogen and dichlorotetrafluoroethane (96.5% by weight, 1,2-dichloro 1,1 ,2,2-tetrafluoroethane; 3.5% by weight, 1,1 -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 liquid chromatography.

The other reaction conditions and composition of the organic products were as shown in Table 1.

TABLE I <img class="EMIRef" id="026553091-00030001" />

<tb> <SEP> Temperature <SEP> C <SEP> <tb> Product <SEP> % <SEP> v/v <SEP> 240 <SEP> 30û <SEP> 330 <SEP> 370 <tb> <SEP> Contact <SEP> time <SEP> (secs.) <tb> <SEP> 17.9 <SEP> 16.3 <SEP> 15.6 <SEP> 14.6 <tb> CF3 <SEP> CH2F <SEP> 6.1 <SEP> 9.2 <SEP> 9.8 <SEP> 11.4 <tb> CHF2CHF2 <SEP> 4.4 <SEP> 8.9 <SEP> 11.7 <tb> CHF2CClF2/ <SEP> <tb> CHCIFCF3 <SEP> 3.6 <SEP> 20.1 <SEP> 21.3 <SEP> 21.4 <tb> CCIF2 <SEP> CCIF2/ <SEP> <tb> CCl2FCF3 <tb> CCI2FCF3 <SEP> 89.2 <SEP> 64.8 <SEP> 57.3 <SEP> 46.2 <tb> CF3CH3 <SEP> 0.6 <SEP> 1.5 <SEP> 2.2 <SEP> 3.3 <tb> Others <SEP> 0.5 <SEP> 5.9 <tb> Example 2.

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 IT <img class="EMIRef" id="026553091-00030002" />

<tb> <SEP> Temperature <SEP> C <SEP> <tb> Product <SEP> %v/v <SEP> 240 <SEP> 255 <SEP> <SEP> 300 <SEP> 325 <SEP> <tb> <SEP> Contact <SEP> time <SEP> (secs.) <tb> <SEP> 12.8 <SEP> 12.4 <SEP> 11.4 <SEP> 11.0 <tb> CF3.CH2F <SEP> 11.3 <SEP> 9.9 <SEP> 9.7 <SEP> 8.1 <tb> CHF2CHF2 <SEP> 7.4 <SEP> 17.6 <SEP> 29.6 <SEP> 35.9 <tb> CHF <SEP> 2CClF2/ <SEP> <tb> CHCIFCF3 <SEP> 40.5 <SEP> 48.9 <SEP> 40.1 <SEP> 39.5 <tb> CCIF2.CClF2 <SEP> <tb> CCI2FCF3 <SEP> -39.4 <SEP> 21.4 <SEP> 17.3 <SEP> 10.8 <tb> CF3.CH3 <SEP> 1.4 <SEP> 1.8 <SEP> 2.1 <SEP> 3.1 <tb> Others <SEP> 0.3 <SEP> 1.2 <SEP> 2.6 <tb> Example 3.

The general procedure of Example 2 was repeated but with I,l-dichloro1,2,2,2-tetrafluoroethane as organic starting material. The other reaction conditions and composition of the organic products were as indicated in Table III.

TABLE Ill <img class="EMIRef" id="026553091-00040001" />

<tb> <SEP> Temperature <SEP> C <tb> Product <SEP> %v/v <SEP> 285 <SEP> 310 <tb> <SEP> Contact <SEP> time <SEP> (secs.) <tb> <SEP> 12.5 <SEP> 12.0 <tb> CF3.CH2F <SEP> 71.7 <SEP> 72.0 <tb> CHF <SEP> 2.CHF2 <SEP> 0.9 <SEP> 0.3 <tb> CHClFCFvCF2ClCF2H <SEP> 8.1 <SEP> 6.1 <tb> CCl2FCF3/CClF2.CClF2 <SEP> 11.0 <SEP> 5.7 <tb> CF3.CH3 <SEP> 8.3 <SEP> 15.9 <tb> Example 4.

The general procedure of Example 2 was repeated but with a mixture of 1,2dichloro- 1,1,2,2-tetrafluoroethane, (72% by weight) and 1,1-dichloro-1,2,2,2- tetrafluoroethane (28% by weight) as organic starting material. The molar ratio of H2: the mixed organic starting material was 3:1. The flow rates of hydrogen and organic starting material were 150 cc/min and 50 cc/min, respectively. The reaction temperature was 3000C. The contact time was 12 seconds.

The composition of the organic product was as given in Table IV.

TABLE IV Product % v/v <img class="EMIRef" id="026553091-00040002" />

<tb> CF3.CH2F <SEP> 37.6 <tb> CHF2CHF2 <SEP> 14.9 <tb> CHF2CClF2/CHClFCF3 <SEP> 26.8 <tb> CF3.CH3 <SEP> 13.0 <tb> CCIF2 <SEP> CCIF2/CFCI2CF3 <SEP> 7.7 <tb> Example 5.

The general procedure of Example 4 was repeated except that the flow rate of hydrogen and the mixed organic starting material and hydrogen 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 Product % v/v <img class="EMIRef" id="026553091-00040003" />

<tb> CF3 <SEP> CH2F <SEP> 46.2 <tb> CHF2CHF2 <SEP> 8.0 <tb> CHF2CCIF2/CHCIFCF3 <SEP> 26 <tb> CF3 <SEP> CH3 <SEP> 8.2 <tb> CClF2CClF2/CFCl2CF1 <SEP> 11.2 <SEP> <tb> Example 6.

The general procedure of Example 5 was repeated except that the flow rates of hydrogen and organic starting material were 90 cc/min and 30 cc/min, respectively the contact time was 19 seconds and the reaction temperature was 350"C.

The composition of the organic product was as given in Table Vl.

TABLE VI Product % v/v <img class="EMIRef" id="026553091-00050001" />

<tb> CM, <SEP> CHEF <SEP> 41.8 <tb> CHF2CHF2 <SEP> 16.3 <tb> CHF2 <SEP> CCIF2/CHCIFCF3 <SEP> 24.8 <tb> CF3CH3 <SEP> 11.8 <tb> CCIF2 <SEP> CClF2/CFCl2CF3 <SEP> 5.3 <tb> Example 7.

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 in Table VII.

TABLE VII <img class="EMIRef" id="026553091-00050002" />

<tb> <SEP> Temperature <SEP> C <tb> <SEP> 350420 <tb> Product <SEP> % <SEP> v/v <SEP> 280 <tb> <SEP> Contact <SEP> time <SEP> (secs.) <tb> CF3 <SEP> CH2F <SEP> 82.0 <SEP> 94.1 <SEP> 95.8 <tb> CHF2 <SEP> CHF2 <SEP> 0.8 <SEP> 0.8 <SEP> 0 <tb> CF3 <SEP> CH3 <SEP> 1.4 <SEP> 2.9 <SEP> 3.3 <tb> CHCIFCF <SEP> 3 <SEP> 15.7 <SEP> 2.3 <SEP> 0 <tb> C2F4 <SEP> 0 <SEP> 9 <SEP> 0.9 <tb> Example 8.

The apparatus comprised a heat-resistant glass tube 30 cms long and 2.5 cms internal diameter surrounded by an electric furnace. Two particulate catalysts were employed which consisted of palladium (2% w/w and 5% w/w) supported on alumina.

Hydrogen and a mixture of 1,2-dichloro-1,1,2,2-tetrafluoroethane (72% by weight) and l,l-dichloro-l,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 I, 2 and 3 were 0.5:1, 0.5:1 of 0.75:1, respectively. The flow rates of H2 and CCI2FCF3 for these Runs were 50 and 25 cc/min, 50 and 25 cc/min, and 63 cc/min and 21 cc/min, respectively. The %v/v of organic materials in the exit gas was determined by gas liquid chromatography.

TABLE VIII <img class="EMIRef" id="026553091-00060001" />

<tb> <SEP> Run <SEP> 1 <SEP> Run <SEP> 2 <SEP> Run <SEP> 3 <tb> <SEP> Temperature <SEP> C <SEP> <tb> <SEP> 300 <SEP> 295 <SEP> 300 <tb> Product <SEP> % <SEP> v/v <SEP> Contact <SEP> time <SEP> (secs) <tb> <SEP> 10.6 <SEP> 10.3 <SEP> 16.3 <tb> <SEP> % <SEP> Pd <SEP> in <SEP> catalyst <SEP> (w/w) <tb> <SEP> 2 <SEP> 5 <SEP> 2 <tb> <SEP> Molar <SEP> Ratio <SEP> H2: <SEP> CFCl2CF3 <SEP> <tb> <SEP> 2:1 <SEP> 2:1 <SEP> 3:1 <tb> CF3CH2F <SEP> 20 <SEP> 18.8 <SEP> 24.9 <tb> CHF2CHF2 <SEP> - <SEP> <tb> CHCIFCF3/CHF2CCIF2 <SEP> 2.6 <SEP> 0.4 <SEP> 0.3 <tb> CF3CH3 <SEP> 0.4 <SEP> 0.5 <SEP> 0.3 <tb> CClF2CClF2/CFCl2CF3 <SEP> 62.5 <SEP> 71.9 <SEP> -64.4 <tb> Other <SEP> fluorochlor <SEP> water <tb> C2 <SEP> compounds <SEP> 10.9 <SEP> 5.7 <SEP> 8.0 <tb> Example 9.

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 sphere (3 mm diameter) consisting of 2% w/w Pd supported on alumina.

Hydrogen and a mixture of 1,2-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 1.45:1, 1.6:1 and 1.6:1, respectively. The flow rates of H2: CFCI2CF3 for these runs were 3.14 1 and 0.98 I/min, 3.811 and 1.15 I/min and 3.8 1 and 1.15 I/min, respectively.

TABLE IX <img class="EMIRef" id="026553091-00070001" />

<tb> <SEP> Run <SEP> 1 <SEP> <SEP> | <SEP> <SEP> Run <SEP> 2 <SEP> | <SEP> Run <SEP> 2 <SEP> <tb> <SEP> Temperature <SEP> C <SEP> <tb> <SEP> 250 <SEP> 275 <SEP> 330 <tb> <SEP> Product <SEP> v/v <SEP> Contact <SEP> time <SEP> (secs) <tb> <SEP> 30 <SEP> 20 <SEP> 20 <tb> <SEP> Molar <SEP> ratio <SEP> H2: <SEP> CFCI2CF3 <tb> <SEP> 3.2:1 <SEP> 3.2:1 <SEP> 3.3:1 <tb> CF3CH2F <SEP> 46.1 <SEP> 35.5 <SEP> 26.8 <tb> CHF2CHF2 <SEP> <tb> CHCIFCF3/CHF2CCIF2 <SEP> 3.4 <SEP> 5.4 <SEP> 2.0 <tb> CF3CH3 <SEP> 1.6 <SEP> 1.9 <SEP> 1.2 <tb> CCIF2CClF3/CFCl2CF3 <SEP> 45.8 <SEP> 54.6 <SEP> 69 <tb> Other <SEP> fluorochloro <SEP> C2 <tb> compounds <SEP> 0.5 <SEP> 0.5 <SEP> 0.4 <tb> 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 divider and condenser. The apparatus was operated at atmospheric pressure and after removal of lights boiling at -400C to -270C said 1,1,1,2-tetrafluoroethane was recovered as a top-product boiling at -26"C.

Example 10.

The apparatus comprised a mild steel tube (5 çms 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 alumina.

5 Kgs per hour of a mixture of 1,2-dichloro-l,l ,2,2-tetrafluoroethane (50% by weight) and l,l-dichloro-l,2,2,2-tetrafluoroethane (50% by weight) and 770 I/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 340"C. 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- I ,2,2,2-tetrafluoroethane being 2.2: 1.

The organic reaction produced after washing with dilute caustic soda solution and drying over calcium chloride was condensed at -700C and comprised (v/v): 25% CF3CH2F 5% CF3CH3 5% CHClFCF 65% CF2ClCF2C3l/CF3CFCl2 WHAT WE CLAIM IS: 1. A process for the manufacture of tetrafluoroethane 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

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (16)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    TABLE IX <img class="EMIRef" id="026553092-00070001" />
    <tb> <SEP> Run <SEP> 1 <SEP> <SEP> | <SEP> <SEP> Run <SEP> 2 <SEP> | <SEP> Run <SEP> 2 <SEP> <tb> <SEP> Temperature <SEP> C <SEP> <tb> <SEP> 250 <SEP> 275 <SEP> 330 <tb> <SEP> Product <SEP> v/v <SEP> Contact <SEP> time <SEP> (secs) <tb> <SEP> 30 <SEP> 20 <SEP> 20 <tb> <SEP> Molar <SEP> ratio <SEP> H2: <SEP> CFCI2CF3 <tb> <SEP> 3.2:1 <SEP> 3.2:1 <SEP> 3.3:1 <tb> CF3CH2F <SEP> 46.1 <SEP> 35.5 <SEP> 26.8 <tb> CHF2CHF2 <SEP> <tb> CHCIFCF3/CHF2CCIF2 <SEP> 3.4 <SEP> 5.4 <SEP> 2.0 <tb> CF3CH3 <SEP> 1.6 <SEP> 1.9 <SEP> 1.2 <tb> CCIF2CClF3/CFCl2CF3 <SEP> 45.8 <SEP> 54.6 <SEP> 69 <tb> Other <SEP> fluorochloro <SEP> C2 <tb> compounds <SEP> 0.5 <SEP> 0.5 <SEP> 0.4 <tb> 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 divider and condenser. The apparatus was operated at atmospheric pressure and after removal of lights boiling at -400C to -270C said 1,1,1,2-tetrafluoroethane was recovered as a top-product boiling at -26"C.
    Example 10.
    The apparatus comprised a mild steel tube (5 çms 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 alumina.
    5 Kgs per hour of a mixture of 1,2-dichloro-l,l ,2,2-tetrafluoroethane (50% by weight) and l,l-dichloro-l,2,2,2-tetrafluoroethane (50% by weight) and 770 I/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 340"C. 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- I ,2,2,2-tetrafluoroethane being 2.2: 1.
    The organic reaction produced after washing with dilute caustic soda solution and drying over calcium chloride was condensed at -700C and comprised (v/v): 25% CF3CH2F 5% CF3CH3 5% CHClFCF 65% CF2ClCF2C3l/CF3CFCl2 WHAT WE CLAIM IS: 1. A process for the manufacture of tetrafluoroethane 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 elevated temperature in the presence of a hydrogenation catalyst.
  2. 2. A process as claimed in Claim I characterised in that the haloethane starting material is I 2-dichloro- 1,1 ,2,2-tetrafluoroethane.
  3. 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. 4. A process as claimed in Claim I characterised in that the haloethane starting material is a mixture of 1,2-dichloro-1,1,2,2-tetrafluoroethane and l,l-dichloro- I ,2,2,2-tetrafluoroethane.
  5. 5. A process as claimed in Claim 4 characterised in that the molar ratio of 1,2dichloro- 1,1 ,2,2-tetrafluoroethane to 1,1 -dichloro- I ,2,2,2-tetrafluoroethane is in the range 3:1 to 1:1.
  6. 6. A process as claimed in any one of the preceding Claims 1 to 5 characterised in that at least the stoichiometric amount of hydrogen is employed to remove the halogen atom or atoms.
  7. 7. A process as claimed in any one of the preceding Claims I to 6 characterised in that there is employed up to four moles of hydrogen per mole of haloethane.
  8. 8. 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-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-tetrafluoroethane corresponding to 0.5 to 0.75 moles hydrogen per total mole fluorochloroethane, respectively.
  9. 9. A process as claimed in Claim 5 characterised in that the molar ratio of 1,2dichloro- 1,1 ,2,2-tetrafluoroethane to 1,1 -dichloro- 1 ,2,2,2-tetrafluoroethane is essentially 1:1 and in which there is employed 2 to 3 moles of hydrogen per mole of l,l.dichloro-l,2,2,2-tetrafluoroethane corresponding to 1 to 1.5 moles hydrogen per total mole fluorochloroethane, respectively.
  10. 10. A process as claimed in any one of the preceding claims characterised in that the hydrogenation catalyst is palladium.
  11. II. A process as claimed in Claim 10 characterised in that the palladium is carried on an activated carbon support.
  12. 12. A process as claimed in Claim 10 characterised in that which the palladium is carried on an alumina support.
  13. 13. A process as claimed in any one of the preceding claims characterised in that the reaction is carried out in the vapour phase at a temperature of at least 2000C not greater than 450"C.
  14. 14. A process as claimed in Claim 13 characterised in that the reaction temperature is in the range 225"C to 4000 C.
  15. 15. A process for the manufacture of 1,1,1 ,2-tetrafluoroethane and/or 1,1,2,2tetrafluoroethane substantially as described with reference to the Examples.
  16. 16. 1,1,1 ,2-tetrafluoroethane and/or 1,1,2,2-tetrafluoroethane whenever manufactured by a process according to any one of the preceding claims.
GB2180677A 1977-05-24 1977-05-24 Manufacture of halogenated hydrocarbons Expired GB1578933A (en)

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GB2180677A GB1578933A (en) 1977-05-24 1977-05-24 Manufacture of halogenated hydrocarbons
ZA00782480A ZA7802480B (en) 1977-05-24 1978-05-01 Manufacture of halogenated hydrocarbons
GR56139A GR63074B (en) 1977-05-24 1978-05-04 Manufacture of halogenated hydrocarbons
MX17339578A MX149569A (en) 1977-05-24 1978-05-09 Improved process for obtaining tetrafluoroethane
AU35909/78A AU515866B2 (en) 1977-05-24 1978-05-09 Manufacture of tetrafluoro ethane
AR27223678A AR223815A1 (en) 1977-05-24 1978-05-18 Process for the preparation of tetrafluoroethane
BE187878A BE867285A (en) 1977-05-24 1978-05-19 Process for the production of halogenated hydrocarbons
IT2362478A IT1094775B (en) 1977-05-24 1978-05-19 Process for the preparation of halogenated hydrocarbons
NL7805499A NL175991C (en) 1977-05-24 1978-05-22 A process for the preparation of tetrafluoroethane.
CA000303896A CA1117144A (en) 1977-05-24 1978-05-23 Manufacture of halogenated hydrocarbons
FR7815223A FR2391980B1 (en) 1977-05-24 1978-05-23
DE19782822471 DE2822471C2 (en) 1977-05-24 1978-05-23
BR7803299A BR7803299A (en) 1977-05-24 1978-05-23 Process for the manufacture of tetrafluoroethane
JP6117178A JPS5638131B2 (en) 1977-05-24 1978-05-24
ES470170A ES470170A1 (en) 1977-05-24 1978-05-24 Improvements to prepare tetrafluoroethane

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AR (1) AR223815A1 (en)
AU (1) AU515866B2 (en)
BE (1) BE867285A (en)
BR (1) BR7803299A (en)
CA (1) CA1117144A (en)
DE (1) DE2822471C2 (en)
ES (1) ES470170A1 (en)
FR (1) FR2391980B1 (en)
GB (1) GB1578933A (en)
GR (1) GR63074B (en)
IT (1) IT1094775B (en)
MX (1) MX149569A (en)
NL (1) NL175991C (en)
ZA (1) ZA7802480B (en)

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EP0164954A2 (en) * 1984-06-14 1985-12-18 Imperial Chemical Industries Plc Process for the preparation of 1-chloro-1,2,2,2-tetrafluorethane
EP0324478A1 (en) * 1988-01-15 1989-07-19 AUSIMONT S.r.l. Process for preparing 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
EP0366404A1 (en) * 1988-10-25 1990-05-02 E.I. Du Pont De Nemours And Company Improved process for the preparation of 1,1,1,2-tetrafluoroethane
EP0399817A2 (en) 1989-05-23 1990-11-28 E.I. Du Pont De Nemours And Company Compositions and process of using in refrigeration
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
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
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
US5053564A (en) * 1989-01-19 1991-10-01 Societe Atochem 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
GB2243606A (en) * 1989-12-06 1991-11-06 Rhone Poulenc Chemicals Improvement in or relating to the reduction of halogenated organic compounds.
US5068473A (en) * 1989-02-03 1991-11-26 E. I. Du Pont De Nemours And Company Hydrogenolysis/dehydrohalogenation process
US5097082A (en) * 1990-06-05 1992-03-17 E. I. Du Pont De Nemours And Company Production of saturated halohydrocarbons
US5124495A (en) * 1989-12-15 1992-06-23 Societe Atochem Selective hydrogenolysis of perhalogenated ethane derivatives
WO1992012113A1 (en) * 1990-12-26 1992-07-23 E.I. Du Pont De Nemours And Company Catalytic hydrogenolysis
US5136113A (en) * 1991-07-23 1992-08-04 E. I. Du Pont De Nemours And Company Catalytic hydrogenolysis
US5146018A (en) * 1989-02-03 1992-09-08 E. I. Du Pont De Nemours And Company Hydrogenolysis/dehydrohalogenation process
US5146013A (en) * 1990-11-16 1992-09-08 Solvay & Cie (Societe Anonyme) Process for the production of chloroform from carbon tetrachloride, catalytic compositions and process for obtaining them
AU628912B2 (en) * 1988-12-28 1992-09-24 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
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
US5208397A (en) * 1991-04-09 1993-05-04 E. I. Du Pont De Nemours And Company Hydrogenolysis of halocarbon mixtures
US5208396A (en) * 1990-06-05 1993-05-04 E. I. Du Pont De Nemours And Company Production of saturated halohydrocarbons
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
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
WO1994002440A1 (en) * 1992-07-17 1994-02-03 E.I. Du Pont De Nemours And Company Separation of tetrafluoroethane isomers
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
US5300712A (en) * 1993-05-27 1994-04-05 E. I. Du Pont De Nemours And Company Homogeneous catalytic hydrodechlorination of chlorocarbons
US5302765A (en) * 1992-05-29 1994-04-12 E. I. Du Pont De Nemours And Company Catalytic process for producing CF3 CHClF
US5326914A (en) * 1993-05-27 1994-07-05 E. I. Du Pont De Nemours And Company Homogeneous catalytic hydrodechlorination of chlorocarbons
US5364992A (en) * 1989-10-10 1994-11-15 E. I. Du Pont De Nemours And Company Halocarbon hydrogenolysis
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
US5426253A (en) * 1988-06-21 1995-06-20 Asahi Glass Company Ltd. Process for producing 1,1,1,2-tetrafluoroethane
US5447896A (en) * 1992-06-23 1995-09-05 E. I. Du Pont De Nemours And Company Hydrodehalogenation catalysts and their preparation and use
US5463151A (en) * 1989-07-12 1995-10-31 Ausimont S.R.L. Process for preparing 1,1,1,2-tetrafluoroethane
US5463152A (en) * 1994-12-08 1995-10-31 E. I. Du Pont De Nemours And Company Halofluorocarbon hydrogenolysis
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
US5481051A (en) * 1994-12-08 1996-01-02 E. I. Du Pont De Nemours And Company 2,2-dichlorohexafluoropropane hydrogenolysis
US5504265A (en) * 1990-10-11 1996-04-02 E. I. Du Pont De Nemours And Company Saturated linear polyfluorohydrocarbons, processes for their production, and their use in cleaning compositions
US5516947A (en) * 1994-03-11 1996-05-14 E. I. Du Pont De Nemours And Company Process for converting chlorodifluoromethane and/or dichlorodifluoromethane
US5545777A (en) * 1989-02-02 1996-08-13 Asahi Glass Company Ltd. Process for producing a hydrogen-containing 2,2-difluoropropane
US5569797A (en) * 1992-01-07 1996-10-29 E. I. Du Pont De Nemours And Company Method of removing olefinic impurities from hydrochlorofluorocarbons
US5600040A (en) * 1992-07-17 1997-02-04 E. I. Du Pont De Nemours And Company Separation of tetrafluoroethane isomers
US5602288A (en) * 1992-05-29 1997-02-11 E. I. Du Pont De Nemours And Company Catalytic process for producing CF3 CH2 F
US5621151A (en) * 1990-10-09 1997-04-15 E. I. Du Pont De Nemours And Company Halocarbon hydrogenolysis
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
US5744660A (en) * 1992-06-10 1998-04-28 Imperial Chemical Industries Plc Products of tetrafluorothanes
US5750808A (en) * 1995-07-11 1998-05-12 E. I. Du Pont De Nemours And Company Dehydrohalogenation processes
US5830325A (en) * 1995-02-01 1998-11-03 E. I. Du Pont De Nemours And Company Separating and removing 1, 1, 1-trifluoroethane by using azeotropic distillation
US5841008A (en) * 1994-11-23 1998-11-24 E. I. Du Pont De Nemours And Company Hydrofluorocarbon production using heat carriers in high temperature hydrogenolysis
US5852223A (en) * 1994-07-29 1998-12-22 Daikin Industries, Ltd. Purification methods of 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
US6291729B1 (en) 1994-12-08 2001-09-18 E. I. Du Pont De Nemours And Company Halofluorocarbon hydrogenolysis
US6525231B1 (en) 1992-10-22 2003-02-25 E. I. Du Pont De Nemours And Company Producing hydrofluoro compounds by hydrogenolysis of iodides
US7151197B2 (en) * 2001-09-28 2006-12-19 Great Lakes Chemical Corporation Processes for purifying chlorofluorinated compounds and processes for purifying CF3CFHCF3
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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
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US5852223A (en) * 1994-07-29 1998-12-22 Daikin Industries, Ltd. Purification methods of pentafluoroethane
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BE867285A (en) 1978-11-20
MX149569A (en) 1983-11-25
ES470170A1 (en) 1980-12-16
NL175991C (en) 1985-02-01
FR2391980B1 (en) 1982-12-03
ZA7802480B (en) 1979-04-25
BR7803299A (en) 1979-01-02
JPS5638131B2 (en) 1981-09-04
AU3590978A (en) 1979-11-15
GR63074B (en) 1979-08-08
BE867285A1 (en)
AR223815A1 (en) 1981-09-30
NL175991B (en) 1984-09-03
IT1094775B (en) 1985-08-02
NL7805499A (en) 1978-11-28
FR2391980A1 (en) 1978-12-22
IT7823624D0 (en) 1978-05-19
JPS53147005A (en) 1978-12-21
CA1117144A1 (en)
CA1117144A (en) 1982-01-26

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