US006849772B2

(12) United States Patent (10) Patent N0.: US 6,849,772 B2

Anciaux et al. (45) Date of Patent: Feb. 1, 2005

(54) PROCESS FOR PRODUCING AND 3,862,995 A 1/1975 Martens et al. ........ .. 200/653.6
PURIFYING 1,1-DIFLUOROETHANE, AND 5,396,001 A 3/1995 Pennetreau ............... .. 870/179
PRODUCT THUS OBTAINED 5,626,725 A * 5/1997 Balthasart et al. 203/91
5,714,652 A 2/1998 Grunchard et al. 570/165
(75) Inventors: Charles-Marie AnciauX, Tavaux 5,744,661 A 4/1998 Luly et al. ................ .. 570/177
(FR); Vincent Wilmet, Wavre (BE); 5,874,657 A 2/1999 Miller et al. .............. .. 570/178

Dominique Lecroc, Dole (FR)

FOREIGN PATENT DOCUMENTS
(73) Assignee: Solvay (Societe Anonyme) (BE) BE 766395 10/1971
CN 1069019 2/1993
( * ) Notice: Subject to any disclaimer, the term of this CN 1074434 7/1993
patent is extended or adjusted under 35 EP 0370688 5/1990
U.S.C. 154(b) by 0 days. EP 0592711 4/1994
EP 0600536 6/1994
(21) Appl. No.: 10/265,993 EP 0637579 2/1995
EP 0739875 10/1996
(22) Filed: Oct. 7, 2002 RU 2098399 12/1997
SU 341788 4/1997
(65) Prior Publication Data WO 90/0875 0 53/1990
WO 96/40606 12/1996
US 2003/0109759 A1 Jun. 12, 2003
WO 97/25300 7/1997
Related US. Application Data
OTHER PUBLICATIONS
(62) Division of application No. 09/201,308, ?led on Nov. 30,
1998, now abandoned. 1,1di?uoroethane, Dictionary of Chemical Engineering, p.
(30) Foreign Application Priority Data 17, 1992.
Dec. 1, 1997 .. 97 15265
(FR) ..........................................
* cited by examiner
(51) Int. C1.7 ....................... .. C07C 17/00; C07C 17/08;
C07C 19/08; C07C 17/38 Primary ExaminerElvis O. Price
(52) us. Cl. ..................... .. 570/164; 570/165; 570/166;
(74) Attorney, Agent, or FirmConnolly Bove Lodge &
570/167; 570/168; 570/169; 570/177; 570/178; HutZ LLP
203/80; 203/91
(58) Field of Search ............................... .. 570/164, 165, (57) ABSTRACT
570/166, 167, 168, 169, 177, 178; 203/80,
91 1,1-Di?uoroethane containing less than 10 mg/kg of vinyl
chloride is obtained by treatment, With hydrogen ?uoride, of

(56) References Cited a crude 1,1-di?uoroethane containing less than 1 mol of

hydrogen chloride per mole of 1,1-di?uoroethane.
U.S. PATENT DOCUMENTS
2,452,975 A 11/1948 Whalley ................... .. 260/653 24 Claims, 2 Drawing Sheets
U.S. Patent Feb. 1,2005Sheet 1 0f 2 US 6,849,772 B2

FIG. 1

5 _L
L Q 1-1
+ 10.

3%. 4 1-5
23 PM?
/7 W I
5 23 f ,1415
f 1' Z + 12\:'K /
24 m

13

i
/ 21 20/

J
U.S. Patent Feb. 1,2005Sheet 2 0f 2 US 6,849,772 B2

FIG. 2
 US 6,849,772 B2
1 2
PROCESS FOR PRODUCING AND With hydrogen ?uoride, Which is characteriZed in that the
PURIFYING 1,1-DIFLUOROETHANE, AND crude 1,1-di?uoroethane has, per mole of 1,1
PRODUCT THUS OBTAINED di?uoroethane, a hydrogen chloride (HCl) content of less
than 1 mol, advantageously less than 0.5 mol, preferably less
This application is a divisional of US. application Ser. than 0.1 mol and even less than 0.03 mol. Usually, the vinyl

No. 09/201,308, ?led Nov. 30, 1998, noW abandoned. chloride content in the 1,1-di?uoroethane to be puri?ed
The present invention relates to processes for producing ranges betWeen about 10 and about 20,000 mg/kg (ppm).
HoWever, the process according to the invention can also be
and purifying 1,1-di?uoroethane. used to purify 1,1-di?uoroethane containing larger amounts
1,1-Di?uoroethane (HFC-152a) is, for example, intended
of VC. Generally, it also has, per kg of 1,1-di?uoroethane,
for use in sWelling plastic foams (extrusion of polystyrene) 10
a 1-chloro-1-?uoroethane content of less than 50 g, advan
or as a propellant in aerosols. tageously less than 10 g and preferably less than 5 g, and a
Processes for producing 1,1-di?uoroethane by hydro?u
1,1-dichloroethane content of less than 20 g, advantageously less
orination of vinyl chloride (VC), 1-chloro-1-?uoroethane than 5 g and preferably less than 2 g. It generally contains, per
(HCFC-151a) or 1,1-dichloroethane (HCC-150a) have been knoWn kg of HFC-152a, from 2 to 500 g of HF,
for a long time (see, for example, BE-A-766,395 and 15
advantageously from 5 to 250 g, preferably from 10 to 200
US. Pat. No. 2,452,975). g. Such a crude 1,1-di?uoroethane is obtained, for example,
HoWever, it has been observed that the knoWn processes by at least partially removing the hydrogen chloride con
generally lead to a ?nal product Which is still tained in a crude reaction product resulting from the reaction
contaminated to an unacceptable level With vinyl chloride. betWeen hydrogen ?uoride and a chloro precursor of HFC
It has consequently been attempted to overcome these 20 152a, such as vinyl chloride.
draWbacks by subjecting the crude 1,1-di?uoroethane The present invention consequently also relates to a
obtained from the synthesis to a puri?cation. Several tech process for producing 1,1-di?uoroethane, comprising
niques have been applied, among Which mention may be a) a reaction betWeen hydrogen ?uoride and a chloro pre
made of hydro?uorination of the crude synthetic product. cursor of 1,1-di?uoroethane, optionally in the
Mention may be made in particular of a process for 25 presence of a hydro?uorination catalyst, this
obtaining 1,1-di?uoroethane by hydro?uorination of vinyl reaction giving rise to a crude reaction product,
chloride in the presence of SnCl4 With puri?cation of the b) a separation of hydrogen chloride from the crude reaction
1,1-di?uoroethane obtained, by distillation in the presence product, and
of anhydrous hydrogen ?uoride (inventors certi?cate c) a further treatment of the crude reaction product, Which is

SU-341,788). HoWever, more than 0.6% vinyl chloride 30 substantially depleted of HCl, With hydrogen ?uoride, this

remains in the HFC-152a thus obtained. further treatment giving rise to a formation of puri?ed

Mention may also be made of patent application WO-96/ 1,1-di?uoroethane.

40606, in Which the crude mixture obtained from the syn The account hereinbeloW focuses on this process for
thesis reactor is introduced directly into a step of reactive producing 1,1-di?uoroethane from a chlorohydrocarbon.
distillation in the presence of HF and optionally in the 35 HoWever, it is clear that all of the characteristics of the

presence of a catalyst such as SnCl4 or BF3. The conditions further treatment can also apply to the general process for
in the distillation column are such that a mixture of puri?ed purifying 1,1-di?uoroethane mentioned above.
HFC-152a and HCl are obtained at the top of the column and The solution proposed by the invention has the advantage
essentially HF, Which is recycled into the reactor, is obtained of comprising, at the synthesis reactor outlet, a simple and
at the bottom of the column. 40 common step of depletion of the hydrogen chloride content
It Will readily be understood that, in this so-called in the synthetic product obtained from the main reactor, and
reactive distillation column, one or more reactions there a further step in Which the product obtained is subjected to
fore occur, simultaneously With the distillation, and that the a reaction similar to that Which has taken place in the
behaviour of such a column for maintaining the optimum synthesis reactor, ie with hydrogen ?uoride, so as to
operating conditions Will be complicated, especially in the 45 convert, entirely or almost entirely, the vinyl chloride still

presence of a catalyst. present in the reaction product.

Other techniques have also been proposed to purify The impossibility of achieving a vinyl chloride content of
1,1-di?uoroethane of any vinyl chloride. Mention may be less than 10 mg/kg in 1,1-di?uoroethane at the synthesis
made, inter alia, of the oxidation of vinyl chloride With reactor outlet, even after a simple distillation of the HFC
various oxides (see EP-A-0,370,688), hydrogenation of 50 152a produced, has been observed. The reason for this is

vinyl chloride (see WO-90/08750), photochlorination of that, in the latter case, an aZeotrope forms betWeen the vinyl
vinyl chloride (see abstract to CN-A-1,074,434 in Chemical chloride and the HFC-152a, these tWo compounds moreover
Abstracts: 120: 269 634 k) and adsorption of vinyl chloride having a very loW relative volatility. Areactive distillation of
onto active charcoal (EP-A-0,600,536). the crude reaction product as obtained from the reactor, ie
HoWever, none of these processes makes it possible 55 not depleted of HCl, does not increase the possibility of
readily and continuously to obtain 1,1-di?uoroethane per achieving very loW vinyl chloride contents. The solution
manently containing less than 10 mg of VC per kg of proposed according to the invention overcomes these draW
HFC-152a. backs.
The aim of the present invention is to purify crude According to a preferred embodiment of the invention,
1,1-di?uoroethane such that it invariably has a very loW 60 the synthetic reaction takes place in the liquid phase in an

content of vinyl chloride (preferably <10 mg/kg) and such organic solvent. In general, vinyl chloride is used as chloro
that it is suitable for the applications for Which this product precursor of 1,1-di?uoroethane. Such a reaction has already
is intended. Advantageously, this process Will be simple and been described in patent applications EP-A-0,637,579 and
uncomplicated to carry out. EP-A-0,739,875. It can also be envisaged to feed another
This problem is solved, according to the invention, by a 65 chlorohydrocarbon into the synthesis reactor, in particular

process for purifying 1,1-di?uoroethane of any vinyl HCC-150a or HCFC-151a, in total or

partial replacement for
chloride, comprising treatment of a crude 1,1-di?uoroethane the vinyl chloride.
 US 6,849,772 B2
3 4
According to one embodiment of the invention, the HCl those already present in the synthetic reaction, it does not
is separated from the crude reaction product obtained from complicate the rest of the process for the puri?cation of the
the synthesis reactor by WithdraWing the HCl from the top puri?ed 1,1-di?uoroethane.
of a distillation column, from Which the tail fraction is The crude reaction product, substantially depleted of HCl,
collected in order to subject it to the further treatment. Which is used in the further treatment typically has a
According to an improved embodiment of the invention, composition similar to that given above, for the crude
a product mainly containing 1,1-di?uoroethane to be puri 1,1-di?uoroethane used in the general puri?cation process.
?ed is extracted laterally from the said distillation column, If necessary, HF can be added to the crude reaction product
While a product mainly containing products heavier than to be puri?ed.
1,1-di?uoroethane, in particular HF and synthetic interme 10 Advantageously, crude 1,1-di?uoroethane is subjected to
diates such as 1,1-chloro?uoroethane (HCFC-151a) and 1,1- the further treatment continuously, at a ?oW rate typically of
dichloroethane (HCC-150a), are taken from the column from 0.01 to 5 kg of crude 1,1-di?uoroethane per hour and
tail fraction. per liter of reaction medium, preferably from 0.05 to 2 kg.
In this embodiment, the efficacy of the further treatment Generally, the temperature at Which the further treatment
is improved appreciably by reducing the content of synthetic 15 is carried out is at least 40 C. and does not exceed 130 C.
intermediates Which are liable to reform vinyl chloride Preferably, it is at least 50 C. and does not exceed 120 C.
during the reaction. It can be envisaged to reduce this The pressure is chosen as a function of the temperature
content of synthetic intermediates even further by inserting
of the reaction mixture. It is generally at least
an additional distillation column betWeen the HCl distilla equal to 2 bar. It usually does not exceed 50 bar.
tion and the further treatment and by conveying therein the 20 The present invention also relates to 1,1-di?uoroethane,
reaction product Which is substantially depleted of HCl. The obtained by hydro?uorination of a chlorohydrocarbon,
insertion of a re?ux column betWeen the synthesis reactor Which has a purity of greater than 99.8% by Weight, pref
and the HCl distillation column also improves this reduction erably greater than 99.9% by Weight, and a vinyl chloride
into substances liable to reform vinyl chloride. In one variant, content of less than 10 mg/kg, preferably less than 5 mg/kg,
the HCl distillation column can consist merely of a
25 or even less than 2 mg/kg.
head section, mounted on the hydro?uorination reactor Other speci?c aims of the invention
Which serves as a boiling vessel. are indicated in the claims Which folloW.
The further treatment can be carried out in the liquid Other details and particular features of the invention Will
phase or in the gas phase. Advantageously, it is carried out in
also emerge from the description of a number of embodi
the liquid phase, preferably in a reaction medium con
30 ments given beloW Without any limitation and
taining at least 200 g of HF per kg. In a particularly preferred
With reference to the attached draWings.
manner, it is carried out in a liquid medium containing at
least 500 g of HF per kg, or even at least 800 g per kg. BRIEF DESCRIPTION OF THE DRAWINGS
According to an advantageous embodiment of the
invention, the further treatment takes place in the presence 35 EXAMPLE 1
of a hydro?uorination catalyst, Which is preferably the same Aplant for producing 1,1-di?uoroethane according to the
as the one used in the synthetic reaction, if this reaction has invention is illustrated diagrammatically in FIG. 1.
used such a catalyst, or in any case a catalyst Which can be
This ?gure shoWs a reactor 1 for the synthesis of 1,1
used in the synthetic reaction. di?uoroethane, fed With vinyl chloride via a feed pipe 2 and
As catalysts Which can be used, mention may be made 40 With hydrogen ?uoride via another feed pipe 3. In the
of derivatives of metals chosen from the metals from groups
preferred embodiment illustrated, a catalyst is introduced
IIIa, IVa, IVb, Va, Vb and VIb of the Periodic Table of the
into the reactor 1 via an inlet pipe 4 Which opens into an
Elements, and mixtures thereof. The tin, molybdenum,
titanium, vanadium, antimony and tungsten derivatives are
organic solvent delivery pipe 5.
The synthetic reaction is carried out under knoWn oper
preferred. Tin derivatives are particularly suitable. Halides,
45 ating conditions. In this respect, reference may be made,
such as chlorides, ?uorides and chloro?uorides, as Well as
for example, to patent applications ERA-0,637,579 and EP-A
oxides and oxyhalides are preferably used as metal deriva
tives. SnCl4 is most particularly preferred. In the liquid 0,739,875.
Advantageously, a temperature and a pressure are estab
phase, the amount of catalyst to be provided, per liter of

reaction medium, can be from about 0 to 1 mol, in 50 lished in the reactor such that the 1,1-di?uoroethane
formed leaves the liquid mixture in the reactor
particular from 0.1 to 200 mmol, advantageously from
continuously, in the form of a gaseous, crude reaction
0.2 to 100 mmol and preferably from 0.5 to 20 mmol.
product Which is conveyed conventionally into a re?ux
When the further treatment is carried out in an organic
column 6, via the pipe 7 provided at the top of reactor 1.
solvent, this is preferably the same as the solvent for the
synthetic reaction. As suitable organic solvent, mention may 55 The synthesis reactor can be any knoWn reactor Which is
capable of operating under the Working conditions of the
be made in particular of perchloroethylene or saturated
process. For example, a reactor heated by an oil bathnot
halohydrocarbons, preferably chloro, ?uoro or chloro?uo
rohydrocarbons containing from 1 to 8 carbon atoms, or
representedmay be envisaged.
The re?ux column 6 operates under conditions such that
mixtures thereof. Using the same catalyst, for example SnCl4, in
60 it alloWs recycling into the reactor, via the return pipe 8
the synthetic reaction and the further treatment, the
Which opens into the pipe 5, of most of the HCFC-151a and
process is greatly simpli?ed, and this is all the more the case
HCC-150a synthetic intermediates, as Well as HF and any
since the further treatment can be carried out under similar
other components in the reaction medium, in particular
conditions, in particular in a reactor in Which the catalyst
organic solvent. The product in the head fraction of this
concentrations can be ?nely controlled, and the residence
65 re?ux column 6 typically contains about 60% by Weight
times required to obtain an optimum reaction can be deter
of HFC-152a, about 30% by Weight of HCl, about 10% by
mined precisely. Furthermore, since the further treatment
does not use any chemical compound or reagent other than Weight of HF, about 2 to 20 g/kg of
HCFC-151a/HCC-150a
 US 6,849,772 B2
5 6
and from a feW tens (for example 20) to a feW thousands of EXAMPLE 3
mg (for example 10,000) of vinyl chloride per kilo.
Another embodiment variant, represented in FIG. 2, has
As may be observed, this head fraction leaving the re?ux
column via the pipe 9 is still highly contaminated With vinyl been provided.
chloride and With synthetic intermediates. The parts of this plant Which are identical to those of the

The pipe 9 opens into an intermediate part of a distillation plant according to Example 1 bear the same reference
column 10 Whose operating conditions are such that a numbers and these parts Will not be described again.
separation of HCl in the gaseous state is obtained at the top
Unlike the plant according to Examples 1 and 2, the
of the column, this HCl being evacuated via the outlet pipe
10 product WithdraWn from the bottom of the distillation col
11. A crude reaction product substantially depleted of HCl is
umn 10 is conveyed into an intermediate part of an addi tional
WithdraWn from the bottom of column 10 and is conveyed, via
distillation column 25 via the pipe 26. It is the head
the pipe 12, to the post-reactor 13 in Which the further
fraction of this column 25 Which is conveyed into the
treatment according to the invention is carried out.
post-reactor 13 via the pipe 27. The tail fraction is recycled
The post-reactor 13 can be of the same type as the 15
into the re?ux column 6 via the return pipe 28.
synthesis reactor 1. In the illustrated embodiment of the
invention, the reaction medium therein is liquid and is This embodiment thus alloWs yet a further improvement
composed essentially of hydrogen ?uoride, optionally With in the reduction of the synthetic intermediates in the product

an organic solvent in addition. Advantageously, a hydro?u conveyed into the post-reactor 13.
orination catalyst is in the reaction medium of the post 20
reactor. EXAMPLE 4
The vinyl chloride and the HCFC-151a and HCC-150a
synthetic intermediates Which are still contained in the tail In a plant corresponding to that described in Example
fraction of the distillation column 10 are almost quantita 1, HFC-152a Was puri?ed of any vinyl chloride, in the post
2
tively converted into HFC-152a in the post-reactor 13. The 5 reactor 13, by treatment With HF.
vinyl chloride content relative to the HFC-152a leaving the
The initial composition of the reaction medium
post-reactor in gaseous form, via the (excluding catalyst) in the post-reactor 13, into Which the
pipe 14, is typically less than 1 mg/kg.
crude HFC-152a is introduced, the operating conditions of
In the embodiment illustrated, it has been envisaged to
the post-reactor and the vinyl chloride contents before and
pass the HFC-152a thus puri?ed of VC into another re?ux 3
0 after the post-reactor are given in Table 1 beloW.
column 15, in Which a fraction heavier than this substance

is condensed and recycled into the

TABLE I
post-reactor 13 via the return pipe 16.
The head fraction from the re?ux column 15 can in Composition
addition be conveyed into an intermediate part of an addi 3
of the
5 initial Operating conditions
tional distillation column 17 via a delivery pipe 18.
reaction of the post-reactor [VC] [VC]
The puri?ed HFC-152a escapes at the top of the distilla
medium [SnCl4] in- out
tion column 17 and is conveyed, via the outlet pipe 19,
(excluding T. P (% by Q let let
toWards the optional additional treatments, Which are knoWn catalyst) (O C.) (bar) Wt.) (g/hl) ppm ppm
per se, of neutraliZation, drying and ?nal distillation. 4
0 HF/HFC-152a 65-70 12 10 100 60 <1
At the bottom of the column 17, a heavy fraction is 50/50% vol.
collected in the pipe 20 and, in the example illustrated, is HF/PER 88-93 10 5 100-150 1700 <1
33/66% VOl. 10 <1
returned into the re?ux column 6. 45 HF pure 93-95 10 3 130-235 3000 <1
Heavy fractions are regularly purged from the tWo reac 1000 <1
tors 1 and 13 and are evacuated via the purge pipes 21 and 200-235 8000 <1
5000 <1
22.
Notes:
50 Q = feed ?oW rate of crude HFC-152a per litre of reaction medium [VC] inlet
EXAMPLE 2 = Weight content of VC in the crude HFC-152a fed into the

In the plant represented in FIG. 1, an embodiment variant post-reactor 13

[VC] outlet = Weight content of VC in the treated and distilled HFC-152a
has been provided, Which differs from the one described in (pipe 19)
Example 1 in that the pipe 12 is dispensed With. PER = perchloroethylene
[SnCl4] = Weight content of SnCl4 relative to the initial reaction medium.
55
In the plant according to the present example, a crude
reaction product containing HFC-152a is extracted laterally
from the distillation column 10, in the bottom of this EXAMPLE 5
column, and is conveyed into the post-reactor 13 via a pipe
23, represented by dotted lines. Apipe 24 ?tted at the bottom In this example, the ef?cacy of a post-reactor 13 in a plant

of the column 10 and also represented by dotted lines according to Example 1 and of a post-reactor 13 operating

alloWs a fraction heavier than HFC-152a, in particular synthetic under the same conditions, in a plant according to Example
intermediates of the latter, to be removed from the column 2, Were examined. The feed ?oW rate of crude HFC-152a
and returned via the pipe 20 into the re?ux column 6. into the post-reactor Was 0.6 kg/h.l.
The reaction product introduced into the post-reactor 13 65
The average concentrations of VC, HCFC-151a and of
thus contains feWer synthetic intermediates capable of HCC-150a, measured at different places in the plant, are
reforming vinyl chloride during reaction. reported in Table 2, in mg or g per kilo of HFC-152a.
 US 6,849,772 B2
8
ence of a hydro?uorination catalyst, this reaction giv

TABLE 2 ing rise to a crude reaction product which contains

VC HCFC-151a HCC-150a
vinyl chloride;
b) a separation of hydrogen chloride from the crude
(mg/kg) (g/kg) (g/kg)
reaction product which contains vinyl chloride; and
Plant of Example 1
c) a further treatment of the crude reaction product which contains

Pipe 9 150 18 4 vinyl chloride, which is substantially depleted

Pipe 19 1.2
of HCl, with hydrogen ?uoride, this further treatment
Plant of Example 2
10 giving rise to a formation of
Pipe 9 140 15 4 puri?ed 1,1 di?uoroethane.
Pipe 23 100 4.5 0.6 5. The process of claim 4, wherein the HCl separation
Pipe 19 0.6
is carried out in a distillation column with removal of HCl
from the top of the column and withdrawal of the crude
It emerges clearly from this test that a lowering of the 15 reaction product, substantially depleted of HCl, intended for
content of 1,1-di?uoroethane synthetic intermediates (by the further treatment, from the bottom of the column.
more than a half in the present case) in the product subjected 6. The process of claim 1, in which the treatment is
to the further treatment in the post-reactor 13 has the effect carried out in the liquid phase in a reaction medium
of drastically reducing the vinyl chloride content in the containing at least 200 g of HF per kg.
puri?ed 1,1-di?uoroethane. 20 7. The process of claim 1, in which the treatment
EXAMPLE 6 is carried out in the liquid phase in a reaction
In this example, a plant according to Example 2 was run
medium containing at least 500 g of HF per kg.
8. The process of claim 1, in which the treatment is carried
with various ?ow rates of crude HFC-152a, of from 0.6 to
out in the presence of a hydro?uorination catalyst chosen
0.9 kg per hour and per liter of 25 from the group comprising derivatives from groups
liquid medium in the post-reactor 13.
IIIa, IVa, IVb, Va, Vb or VIb of the Periodic Table
The results obtained are given in Table 3 below.
of the Elements, and mixtures thereof.
9. The process of claim 8, wherein said catalyst is tin,
TABLE 3
30 molybdenum, titanium, vanadium,
Flow rate Concentration (per kg of HFC-152a) antimony or tungsten derivative.
10. The process of claim 4, wherein the HCl separation is
of HFC-152a Sampling VC HCFC-151a HCC-150a
(kg/hi) Point (mg/kg) (g/kg) (g/kg) carried out in a distillation column with removal of HCl
from the top of the column, lateral extraction of the crude
0.6 Pipe 9 30 4.4 0.75 35 reaction product substantially depleted of HCl, intended for
Pipe 23 23 2.4 0.3
Pipe 19 0.6 the further treatment, and withdrawal of a tail fraction
0.7 Pipe 9 45 7.3 1.5 containing products heavier than 1,1-di?uoroethane.
Pipe 23 42 4 0.6
11. The process of claim 10, further comprising said tail
Pipe 19 0.6

0.8 Pipe 9 43 8 1.8 fraction being returned into step a).

Pipe 23 41 3.9 0.6 40 12. The process of claim 5, comprising an additional
Pipe 19 0.7
0.9 Pipe 9 52 11.7 2.9
distillation of the said crude reaction product, substantially
Pipe 23 53 6.8 1.1 depleted of HCl, obtained from the said HCl distillation
Pipe 19 0.9 column, with withdrawal, from the top of the column, of the

product intended for the further treatment, and withdrawal,

It emerges from this table that the puri?cation process 45 from the bottom of the column, of a tail fraction containing
remains effective even for high production ?ow rates. products heavier than 1,1-di?uoroethane.
It should be understood that the present invention is not 13. The process of claim 12, further comprising said tail
limited to the embodiments described above and that many fraction being returned into step a).
modi?cations can be made thereto without departing from 50 14. The process of claim 4, wherein the crude reaction
the scope of the attached claims. product contains less than 1 mol of hydrogen chloride per
What is claimed is: mole of 1,1-di?uoroethane.
1. Aprocess for purifying 1,1-di?uoroethane of any vinyl 15. The process of claim 1, wherein the process is carried
chloride, comprising treatment, with hydrogen ?uoride, of a out in the liquid phase.
crude 1,1-di?uoroethane containing less than 1 mol of 55 16. The process of claim 4, wherein the further treatment
hydrogen chloride per mole of 1,1-di?uoroethane. is carried out in the liquid phase.
2. The process of claim 1, in which the crude 1,1 17. The process of claim 1, wherein the crude product is
di?uoroethane has, per kg of 1,1-di?uoroethane, a 1-chloro obtained from a synthesis reactor by withdrawing the HCl
1-?uoroethane content of less than 50 g and a 1,1 from the top of a distillation column and the crude product
dichloroethane content of less than 20 g. 60 from the bottom.
3. The process of claim 1, in which the crude 1,1 18. The process of claim 4, wherein the crude product is
di?uoroethane is subjected to the said treatment obtained from a synthesis reactor by withdrawing the HCl
continuously, at a ?ow rate of from 0.01 to 5 kg per hour and from the top of a distillation column and the crude product
per liter of reaction medium. from the bottom.
4. Aprocess for producing 1,1-di?uoroethane, comprising 65 19. The process of claim 1, wherein the crude 1,1
a) a reaction between hydrogen ?uoride and a chloro di?uoroethane contains less than 0.5 mol of hydrogen chlo
precursor of 1,1-di?uoroethane, optionally in the pres ride per mole of 1,1-di?uoroethane.
 US 6,849,772 B2
9 10
20. The process of claim 4, wherein the crude 23. The process of claim 1, Wherein the crude 1,1
1,1 di?uoroethane contains less than 0.5 rnol of di?uoroethane contains less than 0.03 rnol of
hydrogen chlo ride per mole of 1,1-di?uoroethane. hydrogen chloride per mole of 1,1-di?uoroethane.
21. The process of claim 1, Wherein the crude 1,1
24. The process of claim 4, Wherein the crude 1,1
di?uoroethane contains less than 0.1 rnol of hydrogen chlo- 5
di?uoroethane contains less than 0.03 rnol of hydrogen
ride per mole of 1,1-di?uoroethane.
22. The process of claim 4, Wherein the crude chloride per mole of 1,1-di?uoroethane.
1,1 di?uoroethane contains less than 0.1 rnol of
hydrogen chlo ride per mole of 1,1-di?uoroethane. * * * * *