Description

The invention relates to a method for the production of pure tetrafluoroethylene from a gas, which in
the Pyrolysis of a fluorocarbon compound with 1 to 4 C atoms, which are a hydrogen and a chlorine
atom may contain arises according to claim 1.
Tetrafluoroethylene is on an industrial scale Pyrolysis of fluorocarbon compounds in general in the
range of 400 to 1000 ° C won. To do this frequently fluorocarbon compounds having 1 to 4 carbon
atoms used, in addition to C and F atoms still a H atom and also contain a Cl or Br atom. That at the
Pyrolysis gas mixture is usually from split HF; HCl or HBr by washing with water or an aqueous
solution of said substances, the gas stream is dried and condensed. Here are Tetrafluoroethylene
(hereinafter referred to as TFE), not reacted starting material and undesirable By-products are
liquefied while nitrogen, Carbon oxide and according to their partial pressure also something TFE,
other pyrolysis products as well as pyrolysis The starting material remain in gaseous form. The
liquefied Product is now worked up by distillation, with in a first column the compounds and
äzeotropische mixtures are distilled off overhead  their boiling point deeper under the chosen
conditions than the boiling point of the TFE, which is easier than Boiling TFE (hereinafter also referred
to as "low boilers"). The bottom product of this first column is then in usually distilled in a second
column, from the distilled overhead more or less pure TFE is, while in the bottom of this column the
compounds and azeotropic mixtures remain whose boiling point under the selected conditions higher
than the boiling point TFE, which is heavier than TFE (hereinafter also called "high boiler"). The High
boilers, possibly also the low boilers, are then further worked up by distillation, especially to the
unreacted pyrolysis Recover the starting material as pure as possible and in attributed to the
pyrolysis.
The boiling behavior of various, in addition to TFE in the liquid pyrolysis gas condensate contained
compounds and azeotropic mixtures, is for the purification of the TFE unfavorable and makes this
apparatus and respect the required energy consuming. To the distillative Processing of pyrolysis to
improve are various methods are known, of which the following of the present invention of interest
are.
In DE-AS 12 95 543 is a method for separation from TFE from the pyrolysis of chlorodifluoromethane
or Bromdifluormethan contained mixtures extractive distillation with the addition of methanol, Di ethyl
ether, acetone or ethyl acetate. To  the process of DE-PS 11 61 877 are chlorinated Hydrocarbons
such as methylene chloride, chloroform, Methyl chloride, carbon tetrachloride, dichloroethylene,
Trichlorethylene and tetrachlorethylene used. These Processes have the disadvantage that the boiling
points of the Extractants are much higher than their users training temperature in the extractive
distillation. hereby need to recover significant amounts of energy, Reproduction and cooling before
application for the expended extraction agent, especially also the quantities to be applied are large, in
particular if the extractive distillation with the main amount of liquid pyrolysis condensates, as in the
bottom product the first column is present is carried out. As well become comparatively larger and
thus more expensive Devices such as heat exchangers, distillation columns and so on needed.
From EP 38 970 A1 a method is known, according to which the resulting after the condensation of
pyrolysis gases, Nitrogen and carbon monoxide containing exhaust gas for Recovery of the contained
TFE with Difluoromonochloromethane, tetrafluoromonochloroethane or
Hexafluoromonochloropropane is washed. The accruing TFE-containing washing liquid is in the
liquefaction the pyrolysis products recycled. From an introduction this washing liquid in certain places
during of the distillative cleaning process for the liquid Pyrolysis products is not mentioned, it would
be too inappropriate, since the washing liquid next to TFE contains unwanted pyrolysis products that
would interfere if not the cleaning process from the beginning run through.
A method has now been found which makes it possible to to recover pure TFE from pyrolysis gases,
with a Low boiling point distillation aids is used, which leads to lower energy consumption and / or
higher purity of the generated TFE and higher throughputs in the distillative purification allows. If the
pyrolysis product to be purified from the thermal decomposition of difluoromonochloromethane
comes, is the energy needs and equipment especially low.
The new method of obtaining pure Tetrafluoroethylene from a gas that is pyrolysis from a
fluorocarbon compound having 1 to 4 C atoms, which may contain one hydrogen and one chlorine
atom, arises and after removal of hydrogen chloride or hydrogen fluoride and optionally from Water
vapor 20 to 70 wt .-% tetrafluoroethylene contains, by Condensation of the gas optionally under
pressure, Destil Lation of the liquid condensate in several consecutive switched columns, being from
the direction of flow the pyrolysis condensate first column overhead lighter than tetrafluoroethylene
boiling compounds and azeotropic mixtures and from the flow direction of the condensate second
column overhead tetrafluoroethylene is subtracted while heavier than tetrafluoroethylene boiling
compounds and azeotropic mixtures from the swamp withdrawn from the second column and to
obtain more Fluorocarbon compounds worked up by distillation be, is characterized in that in the
second Column per 1 kg of withdrawn from this column  Tetrafluoroethylene 0.6 to 2 kg of
difluoromonochloromethane above the feed of the bottom product of the first Column are introduced.
For the inventive production of tetrafluoroethylene by pyrolysis are preferably the following
Fluorocarbon compounds suitable: Tetrafluoromonochloroethane, trifluoromethane and
Perfluorocyclobutane. Because of the favorable results is Difluoromonochloromethane as an input
product for the Pyrolysis is particularly preferred. It can also be mixtures the said compounds as an
input product for the Pyrolysis can be used.
Unless the feedstock bound for pyrolysis Hydrogen contains, arises in the pyrolysis depending on
Type of compound used or the Hydrogen fluoride mixture and / or Hydrogen chloride. These become
functional, as above already mentioned, by dissolving in water or in a aqueous solution already
containing hydrogen fluoride or hydrogen chloride, removed. The subsequently dried pyrolysis gas
should be appropriate 20 to 70 wt .-%, based on the total gas, TFE contain. In principle, lower contents
are also available TFE possible, but this will make the economy of the process without achieving
benefits worse. The described above, treated pyrolysis gases, the more contain as 70 wt .-%
tetrafluoroethylene require in the pyrolysis usually conditions (for example high temperature), which is
the formation of undesirable By-products favor, thus worsen the  Yield, based on used for the
pyrolysis Fluorocarbon compound, and may be one unjustifiably high cleaning effort.
The condensation of the washed and dried Pyrolysis gas is carried out at 0.1 to 1.5 MPa Cool down to
the appropriate temperature. Preferably is worked in the pressure range of 0.15 to 0.5 MPa. Last value
should also be for security reasons (Risk of explosion) are not exceeded.
The condensed by condensation part of the pyrolysis gas is now in a first distillation column, the order
to achieve a sufficient separation effect, 30 to 150 should have theoretical plates for separating the
Low boilers distilled overhead. This column can be operated at a pressure of 0.3 to 1.8 MPa, is
preferably in the pressure range of 0.4 to 0.5 MPa worked, whereby the upper value of the preferential
range, as already stated above, due to safety considerations is determined. The top product of the
first column becomes, as well as the non-condensable offgas from the pyrolysis, treated according to
known methods to those in it contained relatively low levels of TFE win. The bottom product of the
first column is in a second column, also to achieve a sufficient separation efficiency 30 to 150
theoretical plates should have introduced and over here pure TFE distilled off. The second column can
in the pressure range be operated from 0.3 to 1.2 MPa, and here too a range of 0.4 to 0.5 MPa from
those discussed above Reasons is preferred.  
According to the invention in this second column above the feed of the bottom product from the first
column each 1 kg of the withdrawn from this column Tetrafluoroethylene 0.6 to 2 kg of
difluoromonochloromethane fed as distillation aids. The high of Infeed is expediently chosen so that a
Violation of difluoromonochloromethane to pure TFE below 10 Tpm (= parts of
difluoromonochloromethane each 1 million parts of pure TFE), preferably below 5 Tpm is held. Be
below 0.6 kg of difluoromonochloromethane used per kg of TFE, the effect of the invention in
columns of industrially feasible separation number no longer reached, additional amounts of over 2
kg Although difluoromonochloromethane per kg of TFE is possible, but bring no additional benefits,
but only increase the costs; preferably 0.75 used up to 1.5 kg of difluoromonochloromethane per kg
of TFE.
By using the process according to the invention, only trifluoromethane and difluoroethylene need be
completely separated off in the first (low-boiling) column, while the difluoromethane which has
entered the pyrolysis gas condensate can be distributed between top product and bottom product.
The lower requirements for the separation allow a reduction in the return amount. There are per 1 kg
withdrawn from the top of the second column TFE 6 to 25 kg, preferably 6 to 15 kg, condensed
overhead product of the first column and recycled to this column. Although a portion of the
difluoromethane is introduced with the bottom product of the first column in the second (TFE)
column, this column can be operated with a relatively lower reflux ratio, without compromising the
purity of the generated TFE, since the difluoromethane with the bottom product of this Column is
discharged. For every 1 kg of tetrafluoroethylene withdrawn from the top of the second column, 3 to
10 kg, preferably 3 to 5 kg of top product, of the second column are condensed and returned to this
column if TFE of conventional purity is to be produced. However, it is also possible to obtain TFE of
particular purity, in the range of the return of 5 to 10 kg per capita TFE produced, especially if the
second column relatively much, for example 1.5 to 2 kg of difluoromonochloromethane per kg of TFE
generated.
The bottom product of the second (TFE) column is after known processes further worked up by
distillation, it is expedient to extractive distillation subjected to the azeotropic mixture
Difluoromonochloromethane and hexafluoropropene separate. For this purpose, known extraction
agents such as methanol, Acetone, diethyl ether or ethyl acetate, with much less extractant needed
and in a more favorable temperature range can be worked as if this Extractive distillation, according
to the prior art, with the entire pyrolysis gas would be performed.
Unpredictable to the skilled person is the fact that when using the method according to the invention
Separation efficiency of the second (TFE) column worsens, if the reflux ratio is too high (well over 10
kg Top product per kg generated TFE) is selected. insofar the separation according to the invention is
opposite  to what happens during normal distillative separation would be expected. The method of
the invention distinguishes from conventional absorption or extractive distillations in that the
distillation assistant in comparatively only small proportions are present.
As already mentioned above, this makes it possible Inventive process, tetrafluoroethylene in good
Yield and purity with reduced energy and to produce equipment costs. With particular advantage the
new method is used for the production of TFE from pyrolysis gases by thermal decomposition of
difluoromonochloromethane or mixtures thereof predominantly contained, were produced.
The following examples are intended to illustrate the invention in more detail explain:
example 1
Gaseous difluoromonochloromethane is in a electrically heated tube thermally split. The Fission
gases leave the pipe at a temperature of 730 ° C, they are then treated with an aqueous Solution
containing 30% by weight, based on the solution, Hydrogen chloride contains and with cooling water
of 12 ° C is cooled, then washed by chilled water, then cooled to 12 ° C, dilute sodium hydroxide
solution and finally with concentrated sulfuric acid dried. After drying, the fission gases are added
Condensed 1-80 ° C, the exhaust discarded.
There are 2705 g / h of condensate obtained after Gas chromatographic analysis following
composition having:
This condensate is in a first column of 25 mm inner diameter filled with metal rings and a theoretical
plate number of 84, below distilled at a pressure of 0.5 MPa, whereby 6700 g / h  the condensed
overhead product in the column recycled and 81.4 g / h of the overhead product removed become.
The discharged top product has to Gas chromatographic analysis of the following composition:
Difluoroethylene | 0.47 g / h
trifluoromethane 4.19 g / h
Tetrafluoroethylene 76.66 g / h
difluoromethane 0.07 g / h
It can for the recovery of tetrafluoroethylene after be worked up known purification process.
The bottom product of the first column is in a second Column of 25 mm inner diameter, with metal
rings is filled and a theoretical plate number of 84 distilled again under a pressure of 0.5 MPa. In half
of the total length of this column are 600 g / h Difluoromonochloromethane introduced. The return
will be like this adjusted that the overhead product in 100 g of tetrafluoroethylene not more than 0.05
mg of difluoromethane respectively Contains trifluoroethylene. This is achieved when 3300 g / h of
the condensed overhead product in the second Column are recycled, 948.4 g / h of the overhead
product are removed. It contains after gas chromatographic analysis
Tetrafluoroethylene | 948.4 g / h
difluoromethane 0.0047 g / h (<0.0005 g / 100 g TFE)
trifluoroethylene <0.0005 g / h
2275.2 g of bottom product are from the second column dissipated, it has after gas chromatographic
analysis following composition  
The bottom product can be used to obtain the Difluoromonochloromethane, hexafluoropropylene and
others Subjected products further distillation steps become. Here, the Difluormonochlormethan in a
temperature range can be obtained by distillation, the use of water vapor as a heating medium and
Water as a coolant allowed, with only about 1/5 of Energy costs must be spent, as at the Cryogenic
distillation of tetrafluoroethylene containing mixtures. The after separation of Hydrogen chloride,
hydrogen fluoride and water vapor contained fissile gas condensate contains 38.0 wt .-%
Tetrafluoroethylene. There will be 1 kg each from the second Column deducted tetrafluoroethylene
0.63 kg difluoromonochloromethane is introduced into the second column,
7 kg of condensed overhead product of the first column recycled into this and
3.5 kg condensed overhead product of the second column returned to this.
Comparative test
The procedure is as described in Example 1, however is in the second column no
Difluormonochlormethan fed. The reflux ratio of the first and second column is again adjusted so that
the Top product of the second column per 100 g of tetrafluoroethylene not more than 0.05 mg of
difluoromethane respectively Contains trifluoroethylene. This requires 19 100 g / h condensed
overhead of the first column in this Column and 7600 g / h condensed overhead product of second
column are returned to this column. At the top of the first column 80.2 g / h are discharged.
Composition:
Difluoroethylene | 0.57 g / h
trifluoromethane 4.17 g / h
Tetrafluoroethylene 75.16 g / h
difluoromethane 0.29 g / h
At the top of the second column 953.7 g / h are discharged.
Composition:
Tetrafluoroethylene | 953.7 g / h
difluoromethane 0.0048 g / h (0.0005 g / 100 g TFE)
trifluoroethylene <0.0005 g / h
From the bottom of the second column 1676.1 g / h are discharged.
The fission gas condensate contains 38.0% by weight of tetrafluoroethylene. There will be 1 kg each
from the second Column deducted tetrafluoroethylene
20 kg of condensed overhead product of the first column returned to this,
8 kg condensed overhead product of the second column returned to this.
The energy required to cryogenic distillation in the first and second column in the comparative
experiment much higher reflux ratios than in the driving the example according to the invention is
considerable, In contrast, the energy saving falls in the Comparative experiment in which 600 g / h
difluoromonochloromethane less to be recovered, hardly since this distillation is energetically
essential more favorable temperature range can be made.
Example 2
The procedure is as described in Example 1, with following differences:
The second column has an inner diameter of 25 mm and is filled with metal rings, but is shorter and
has only a theoretical plate number of 63. In  half of the total length of this column are 1140 g / h
Difluoromonochloromethane introduced. Again that will be Return ratio of the first and second column
so adjusted so that the top product of the second column per 100 g of tetrafluoroethylene no more
than ever 0.05 mg difluoromethane or trifluoroethylene contains. For this 6600 g / h condensed Top
product of the first column in this column and 3800 g / h of condensed overhead product of the
second column be returned to this column. At the top of the first column are discharged 82.5 g / h.
Composition:
Difluoroethylene | 0.47 g / h
trifluoromethane 4.19 g / h
Tetrafluoroethylene 77.76 g / h
difluoromethane 0.07 g / h
At the top of the second column 951.3 g / h are discharged.
Composition:
Tetrafluoroethylene | 951.3 g / h
difluoromethane 0.0046 g / h (<0.005 g / 100 g TFE)
trifluoroethylene <0.0005 g / h
From the bottom of the second column 2812.3 g / h discharged.
The fission gas condensate contains 38.0% by weight. Tetrafluoroethylene. There will be 1 kg each
from the second Column deducted tetrafluoroethylene
Introduced 1.2 kg of difluoromonochloromethane into the second column,
6.9 kg of condensed overhead product of the first column in this recycled and
4 kg of condensed overhead product of the second column returned to this.

Claims (5)

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A process for recovering pure tetrafluoroethylene from a gas formed in the pyrolysis of a fluorocarbon
compound having 1 to 4 carbon atoms, which may contain a hydrogen and a chlorine atom, and after
separation of hydrogen chloride or hydrogen fluoride and optionally of water vapor Contains 20 to 70
wt .-% tetrafluoroethylene, by condensation of the gas, optionally under pressure, distillation of the
liquid condensate in several successive columns, from the first column in the flow direction of the
pyrolysis condensate above the lighter than tetrafluoroethylene boiling compounds and azeotropic
mixtures and from the In the flow direction of the second column condensate tetrafluoroethylene is
withdrawn, while the heavy as tetrafluoroethylene boiling compounds and azeotropic mixtures
withdrawn from the bottom of the second column and worked up by distillation to obtain further
fluorocarbon compounds be characterized in that in the second column per 1 kg of the withdrawn
from this column tetrafluoroethylene 0.6 to 2 kg of difluoromonochloromethane are introduced above
the feed of the bottom product of the first column.
2. The method according to claim 1, characterized that each deducted 1 kg from the top of the
second column Tetrafluoroethylene 3 to 5 kg top product of the second Column condensed and
returned to this column become.  
3. The method according to claim 1 or 2, characterized characterized in that each 1 kg from the head
of the second Column deducted tetrafluoroethylene 6 to 15 kg Condensed overhead of the first
column and in be returned to this column.
4. The method according to one or more of claims 1 to 3, characterized in that the first and second
Column operated in the pressure range of 0.4 to 0.5 MPa become.
5. The method according to one or more of claims 1 to 4, characterized in that a liquid Condensate
from a gas is used that through Pyrolysis of difluoromonochloromethane was generated.