JP2001524460A - Production of fluorine-containing organic compounds - Google Patents

Abstract

(57) Abstract: The production of a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, wherein both the fluorine-containing organic compound and the haloalkene separately form an azeotrope with hydrogen fluoride; Preparation of a fluorine-containing organic compound, wherein the haloalkene / hydrogen fluoride azeotrope is more volatile than the fluorine-containing organic compound / hydrogen fluoride azeotrope.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a method for producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, particularly a method for producing a hydrofluorocarbon from a fluoroalkene, particularly hexafluoropropene, hydrofluorocarbon / hydrogen fluoride. Azeotrope or azeotrope mixture, especially 1,1,1,2,3,3,3-heptafluoropropane / hydrogen fluoride azeotrope or azeotrope mixture, and haloalkene / From an azeotrope or azeotrope of hydrogen fluoride, in particular from an azeotrope or azeotrope of hexafluoropropene / hydrogen fluoride, 1,1,1,2,3,3,3- The present invention relates to a method for producing heptafluoropropane.

[0002] Hydrofluorocarbons are widely used as substitutes for chlorofluorocarbon compounds in a number of applications. Such uses include pharmaceutical uses such as aerosol propellants, use as a flame suppressant, use as a cryogen, and other uses. 1,1,1,2,3,3,3-heptafluoropropane (hereinafter referred to for convenience as "HFC 227ea"), known in the art as hydrofluorocarbon 227ea, has an ozone depletion potential. ) Is particularly useful in pharmaceutical applications because it possesses a combination of properties including low toxicity, nonflammability, solvent properties and boiling point.

[0003] The production of hydrofluorocarbons by hydrofluorination of fluoroalkenes in the liquid or gas phase, optionally in the presence of a catalyst, to the corresponding hydrofluoroalkanes Is known. Hydrogen fluoride is known as a hydrogen fluoride treating agent in such a hydrogen fluoride treatment method.

In such a hydrogen fluoride treatment method, a large number of substances are used as catalysts. For example, in a method for producing a hydrofluorocarbon by reacting a fluoroalkene and hydrogen fluoride in a gas phase, for example, in a method for producing HFC227a from hexafluoropropene, it is possible to use chromium oxyfluoride and an activated carbon catalyst. Are described in German Patent No. 2,712,732 and British Patent No. 902,590, respectively.

For example, in a method for producing a hydrofluorocarbon by reacting a fluoroalkene and hydrogen fluoride in a liquid phase, for example, in a method for producing HFC227ea from hexafluoropropene, a complex of an organic amine and hydrogen fluoride is used. The use of a catalyst consisting of and certain antimony catalysts is described in WO 97/11042 and WO 96/0243, respectively.

What is disclosed in these patent specifications is hereby incorporated by reference.

In the above process, a stoichiometric excess of hydrogen fluoride is usually used relative to the fluoroalkene, and the conversion of the fluoroalkene to the hydrofluorocarbon depends, in particular, on the catalyst used, And, if any, fluctuates due to conditions in the reactor.

The products from such reactions typically consist of the desired fluorine-containing organic compound, organic by-products and hydrogen fluoride. For example, if the haloalkene is hexafluoropropene (hereinafter referred to for convenience as "HFP"), the product stream exiting the reactor for reacting HFP with hydrogen fluoride will typically be Is HFC 227ea, HFP,
Consists of hydrogen fluoride and its azeotrope.

It is common practice to recover as much hydrogen fluoride as possible from products from such hydrofluoride treatment reactions for reuse. This recovery is partially performed by distillation. However, the presence of an azeotrope or azeotrope of HFC 227ea / hydrogen fluoride and an azeotrope or azeotrope of HFP / hydrogen fluoride in the product stream makes hydrogen fluoride mere by distillation. Is recovered from the fluorine-containing organic compound.

A product stream containing a hydrofluorocarbon / hydrogen fluoride azeotrope, such as the HFC 227ea / hydrogen fluoride azeotrope and a haloalkene / hydrogen fluoride azeotrope, such as the HFP / hydrogen fluoride azeotrope It is known that both a mixture of an organic compound substantially free of hydrogen fluoride and an aqueous hydrogen fluoride solution can be recovered by recovering a part of hydrogen fluoride by distillation and then washing with water. . However, in such treatment, hydrogen fluoride is wasted since the aqueous solution of hydrogen fluoride produced by this method is usually neutralized with caustic solution or lime and finally discarded.

In another method, as described in Applicant's WO 97/13179, the product stream from the reaction of the haloalkene with hydrogen fluoride is recovered by distillation of a portion of the hydrogen fluoride. After that, the substrate is treated with a solution in which an alkali metal is dissolved in anhydrous hydrogen fluoride.
However, in such a method, hydrogen fluoride is recovered in the above process for reuse, but has a disadvantage of requiring additional equipment.

Further, in producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, a haloalkene / hydrogen fluoride azeotrope is recovered from the fluorine-containing organic compound / hydrogen fluoride azeotrope by fractional distillation. It is also known that hydrogen fluoride can be recovered from a fluorine-containing organic compound / hydrogen fluoride azeotrope by treatment with water. However, treating the fluorine-containing organic compound / hydrogen fluoride azeotrope with water to remove hydrogen fluoride requires expensive equipment and wastes hydrogen fluoride.

[0013] While aqueous scrubbing is an efficient method for removing hydrogen fluoride from organic compounds after reacting the hydrogen fluoride with a haloalkene, however, aqueous scrubbing results in the loss of hydrogen fluoride from the process. It will be appreciated that this is an expensive method in that respect. Preferably, as much of the hydrogen fluoride as possible is separated from the product stream prior to performing the aqueous scrubbing, and more preferably, substantially all of the hydrogen fluoride is separated from the product stream, eliminating aqueous scrubbing Is particularly preferred.

In the production of a fluorine-containing organic compound by the reaction between a haloalkene and hydrogen fluoride, a haloalkene / hydrogen fluoride azeotrope is used to form a fluorine-containing organic compound / hydrogen fluoride formed during the reaction. If more volatile than the boiling mixture, i.e., if it has a lower boiling point, (a) feed the reaction product to the distillation column, (b) introduce the haloalkene into the distillation column, and It was found that by distilling the resulting mixture, a fluorine-containing organic compound substantially free of hydrogen fluoride and a haloalkene / hydrogen fluoride azeotrope could be separated.

The separated haloalkene / hydrogen fluoride azeotrope is recycled to the reactor and used in another reaction or, as described in more detail below, preferably at least a portion thereof is converted to a haloalkene. It can be separated into a liquid phase rich in hydrogen fluoride and a liquid phase rich in hydrogen fluoride. According to a first aspect of the present invention, there is provided a method for producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, wherein both the fluorine-containing organic compound and the haloalkene are separately co-existed with hydrogen fluoride. A process for the preparation of a fluorine-containing organic compound which forms a boiling mixture and wherein the haloalkene / hydrogen fluoride azeotrope is more volatile than the fluorine-containing organic compound / hydrogen fluoride azeotrope. A haloalkene and a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope-like mixture, and optionally a haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture, and / or a haloalkene consisting of hydrogen fluoride. Feeding the mixture resulting from the reaction with hydrogen fluoride to a distillation column; B. Recovering the haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture and the fluorine-containing organic compound separately from the distillation column; Separating at least a portion of the haloalkene / hydrogen fluoride azeotrope or azeotrope mixture recovered from step B into a haloalkene-rich liquid phase and a hydrogen fluoride-rich liquid phase. And a method for producing a fluorine-containing organic compound.

The reaction of the haloalkene with hydrogen fluoride as described in step A of the process according to the first aspect of the present invention can be carried out in the liquid or gas phase, optionally in the presence of a suitable catalyst.

When step C of the process according to the first aspect of the invention is performed, the separation typically comprises separating the haloalkene-rich liquid phase and the hydrogen fluoride-rich liquid phase under gravity. This is done by:

In a first embodiment of the method according to the first aspect of the present invention, the product of the reaction of the haloalkene with hydrogen fluoride is typically treated with hydrogen fluoride from the product by distillation. And then fluorinated organic compound / hydrogen fluoride azeotrope or azeotrope mixture and haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture and hydrogen fluoride Is supplied to the distillation column in Step A.

A portion of the hydrogen fluoride recovered by distillation prior to step A, if recovered, can be recycled to the reactor.

In a second embodiment of the method according to the first aspect of the present invention, the product of the reaction between the haloalkene and hydrogen fluoride is fed directly to the distillation column of step A.

In the fluorine-containing organic compound recovered from step B, hydrogen fluoride present in excess of the hydrogen fluoride required to form an azeotrope can be recovered, for example, by distillation.

The haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture recovered from the step B directly contains a haloalkene supplied to a reactor for producing a fluorine-containing organic compound or a reactor. Any suitable process stream, such as one containing a mixture of a haloalkene and hydrogen fluoride, may be provided.

Similarly, when step C is carried out, the hydrogen fluoride-rich phase and / or the haloalkene-rich liquid phase recovered from this step are directly reacted with a reactor for producing a fluorine-containing organic compound, or A suitable process stream containing the haloalkene fed to the reactor,
For example, it can be fed to a process stream containing a mixture of a haloalkene and hydrogen fluoride.

According to a second aspect of the present invention, there is provided a method for producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, wherein both the fluorine-containing organic compound and the haloalkene are separately separated from each other. A. Form an azeotrope with hydrogen, and the haloalkene / hydrogen fluoride azeotrope is more volatile than the fluorine-containing organic compound / hydrogen fluoride azeotrope; Supplying a mixture comprising a haloalkene and hydrogen fluoride to a reactor; B. optionally, recovering at least a portion of hydrogen fluoride from the reaction product of step A by distillation; A mixture from step A, comprising a haloalkene and a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope mixture, a haloalkene / hydrogen fluoride azeotrope or azeotrope mixture and HF, or When performing B, a haloalkene and
Feeding the mixture from step B comprising a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope mixture and a haloalkene / hydrogen fluoride azeotrope or azeotrope mixture to a distillation column D. Recovering the haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture from the distillation column in Step C; Recovering the fluorine-containing organic compound substantially free of hydrogen fluoride from the distillation column in Step C; A step of separating at least a part of the haloalkene / hydrogen fluoride azeotrope or the azeotrope-like mixture recovered from the step D into a haloalkene-rich phase and a hydrogen fluoride-rich phase. A method for producing a fluorine-containing organic compound is provided.

In the method according to the second aspect of the present invention for performing the step F, the liquid phase rich in hydrogen fluoride is converted into a reactor for performing a reaction between a haloalkene and hydrogen fluoride, or a supply line to the reactor. And at least a portion of the haloalkene-rich liquid phase can be recycled to step C.

In the method according to the second aspect of the present invention, the haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture recovered from the distillation column in step D, or the step The portion not subjected to F can be recycled to the reactor for carrying out the reaction between the haloalkene and hydrogen fluoride or to the feed line to the reactor.

According to another aspect of the present invention, there is provided an azeotrope or azeotrope mixture of HFC 227ea and hydrogen fluoride.

According to yet another aspect of the present invention, there is provided an azeotrope or azeotrope mixture of HFP and hydrogen fluoride.

In the method according to the second aspect of the present invention, when HFC 227ea is produced by reacting HFP with hydrogen fluoride, and when step A is carried out in the presence of a catalyst such as TaF ₅ , NbF ₅ or SbF ₅ , When the reaction is carried out at 20 to 200 ° C, preferably 40 to 120 ° C,
Suitably, it is carried out at a temperature between 0 and 100 ° C. Suitably, the reaction of step A is performed under superatomic pressure, such as in the liquid phase, for a time sufficient for the reactants to react to form HFC 227ea. This pressure is preferably
It is at least 5 bar, more preferably between 10 and 50 bar.

The residence time in the reactor of step A in the method according to the second aspect of the present invention is a time sufficient to convert the starting haloalkene to a fluorine-containing organic compound. The residence time will vary, inter alia, with the required conversion, the ratio of the reactants and the reaction conditions.

The haloalkene from step F in the process according to the second aspect of the invention is preferably recycled to the reactor for producing the fluorine-containing organic compound.

If one desires a low conversion of the haloalkene to the fluorine-containing organic compound,
Preferably, the feedstock is recycled to increase the yield of fluorine-containing organic compounds from the source material. However, if high single pass conversion is required, recirculation may be used.

In step A of the method according to the second aspect of the present invention, the molar ratio of hydrogen fluoride (HF) to the haloalkene supplied to the reactor is suitably at least 1: 1, preferably Is 1.2 to 10: 1. If low conversion is required, a molar ratio of HF to haloalkene of 0.1 to 1: 1 may be used.

In step A of the method according to the second aspect of the present invention, the molar ratio of the haloalkene to the catalyst is suitably 100: 1 or less, preferably 1-50: 1.

The levels of HF, haloalkene and catalyst in step A of the method according to the second aspect of the invention are selected such that the catalyst and the reactants are dissolved in the liquid phase under the reaction conditions used. Is appropriate.

The method according to the second aspect of the present invention may be performed in a batch mode or a continuous mode, as desired. A quasi-batch mode can also be used, in which one or more feeds are continuously fed to the process and one or more other feeds are fed to the process in a batch mode.

The method according to the second aspect of the present invention can be performed in a gas phase. Suitable conditions and catalysts for use in carrying out the process according to the second aspect of the invention in the gas phase are described in more detail in German Patent 2,712,732 and British Patent 902,590.

In step C of the method according to the second aspect of the present invention and step A of the method according to the first aspect of the present invention, the haloalkene and the fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope It is preferable to simultaneously supply the mixture and a mixture comprising a haloalkene / hydrogen fluoride azeotrope or an azeotrope-like mixture to the distillation column, and supply the haloalkene to a position in the distillation column lower than the position at which the mixture is supplied. Is more preferable.

The method according to the first or second aspect of the present invention is characterized in that the relative volatility of the haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture is such that the fluorine-containing organic compound / fluoride As long as it is higher than that of the hydrogen azeotrope or azeotrope-like mixture, it can be applied to the mixture of hydrogen fluoride with any haloalkene and any fluorine-containing organic compound. Most hydrofluorocarbons, hydrochlorofluorocarbons and hydrofluoroethers form azeotropes or azeotrope-like mixtures with hydrogen fluoride, and treatment of such mixtures, in particular, when the fluorine-containing organic compound is hydrofluorocarbon, hydrochlorofluorocarbon, Treatment of a mixture that is a chlorofluorocarbon or hydrofluoroether is a preferred embodiment of the present invention.

Examples of fluorine-containing organic compounds that can be prepared by the method according to the first aspect of the present invention include, in particular, hydrofluorocarbons (HFCs), such as pentafluoroethane and tetrafluoroethane and hydrochlorofluorocarbons (HCFCs) For example, 1,1,1,2-tetrafluoro-2-chloroethane can be mentioned.

Examples of fluorine-containing organic compounds that can be prepared by the method according to the first aspect of the present invention include, in particular, 1,1,1,2-tetrafluoroethane [HFC 134a], chloro-1,1,1- Trifluoroethane [HCFC 133a], Chlorotetrafluoroethane [HCFC 124 / 124a], Pentafluoroethane [HFC 125], 1,1-Difluoroethane [HFC 152a], 1,1,1-Trifluoroethane [HFC 143a] and 1 , 1,1,3,3-pentafluoropropane [HFC 245fa].

When the fluorine-containing organic compound prepared by the method according to the first aspect of the present invention is a hydrofluorocarbon, a hydrochlorofluorocarbon or a chlorofluorocarbon, the number of such fluorine-containing organic compounds is usually 1 to 6, preferably 1 to 6, It will contain from 1 to 4 carbon atoms.

In the following, the invention will be further described with reference to a schematic diagram of an apparatus for carrying out the method of the invention or a drawing illustrating a temperature / composition plot for certain binary systems.

FIGS. 1, 2, 3 and 4 are schematic diagrams of an apparatus for performing the method according to the second aspect of the present invention, in which FIG. 1 illustrates steps A, B, C, D and E FIG. 2 illustrates a case where steps A, B, C, D, E and F are performed, and FIG. 3 illustrates a case where steps A, C, D and E are performed. FIG. 4 illustrates a case where steps A, C, D, E, and F are performed.

FIG. 5 is a schematic diagram of an apparatus for implementing the second embodiment of the method according to the first aspect of the present invention, and FIG. 6 is a diagram showing a temperature / composition plot for the HFC 227ea / HF binary system. FIG. 7 is a drawing showing a temperature / composition plot for the HFP / HF binary system.

Although the methods according to the first and second aspects of the present invention can be applied to any of the aforementioned organic compounds, the preparation of HFC 227ea is described below.

In FIGS. 1 and 2, the supply pipe (1) is connected to a reactor (4) which optionally contains a fluorination catalyst. The product pipe (5) from the reactor (4) is connected to a first distillation column (6) through which the fluid flows; the first distillation column (6) is, for example, a single-stage flash vessel ( single stage flash vessel). The distillation column (6) is typically operated at a pressure of 12 bar, a bottom temperature of 70 ° C. and a top temperature of about 50 ° C. Distillation tower
The bottom pipe (2) from (6) is connected to the supply pipe (1), and fluid flows between them. The top pipe (7) from the distillation column (6) is connected to a second distillation column (8) which is, for example, a packed column, and a fluid flows between the two. The distillation column (8) is typically
Operating at a pressure of 12 bar, a top temperature of 37 ° C. and a bottom temperature of about 60 ° C. The distillation column (8) is provided with a supply pipe (9), a bottom pipe (10), and a top pipe (3) for flowing fluid through the supply pipe (1); supply pipe (9) Is connected to a position lower than the position where the top pipe (7) is connected to the distillation column (8).

In FIG. 2, the top pipe (3) from the distillation column (8) is provided with a pipe (11) for flowing a fluid to the phase separator (12). The phase separator (12) is provided with a pipe (13) for flowing a fluid to the supply pipe (9) and a pipe (14) for flowing the fluid to the top pipe (3).

In operation, fresh hydrogen fluoride and recirculated hydrogen fluoride (from the bottom pipe (2) and the top pipe (3)) through the feed pipe (1) to the reactor (4) And an HFP / hydrogen fluoride azeotrope (from overhead pipe (3)). The product stream (HFC 227ea, hydrogen fluoride and optionally unconverted HFP) from the reactor (4) is fed to the first distillation column (6) via the product pipe (5). In the distillation column (6), hydrogen fluoride recycled to the supply pipe (1) via the bottom pipe (2) is separated from a mixture of HFC 227ea, hydrogen fluoride and unconverted HFP. The mixture of HFC 227ea, residual hydrogen fluoride and HFP is fed from the distillation column (6) to the second distillation column (8) via the top pipe (7). HFP is supplied to the distillation column (8) via the supply pipe (9). A stream consisting of HFP and substantially all of the hydrogen fluoride contained in the stream flowing into the distillation column (8) via the pipe (7) is passed from the top of the distillation column (8) to the pipe (3).
The HFC 227ea, which is a product logistics, is removed from the distillation column (8) via the bottom pipe (10).

As shown in FIG. 2, a part of the stream in the pipe (3) is supplied in a liquid phase to the separator (12) via the pipe (11), where the HFP-rich phase is hydrogen fluoride. It is preferred to separate from the rich phase. The HFP-rich phase is fed from the pipe (13) to the distillation column (8) via the pipe (9). The liquid phase rich in hydrogen fluoride from the separator (12) is returned to the supply pipe (1) via the pipe (14) and the top pipe (3).

In FIGS. 3 and 4, the supply pipe (21) is connected to a reactor (22) which optionally contains a fluorination catalyst. The product pipe (23) from the reactor (22) is connected to a distillation column (24), for example a packed column, to flow the fluid. The distillation column (24) is typically operated at a pressure of about 12 bar, a top temperature of 37 ° C. and a bottom temperature of about 60 ° C.
The distillation column (24) is provided with a bottom pipe (25), a top pipe (26) for flowing fluid to the supply pipe (21), and a supply pipe (27); a supply pipe (27) Is the product pipe
(23) is connected at a lower position than the position connected to the distillation column (24).

In FIG. 4, a pipe (28) for flowing a fluid to a phase separator (29) is provided at the top pipe (26) from the distillation column (24). The phase separator (29) is provided with a pipe (30) for flowing a fluid through a pipe (26) and a pipe (31) for flowing a fluid through a supply pipe (27).

In operation, the reactor (22) is fed via a feed pipe (21) with hydrogen fluoride (from fresh hydrogen fluoride and from a stream rich in hydrogen fluoride (from pipe 26)). Feed stream consisting of hydrogen) and recirculated HFP. The product (HFC 227ea, hydrogen fluoride and optionally HFP) from the separator (29) flows through the product pipe (23) to the distillation column (24).
HFP is supplied to the distillation column (24) via the supply pipe (27). A stream consisting of HFP and substantially all of the hydrogen fluoride contained in the stream flowing into the distillation column (24) via the pipe (23) is passed through the pipe (26) from the top of the distillation column (24). The HFC 227ea product stream is removed from the distillation column (24) via the bottom pipe (25).

As shown in FIG. 4, a portion of the stream in pipe (26) is fed in liquid phase through pipe (28) to separator (29) where the HFP-rich phase is fluorinated. It is preferred to separate from the hydrogen-rich phase. The HFP-rich phase from distillation column (24) is fed via pipe (31) to pipe (29) and then to distillation column (24). The hydrogen fluoride-rich phase from separator (29) is returned to feed pipe (21) via pipe (30) and pipe (26).

In FIG. 5, a supply pipe (31) connected to a reactor (not shown), a supply pipe (33), a bottom pipe (34) and a top pipe are connected to the distillation column (32). (35) is provided. In carrying out the operation, the HFC 227ea / HF azeotrope or azeotrope mixture, the HFP / HF azeotrope or azeotrope mixture and / or the mixture consisting of HF are distilled via pipe (31). The stream comprising HFP is supplied to the column (32),
(32). The HFP / HF azeotrope or azeotrope-like mixture is removed from the distillation column (32) via the top pipe (35), and HFC 227ea substantially free of HF is passed through the bottom pipe (34) to the distillation column (34). Take out from 32).

The present invention is further illustrated by the following examples. Example This example both HFP and HFC 227ea form a HF azeotrope, under constant pressure, the boiling point of HFP / HF azeotrope show that below the boiling point of HFC 227ea / HF azeotrope .

FIG. 6 shows a temperature / composition plot for the HFC 227ea / HF binary system; in FIG. 6, the dotted line represents the vapor phase composition and the solid line represents the liquid phase composition. From FIG.
At 174 psi, the HFC 227ea / HF azeotrope has a boiling point of 123 ° F., and its composition is found to be 42 mol% HF and 58 mol% HFC 227ea.

FIG. 7 shows a temperature / composition plot for the HFP / HF binary system; in FIG. 7, the dotted line represents the vapor phase composition and the solid line represents the liquid phase composition. From FIG. 7, 174 psi
In Table 1, the HFP / HF azeotrope has a boiling point of 98 ° F., the composition of which is 38 mol% HF and 62 mol% HFP.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus for performing a method according to a second aspect of the present invention.

FIG. 2 is a schematic diagram of an apparatus for performing a method according to the second aspect of the present invention;

FIG. 3 is a schematic view of an apparatus for performing a method according to the second aspect of the present invention;

FIG. 4 is a schematic view of an apparatus for performing a method according to the second aspect of the present invention;

FIG. 5 is a schematic view of an apparatus for performing the method according to the first aspect of the present invention;

FIG. 6 is a drawing showing a temperature / composition plot for the HFC 227ea / HF binary system.

FIG. 7 is a drawing showing a temperature / composition plot for a HFP / HF binary system.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 supply pipe 2 bottom pipe 3 top pipe 4 reactor 5 product pipe 6 first distillation column 7 top pipe 8 second distillation tower 9 supply pipe 10 bottom pipe 11 pipe 12 phase separator 13 pipe 14 pipe 21 Supply pipe 22 Reactor 23 Product pipe 24 Distillation tower 25 Column bottom pipe 26 Tower top pipe 27 Supply pipe 28 Pipe 29 Phase separator 30 Pipe 31 Pipe 32 Distillation tower 33 Supply pipe 34 Tower bottom pipe 35 Tower pipe

[Procedure amendment]

[Submission date] March 9, 2001 (2001.3.9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction contents]

As shown in FIG. 4, a portion of the stream in pipe (26) is fed in liquid phase through pipe (28) to separator (29) where the HFP-rich phase is fluorinated. Preferably, it is separated from the hydrogen-rich phase. The HFP-rich phase from the separator (29) is fed via a pipe ( 31) to a pipe (27) and then to a distillation column (24). The hydrogen fluoride-rich phase from the separator (29) is a pipe
(30) and return to the supply pipe (21) via the pipe (26).

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZWF term (reference) 4H006 AA02 AC30 AD12 BC10 BC11 BD33 BD52 BE01

Claims (9)

[Claims] 1. A method for producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, wherein both the fluorine-containing organic compound and the haloalkene are separately
Form an azeotrope or azeotrope with hydrogen fluoride and also include haloalkene /
A process for producing a fluorine-containing organic compound, wherein the hydrogen fluoride azeotrope or azeotrope is more volatile than the fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope. A haloalkene and a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope-like mixture and, optionally, a haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture and / or hydrogen fluoride, B. supplying a mixture resulting from the reaction with hydrogen fluoride to a distillation column; A process for producing a fluorine-containing organic compound, which comprises separately recovering a haloalkene / hydrogen fluoride azeotrope or an azeotrope-like mixture and a fluorine-containing organic compound from a distillation column. 2. A step of separating at least a part of the haloalkene / hydrogen fluoride azeotrope or the azeotrope-like mixture recovered from the step B into a haloalkene-rich liquid phase and a hydrogen fluoride-rich liquid phase. The method of claim 1, further comprising: 3. A method for producing a fluorine-containing organic compound by reacting a haloalkene with hydrogen fluoride, wherein both the fluorine-containing organic compound and the haloalkene are separately
Form an azeotrope or azeotrope with hydrogen fluoride and also include haloalkene /
The hydrogen fluoride azeotrope or azeotrope-like mixture is more volatile than the fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope-like mixture; Feeding a mixture of a haloalkene and hydrogen fluoride to a reactor; B. optionally, recovering at least a portion of the hydrogen fluoride from the reaction product from the reactor of Step A by distillation. A mixture from step A, comprising a haloalkene and a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope mixture, a haloalkene / hydrogen fluoride azeotrope or azeotrope mixture and HF, or When performing B, a haloalkene and
Feeding the mixture from step B comprising a fluorine-containing organic compound / hydrogen fluoride azeotrope or azeotrope mixture and a haloalkene / hydrogen fluoride azeotrope or azeotrope mixture to a distillation column D. E. recovering the haloalkene / hydrogen fluoride azeotrope or azeotrope-like mixture from the distillation column of Step C; Recovering the fluorine-containing organic compound substantially free of hydrogen fluoride from the distillation column in step C. 4. The method further comprises the step of separating at least a portion of the haloalkene / hydrogen fluoride azeotrope or azeotrope mixture recovered from step D into a haloalkene-rich phase and a hydrogen fluoride-rich phase. The method of claim 3. 5. The method according to claim 3, wherein the fluorine-containing organic compound is a hydrofluorocarbon and the haloalkene is a fluoroalkene. 6. The method of claim 5, wherein the hydrofluorocarbon is HFC 227ea and the fluoroalkene is HFP. 7. The process of claim 3, wherein the haloalkene-rich phase from step F is recycled to the distillation column of step C, and the hydrogen fluoride-rich phase from step F is recycled to the reactor of step A.
The method described in. 8. An azeotrope or azeotrope mixture of HFC 227ea and hydrogen fluoride. 9. An azeotrope or azeotrope mixture of HFP and hydrogen fluoride.