DE19716337A1 - Synthesis of 1-chloro-3,3,3-trifluoropropene and its fluorination to 1,1,1,3,3-pentafluoropropane - Google Patents

Abstract

1,1,1,3,3- Pentafluoropropane (CF* small Greek omega *CH* small Greek eta *CHF* small Greek eta *) is manufactured by fluorination of 1,1,1,3 3-pentachloropropane (CC1* small Greek omega *CH* small Greek eta *CHC1* small Greek eta *) with anhydrous hydrofluoric acid (HF). The reaction is carried out in two stages: the first, in the gas phase, provides essentially 1-chloro-3,3,3-trifluoropropene (CF* small Greek omega *CH=CHC1) and the second, in the liquid phase, makes it possible to convert the 1-chloro-3,3,3-trifluoropropene to 1,1,1,3,3-penta-fluoropropane.

Description

The present invention relates to the field of fluorinated hydrocarbons and in particular has a process for producing 1,1,1,3,3-pentafluoropropane (which is known to the person skilled in the art under the name "HFA 245fa") of 1,1,1,3,3-pentachloropropane (240fa).

Due to the action of chlorofluorocarbons (CFCs), the conventional Licher as coolants, propellants (aerosol fuels) and blowing agents (propellants medium) can be used for foams on the stratospheric ozone layer the production and consumption of CFCs are regulated and restricted and consequently new products had to be developed.

Concentrate research on finding substitutes for these compounds first focused on products containing hydrogen (HCFC), then on Products that no longer contain chlorine, the fluorocarbons (HFCs).

Among these compounds, there appears to be a growing interest in C₃ verbin applications (including the HFA 245fa). For example, the Use of 1,1,1,3,3-pentafluoropropane in various patent applications proposed, in particular as a blowing agent for foams (JP 5239251), as a swell medium, as propellant, as cleaning solvent for the electrical industry (DD 2 98 419) and finally as a heat exchange fluid (IP 2272086).

Knunyants et al. (Izvest. Akad. Nauk. S.S.S.R., Otdel. Khim. Nauk. 1960, 1412-1418; C.A. 55: 349c and Kinet. Catal. 1967, 8 (6), 1290-1299; C.A. 69: 3510n) the synthesis of 1,1,1,3,3-pentafluoropropane by means of catalytic hydrogenation of 1,1,3,3,3-pentafluoro-1-propene (CF₃-CH = CF₂) on catalysts based on palla dium, which is applied to aluminum oxide. However, the making is out product is not easy, and so the authors state that they use Selectivity problems due to "substitution reactions" of Fluorine atoms were faced by hydrogen atoms.

In recent times have various patents and patent applications (US-A-2 942 036, EP-A-677 503, EP-A-611 744, EP-A-687 659, WO-A-94/29251, WO-A-94/29252, WO-A-95/4022, WO-A-95/13256) the production of 1,1,1,3,3-pentafluoropropane using the hydrolysis process of chlorofluorinated propane  derivatives claimed such. B. CF₃CHClCF₂Cl, CF₃CCl₂CF₂Cl, CF₃CHClCHF₂, CF₃CCl₂CHF₂ or CF₃CH₂CF₂Cl. Aside from the fact that this hydrolysis reactions are generally not very selective, there is a disadvantage of this Ver drive in the manufacture of the chlorofluorinated starting product, which several Reaction process steps required.

EP-A-690 038 claims the preparation of the compound HFA 245fa by Fluorination of CF₃CH₂CHCl₂ and / or CF₂ClCH₂CHFCl in the liquid phase. Although this fluorination gives good results, such a process appears in industrial scale to be difficult to use and is more economical View is hardly feasible because the starting materials are made by reaction of vinylidene fluoride (CF₂ = CH₂) with dichlorofluoromethane (CHCl₂F) become difficult to access.

WO-A-96/1797 describes the preparation of the compound HFA 245fa by means of Reaction of 1,1,1,3,3-pentachloropropane with anhydrous hydrofluoric acid (Hydrofluoric acid) in the liquid phase in the presence of a fluorination catalyst according to the following reaction equation:

CCl₃CH₂CHCl₂ + 5 HF → CF₃CH₂CHF₂ + 5 HCl

In view of the easy accessibility of the chlorine derivative, this is one of them Fluorination processes undeniably represent a real advance in terms of previously described method. According to the teaching of this patent application the fluorination under completely conventional conditions of fluorine tion in the liquid phase in the presence of antimony chlorofluorides at about 135 ° C and with about 10 to 25% by weight of catalyst, based on the organic substances, carry out. The yields in the various examples of this patent registration are given, but are not very good (57% for example 1.54% for example 2 and 71% for example 3), and apart from example 1, in which it is stated that 11% of the compound 244fa is formed, it is not possible find out what kind and amounts of by-products are formed.  

The applicant has now examined this fluorination reaction very thoroughly and found that there were systematically relatively substantial amounts of by-products form the essentially chlorination products and / or doubling products (coupling products) from 240fa or its reaction products.

These products are less volatile than compound 245fa, which accumulate in the reactor, can not be used again and thus reduce the Overall yield. The amounts of these heavy products over the course of time this fluorination are obviously dependent on the process conditions and are more significant the higher the temperature of the Reaction is and the more substantial the amount of catalyst and / or chlorine is; she generally correspond to about 10 to 20% of the pentachloropropane used. These low volatility products are essentially olefinic or diolefinic C₆ products, the most important of which could be identified and the correspond to the following empirical formulas:

C₆H₄F₇Cl
C₆H₄F₆Cl₂
C₆H₃F₈Cl
C₆H₃F₆Cl₃
C₆H₂F₆Cl₂.

According to their work using the HFA 245fa connection Has affected fluorination of 240fa with anhydrous hydrofluoric acid Applicant now found that a catalytic fluorination process in the gas phase enables a very easy overall conversion of the 240fa light. Since the fluorination of the CCl₃ group is much easier than the fluorination of the CHCl₂ group, have the fluorination products that in the course of such Ver driving are obtained, all a terminal CF₃ group. However, in Contrary to what could be expected, the main product of the reaction was not about the compound HFA 245fa, but the 1-chloro-3,3,3-trifluoropropene:

CF₃CH = CHCl (1233zd).

The selectivities for the 1233zd olefin are generally wide greater than 50% and can reach high values of even 90%. The others Products from fluorination in the gas phase are:

CF₃CH₂CHF₂ (245fa)
CF₃CH₂CHFCl (244fa)
CF₃CH₂CHCl₂ (243fa)
CF₃CH = CHF (1234ze),

and only traces of other by-products are formed.

Under certain conditions, especially with very high molar ratios of HF / 240fa, it is possible to obtain relatively high selectivities with respect to 245fa, which can reach 30 to 40%, and if you fluorinate at high temperatures temperature (300 to 350 ° C) and with high HF / 240fa molar ratios, selectivities for olefin 1234ze can reach about 15%. However, the olefin 1233zd remains the main product. Given the very close volatilities of HFA 245fa (boiling point at 15 ° C) and the olefin 1233zd (boiling point at 20.8 ° C), it is practically impossible to use these to separate both products by a simple distillation, and consequently it is not possible the product 1233zd in the course of the fluorination process, which is used for Production of 245fa is intended to be recycled or reinstalled.

The applicant has now also found that the olefin 1233zd and the other products that may accompany it and those related to fluorination be formed in the gas phase (243fa, 244fa, 1234ze) by means of a catalytic Fluorination process can be implemented in the liquid phase to 245fa. in the Contrary to the fluorination of compound 240fa in the liquid phase, which besides the Compound 245fa provides numerous non-volatile by-products, which the Aus reduce prey, the fluorination of 1233zd and the other fluorie proceeds tion products of the 240fa that already contain a terminal CF₃ group (243fa, 244fa, 1234ze), much smoother and only provides traces of non-volatile products. Compounds 243fa, 244fa and 1234ze can optionally be obtained from Ver Compounds 1233zd and 245fa are separated by distillation before being added to fluorination can be used in the liquid phase, but such is under no circumstances necessary; there is interest, the crude product that is in ver is obtained in the gas phase during the process step, directly at the Fluorie step in the liquid phase.  

The main subject of the present invention is therefore a method of manufacture treatment of 245fa by means of fluorination of 240fa, which is characterized in that the reaction is carried out in two successive process steps:

• - The first process step, fluorination, is carried out in the gas phase and mainly provides compound 1233zd, possibly together with compounds 243fa, 244fa, 245fa and 1234ze;
• - The second process step of fluorination is carried out in the liquid phase and enables the implementation of 1233zd and, if necessary, its companion products (243fa, 244fa and 1234ze) to 245fa.

The invention relates equally to each of the two process steps and consequently claims separately:

• - the production of 1233zd by fluorination of 240fa in the gas phase;
• - the production of 245fa by fluorination of 1233zd in the liquid phase.

1,1,1,3,3-pentachloropropane (240fa), which can be used as the starting product easily in a single process step according to the methods known per se by reaction of carbon tetrachloride (CCl₄) with vinyl chloride (CH₂ = CHCl) are provided, d. H. widely available from two on an industrial scale connections.

Fluorination of 240fa in the gas phase

This first process step consists of a mixture in the gas phase 240fa and hydrogen fluoride in the presence of a fluorination catalyst deln.

Fluorination catalysts used in this first process step can be catalysts in bulk (full catalysts) or on Support materials applied catalysts, wherein the support material in the Reaction environment must be stable, for example activated carbon, aluminum fluoride or Aluminum phosphate.  

Among the bulk catalysts (full catalysts) you can in particular Name chromium oxide after any of those known to those skilled in the art Process can be produced (sol-gel process, precipitation of the hydroxide starting from chromium salts, reduction of chromic anhydride etc.). Derivatives of Metals such as nickel, iron, manganese, cobalt and zinc can work alone or in combination with chromium in the form of bulk catalysts, however equally also in the form of catalysts applied to support materials be used.

The catalysts applied to support materials can be in the form of spheres Chen, extrudates, pellets or, if you are in a fixed bed, in shape of pieces can be used. For the catalysts in bulk is generally the form of pellets or beads is preferred. When you're in a vortex procedure, it is preferred to use a catalyst in the form of Beads or extrudates.

The following are non-limiting examples of catalysts:

• - Microspheres made of chromium oxide, which are obtained according to the sol-gel process, as described in European Patent P 31 69 123.4 granted with effect for the Federal Republic of Germany (corresponding to EP-A-55 652 and French patent FR 2 501 062) is described.
  In these documents, catalysts for the fluorination of aliphatic chlorine compounds in the gas phase based on chromium oxide are described, which consist of microspheres of amorphous Cr₂O₃ with a diameter of 0.1 to 3 mm and are produced by a so-called sol-gel process by a Sol of chromium hydroxide in the form of small droplets is dispersed in an organic solvent which is immiscible or only partially miscible with water and is converted into a gel, the microspheres obtained in this way being washed, dried and then subjected to thermal activation at temperatures between 100 and 500 ° C are subjected. The chromium hydroxide sol can be obtained from an aqueous solution of a chromium salt to which ammonia and hexamethylenetetramine have been added, or by reducing an aqueous chromium trioxide solution with an alcohol. The sol can be gelified in 2-ethylhexanol. 1 to 10% colloidal silicon dioxide, based on dry substance, can be added to the chromium hydroxide sol.
• - Chromium oxide catalysts based on activated carbon (European patent P 31 70 898.6 granted with effect for the Federal Republic of Germany, corresponding to EP-A-55 659 and US-A-4 474 895), with aluminum phosphate (with effect for Federal Republic of Germany granted European patent P 31 63 325.0, corresponding to EP-A-55 958) or on aluminum fluoride (with effect for the Federal Republic of Germany European patent P 34 61 176.2, corresponding to US-A-4 579 974, as well as with Effect for the Federal Republic of Germany granted European Patent P 34 61 175.4, corresponding to US-A-4 579 976) are applied.
  The catalysts according to DE 31 70 898.6 or US-A 4 474 895 are catalysts based on chromium oxide, which is deposited by impregnation with an aqueous solution of chromium trioxide on activated carbon, which has a specific total surface area of more than 1000 m² / g, has a surface of the pores with a radius between 40 and 50 Å of more than 5 m² / g and a surface of the pores with a radius of 250 Å or more than 2 m² / g, the impregnation being a drying at a temperature of connects above 150 ° C; the catalysts contain 0.5 to 2.8 gram atoms of chromium per liter and are preferably in the form of particles with a diameter between 100 μm and 3000 μm; they can be activated by treatment with anhydrous hydrogen fluoride before use.
  The fluorination catalysts according to DE 31 63 325.0 and EP-A-55 958 consist of salts or oxides of chromium in combination with aluminum phosphate, contain 0.1 to 0.3 gram atom of chromium per liter and have a specific total surface area of over 200 m² / g, a surface of the pores with a radius of 4 to 5 nm over 5 m² / g and a surface of the pores with a radius equal to or greater than 25 nm over 2 m² / g; they can be shaped by extrusion / granulation.
  The fluorination catalysts according to DE 34 61 176.2 and DE 34 61 175.4 are catalysts made from a γ-aluminum oxide which is impregnated with chromium sesquioxide Cr₂O₃ in an amount of 1.5 to 4 chromium atoms per liter of aluminum oxide, the catalyst being a temperature between 300 and 400 ° C can be activated with a mixture of hydrogen fluoride and 1,1,2-trichloro-1,2,2-trifluoroethane.
• - Mixed catalysts made of chromium oxide and nickel fluoride based on aluminum fluoride are applied (with effect for the Federal Republic of Germany European patent 691 05 924.1, corresponding to EP-A-0 486 333).

The catalyst described in these documents is a mixed catalyst consisting of oxides, halides and / or oxyhalides of nickel and chromium, which is applied to a support material made of aluminum fluoride or a mixture of aluminum fluoride / aluminum oxide, the weight fraction of nickel or chromium in the catalyst for each of the metals is in particular 0.5 to 20%, the nickel / chromium atomic ratio generally being between 0.5 and 5, preferably 1. The carrier material can contain significant amounts of up to 1000 ppm sodium, without this affecting the catalytic properties.
This mixed catalyst can be prepared in a manner known per se starting from activated alumina. This can be converted in a first step by fluorination using air and hydrogen fluoride into aluminum fluoride or a mixture of aluminum fluoride and aluminum oxide, the yield of the conversion of the aluminum oxide to aluminum fluoride being essentially dependent on the temperature at which the fluorination of the aluminum oxide is carried out (generally between 200 and 450 ° C, preferably between 250 and 400 ° C). The carrier substance is then impregnated with aqueous solutions of chromium and nickel salts or with aqueous solutions of chromic acid, nickel salt and methanol (as a reducing agent for chromium). The chlorides are preferably used as the chromium and nickel salts, but other salts such as the oxalates, formates, acetates, nitrates and sulfates or the nickel dichromate can also be used, provided that these salts are used in the amount of water used are soluble, which can be absorbed by the carrier.
The catalyst can also be prepared by directly impregnating the activated alumina with the solutions of the chromium and nickel compounds mentioned above. In this case, at least a portion of the alumina (70% or more) is converted to aluminum fluoride during the catalyst activation step.
The activated aluminum oxides that can be used to prepare the catalyst are well-known, commercially available products. Generally, they are made by calcining aluminum hydroxide at a temperature between 300 and 800 ° C.
Before it can be used in catalysis, the catalyst has to be conditioned, ie it has to be converted into active and (under the reaction conditions) stable components by a previously mentioned activation step. This treatment can be carried out either "in situ" (ie in the fluorination reactor itself) or in a corresponding apparatus which is stable under the activation conditions, this activation generally comprising the following steps and in the course of this step the catalytic steps (nickel and chromium halides, nickel chromate or dichromate, chromium oxide) are converted into the corresponding fluorides and / or oxyfluorides, accompanied by a release of water and / or hydrogen chloride:

• - Drying at low temperature (100 to 150 ° C, preferably 110 to 120 ° C) in the presence of air or nitrogen,
• - Drying at high temperature (350 to 450 ° C, preferably 390 to 410 ° C) in the presence of nitrogen,
• - Fluorination at low temperature (180 to 300 ° C, preferably at about 200 ° C) using a mixture of hydrogen fluoride and stick substance, the HF content being controlled by the temperature is kept below 300 ° C, and
• - Completion in a stream of pure hydrogen fluoride at a tempera up to 450 ° C.

Through chemical elemental analysis (chrome, nickel, fluorine, aluminum, Oxygen) following this activation can combine the mineral setting of the catalyst obtained can be determined.

• - Mass catalysts based on chromium oxides and nickel oxides (with effect for the Federal Republic of Germany granted European patent 692 04 147.8, corresponding to EP-A-0 546 883).
  These are unsupported catalysts, ie bulk catalysts, based on chromium and nickel oxides in which the nickel / chromium atomic ratio is 0.05 to 5, preferably 0.1 to 3.5, in particular 0.15 to 3, and which are produced by means of a process in which a sol is first formed from chromium (III) and nickel (II) hydroxides, this sol is then gelled and the product thus obtained is finally dried at a temperature between 250 and 450.degree and calcined. The chromium / nickel hydroxide sol can be obtained from chromium (III) sulfate, acetate or nitrate and from nickel chloride, sulfate or nitrate. The sol can additionally contain at least one additive which is selected from crystallized Cr₂O₃ powder, aluminum oxide monohydrate, hexamethylenetetramine and / or urea, colloidal silicon dioxide, wetting agents and thickeners. The formation of the sol generally comprises a heating step to a temperature between 60 and 100 ° C, preferably between 80 and 95 ° C. The sol can be formed in the presence of a chromium and / or nickel complexing agent and can be gelled, for example, using ammonia. The sol can be gelled by dispersing the sol in the form of small droplets in an organic solvent which is immiscible or not readily miscible with water (e.g. 2-ethylhexanol) and gelling at elevated temperature, followed by the microspheres formed in the same organic solvent or in an ammoniacal solution and then washing the microspheres thus obtained with dilute ammonia and then with water, which may then be followed by drying. The product obtained in this way can be processed, for example, into pellets or extrudates.
• - Nickel fluoride catalysts, which are applied to fluorinated aluminum oxide.

The aforementioned patents and patent applications, the contents of which are hereby incorporated by reference By reference, all describe a method of manufacture these catalysts, but also a process for their activation, i. H. the Conversion of the catalyst to stable, active species by means of fluorination gaseous HF diluted with inert compounds (nitrogen or air). During this activation, the metal oxides, which are the active material (e.g. Chromium oxide) or serve as a carrier material (e.g. aluminum oxide), partially or fully converted to the corresponding fluorides.

Catalysts based on chromium oxide (in bulk or on supports) are preferred material applied) and mixed catalysts made of chromium oxide and nickel fluoride.

The catalytic treatment of 240fa in the gas phase with HF according to the inventions The inventive method is preferably at a temperature between 140 ° C. and 400 ° C performed. The minimum temperature doesn't just depend on the reak activity of the 240fa, but mainly from the need to respond to keep mixture of 240fa / HF in gaseous state and any condensate to avoid compound 240fa (boiling point at 182 ° C). To the Kataly Not deactivating the sator too quickly, one is also interested in not working at high temperature. Because of this, the reaction is going ahead preferably carried out at a temperature between 180 ° C and 350 ° C.  

The pressure is not critical and the reaction is preferably under pressure between atmospheric pressure and 1.5 MPa.

The contact time can vary within a wide range, e.g. B. in the range of 0.5 seconds to 100 seconds, however a contact time in the range is preferred between 2 seconds and 30 seconds, this contact time by the the following relationship is defined:

where the symbols used in this formula have the following meanings:

P = pressure in MPa
t = contact time in seconds
d = throughput in mol / hour
V = volume of the catalyst in bulk, calculated in liters
T = temperature of the reactor in ° C.

The HF / 240fa molar ratio can also vary within a very wide range, however, working at a molar ratio is generally preferred between 5 and 30.

It is with certain catalysts and under certain process conditions equally advantageous, in the presence of a small amount of oxygen or Chlorine work to improve the life of the catalyst. They use Detected amount of oxygen or chlorine based on compound 240fa, which the Reaction feeds can vary between 0.1 mol% and 5 mol%. The oxygen and the chlorine can enter the reaction zone either alone or in admixture with it an inert gas, such as. As nitrogen, are introduced. The use of this the two compounds are not detrimental to the selectivity of the reactions Lich and, in order not to reduce the selectivity of the reaction too much, one has an interest in only using as small amounts of these inhibitors as possible to use the deactivation of the catalysts.

The reaction products that the fluorination products of the 240fa (243fa, 244fa, 245fa, 1233zd and 1234ze), the unreacted HF and the HCl formed, who treated according to the methods known per se, d. H. by distillation  and / or washing with water to remove the HCl and, if necessary, in whole or in part to separate the unreacted HF. From an economic point of view you have an interest in removing all of the HCl formed by distillation and in the second process step the mixture of fluorinated orga formed nical products and not implemented HF.

Fluorination of the 1233zd in the liquid phase

The second step, d. H. fluorination in the liquid phase of 1233zd and if applicable, products that can accompany this connection will be countered were carried out a fluorination catalyst.

The catalyst for this fluorination reaction using anhydrous fluorine water Substance acid (hydrofluoric acid) in the liquid phase is selected from derivatives of metals, the main groups IIIa, IVa and Va and the subgroups IVb, Vb and VIb belong. These metal compounds can be used either alone or in a mixture be applied. Among those from the aforementioned groups of the periodic table the elements selected elements can be titanium, niobium, tantalum, Name molybdenum, boron, tin and antimony. The compounds that contain antimony are particularly suitable. Oxides, oxyhalides can be used as metal derivatives and use halides. In particular, the halides are selected, preferably wise chlorides, fluorides and chlorofluorides. Antimony pentachloride (SbCl₅) is esp particularly suitable; its use leads to a clear implementation of the products with a high selectivity in relation to the 1,1,1,3,3-pentafluoropropane.

The amount of catalyst used in this fluorination in the liquid phase can vary widely. It is at least 0.005 mol of Catalyst per mole of organic products to be fluorinated and should be 0.5 mol of the catalyst per mole of the organic products to be fluorinated does not have stride. The amount of catalyst used is preferably between 0.02 mol and 0.25 mol of the catalyst per mol of the organic to be fluorinated Products.  

Fluorination in the liquid phase according to the present invention is under Heating the reagents is done and can be batch or continuous Lich run. The reaction temperature is generally at least 50 ° C, and usually it does not exceed 150 ° C. Preferably the reaction is at a temperature between 80 ° C and 140 ° C.

The discontinuous procedure is carried out in a closed process Reactor in which all reagents are introduced at the start of the process. With as the reaction progresses, the autogenous pressure increases by a maximum worth achieving. According to this method, the molar ratio is between anhydrous hydrofluoric acid and 1233zd and the products that exist accompany if necessary, generally between 2 and 30, in particular between 3 and 15.

The reaction can also be carried out batchwise by adding Begin placing all reagents in a reaction vessel on which a column is arranged, which enables the removal of the hydrogen chloride formed. Of the Pressure becomes constant at a certain value by means of a pressure regulator held. The value for the pressure is determined so that essentially the Hydrogen chloride can be removed and that essentially the organic Products in the reaction medium remain in the liquid state. Dependent on from the temperature of the reaction medium the pressure is generally between 5 bar and 30 bar set.

In a continuous procedure, the reagents are evenly mixed into the Reaction medium containing the catalyst introduced. Preferably over a column attached to the reaction vessel, which constant elimination of a Part or all of the lighter compounds formed in the reaction Detected (hydrogen chloride, 1,1,1,3,3, -pentafluoropropane), and condensation of the heavier products (catalyst, hydrofluoric acid, chlorofluorinated Intermediate products). The reaction pressure is at a certain Value kept constant with the help of a suitable device for pressure regulation. This value is defined by the fact that the chlorine water is separated off Substance is made possible by distillation and on the other hand the reaction environment in should remain in a liquid state; consequently, the pressure varies depending on the temperature of the reaction environment. The reaction pressure is at least  5 bar and should not exceed 60 bar. The pressure is preferably for the Reaction in a pressure interval between 10 and 40 bar. Pressure ranges between 12 and 30 bar have proven to be particularly advantageous.

The compound HFA 245fa can of the reaction products with the itself known methods are separated, and the unreacted fluorine water Substance acid and the under-fluorinated organic products can be used again will.

To maintain the activity of the catalyst, especially the activity of Antimony pentahalides, and deactivation by reduction to antimony To avoid trihalide, one has an interest in countering the fluorination were to carry out a small amount of chlorine. This addition of chlorine can be done in a continuous manner if the fluorination is continuous is performed, and the amount of chlorine associated with the organic to be fluorinated In this case, products added are generally between 0.005 and 0.05 moles of chlorine per mole of organic products added. If the fluorie tion is carried out in a discontinuous manner, the chlorine can periodically be added.

The following examples illustrate the present invention without it limit however. In these examples, all percentages refer to Mol, if nothing to the contrary is said.

example 1

In a tube reactor made of Inconel 600 with 28 mm inner diameter and a volume of 200 ml was given 100 ml of a catalyst based on Nickel fluoride and chromium oxide applied to aluminum fluoride. The physika lisch-chemical properties of this catalyst, which according to the with effect for the Federal Republic of Germany granted European patent 691 05 924.1 (according to European patent application EP-A-0 486 333) was activated by means of a nitrogen / HF mixture in a fixed bed, were the following:

• - Chemical composition (based on weight):
  Fluorine: 58.6%
  Aluminum: 25.9%
  Nickel: 6.4%
  Chromium: 6.0%
• Physical Properties:
  Bulk density (in bulk): 0.85 g / ml
  BET surface area: 23 m² / g
  Volume of the pores with a radius between 4 nm and 63 µm: 0.4 ml / g
  Surface of the pores with a radius larger than 4 nm: 23 m² / g

After the very last "in-situ" activation of the catalyst using a gas shaped mixture of nitrogen / HF at 25 ° C to 250 ° C was added to the reak tion vessel a gaseous mixture of HF and 240fa in such quantities that the HF / 240fa molar ratio was 14. The pressure in the reaction vessel was at Atmo spherical pressure kept constant, and the throughput of the addition of the mixture 240fa + HF was set so that a contact time of 2 seconds was reached has been.

The gases emerging from the reactor were washed with water, over a Calcium chloride bed dried and in a dry ice trap at -78 ° C siert. The experiment was carried out at 250 ° C for 48 hours and it was carried out a balance sheet during the last 24 hours of the trial. During this Period, 1450 g of 240fa was added and 845 g of product in the cold trap, which according to chromatographic analyzes and mass and NMR spec troscopic examinations the following proportions of produc contained:

82% 1233zd, thereof 88% trans isomer and 12% cis isomer;
8.2% 1234ze thereof 85% trans isomer and 15% cis isomer;
0.2% 243fa;
0.6% 244fa;
8.5% 245fa.

The compound 240fa was completely implemented and the overall yield 1233zd + 1234ze + 243fa + 244fa + 245fa was 97.3%.  

Examples 2 to 7

In the same reactor as in Example 1 and with the same catalyst various fluorination attempts of the 240fa in the gas phase, whereby one contact time, temperature and HF / 240fa molar ratio varied. All these Experiments were carried out for 18 hours and the reaction products were at the end of each experiment by means of chromatography in the gas phase analyzed.

The experimental conditions and molar compositions of the products obtained are shown in Table 1 in comparison to the experiment from Example 1.

These attempts make it possible to determine that the implementation of the verbin 240fa is always quantitative. The connection 1233zd is always the predominant one Main product. The compound HFA 245fa is present in larger amounts, depending lower the temperature and the higher the HF / 240fa molar ratio; in the course the best attempt (Example 5) did not give more than 36% 245fa.

Table 1

Examples 8 to 12

In the same reaction vessel as in Example 1, but with 100 ml of a trade usual catalyst made of chromium oxide in mass in the form of 4.8 mm × 4.8 mm pel lets contained that previously in a fixed bed using a nitrogen / HF mixture were activated, various fluorination attempts were carried out on the 240fa by. The pressure was always kept constant at atmospheric pressure.

The physicochemical properties of this catalyst after its activation The following were:

• - Chemical composition (based on weight):
  • - fluorine: 20.0%
  • - Chrome: 56.3%
  • - carbon: 3.5%
  • - oxygen: 20.2%
• - Physical Properties:
  • - Bulk density (in bulk): 1.21 g / ml
  • - BET surface area: 124 m² / g
  • - Volume of the pores with a diameter between 4 nm and 63 µm: 0.14 ml / g
  • - surface area of the pores with a radius larger than 4 nm: 42.3 m 2 / g

The experiments were carried out in a manner quite similar to that in Examples 1 to 7, and the process conditions and molar compositions of the products obtained are shown in Table 2.

As in Examples 1 to 7, it is also found in this case that the 1233zd is always the main product. The two catalysts give very similar results (see examples 2 and 8). At low temperatures (150 ° C) the amount is high formed 245fa very low, and it forms almost exclusively 1233zd.  

Table 1

Example 13

In an autoclave made of INOX 316L with a capacity of 800 ml Pressure indicator, a temperature sensor, a rupture disc and a stirrer direction was equipped with a magnetic stirrer, they gave in each other 15 g of antimony pentachloride SbCl₅ (0.05 mol), 100 g of anhydrous fluorine hydrochloric acid (5 mol) and 66 g of 1233zd (0.50 mol).

The reactor was heated to 120 ° C and the pressure gradually increased to 42.5 bar increased. After 5 1/2 hours the reaction system was ambient brought temperature, and a remaining pressure of 14 bar was observed.

The analyzes of the various phases obtained gave the following results nisse:

• - Degree of implementation at 1233zd: 99.9%
• Selectivity with respect to 1,1,1,3,3-pentafluoropropane: 85.6%
• Selectivity in relation to 244fa: 1.3%
• - Selectivity with respect to 243fa: 12.4%.

The mainly formed by-product was treated as an olefin compound with the Molecular formula C₃HCl₂F₃ (selectivity of 0.7%) determined.  

Example 14

In an autoclave made of INOX 316L with a capacity of 1000 ml Condenser (connected to a pressure gauge / pressure regulator system), a pressure indicator, a temperature probe, a rupture disc and one Stirring device was provided with a magnetic stirrer, 38 g were added in succession Antimony pentachloride (0.127 mol), 154 g anhydrous hydrofluoric acid (7.7 mol) and 167 g of 1233zd (1.28 mol).

The water was left in the condenser (cooler) at a temperature of 20.degree circulate; the reaction vessel was heated to 120 ° C and the pressure regulated to 20 bar by removing the lighter connections. After The reaction system was brought to ambient temperature for 5 1/2 hours; one observe a residual pressure of 1.6 bar.

Analysis of the various phases obtained after complete degassing of the Autoclaves gave the following results:

• - Degree of implementation at 1233zd: 99.9%
• Selectivity with respect to 245fa: 92%
• Selectivity with respect to 244fa: 1%
• - Selectivity with respect to 243fa: 6%.

Example 15

In the same apparatus as that of embodiment 14, 30 g were gradually added Antimony pentachloride (0.1 mol), 200 g anhydrous hydrofluoric acid (10 mol) and 130 g of the reaction mixture from Example 1, which contained:

82% 1233zd
8.2% 1234ze
0.2% 243fa
0.6% 244fa
8.5% 245fa,

d. H. one mole of the precursors of 245fa (1233zd and 1234ze) and products from the Series 240 (243fa, 244fa and 245fa).

As in Example 4, the pressure was set to 20 bar and the temperature of the Reactor brought to 120 ° C over 5 1/2 hours. After cooling down The autoclave was completely degassed at room temperature, and the various  Phases that were obtained were combined and with aqueous potassium and with water washed.

The organic phase obtained no longer contained 1233zd and 1234ze and consisted of:

94% 245fa
0.8% 244fa
4.6% 243fa.

Claims (18)

1. A process for the preparation of 1,1,1,3,3-pentafluoropropane (245fa), characterized in that it is a catalytic fluorination of 1-chloro-3,3,3-tri fluoropropene (1233zd) using anhydrous hydrofluoric acid (hydrofluoric acid ) in the liquid phase. 2. The method of claim 1, wherein the fluorination at a temperature from 50 ° C to 150 ° C, preferably at a temperature between 80 ° C and 140 ° C. 3. The method according to claim 1 or 2, wherein one under discontinuously autogenous pressure of the reaction mixture. 4. The method according to claim 1 or 2, wherein continuously under one Pressure of 5 to 60 bar, preferably between 10 and 40 bar, in particular between 12 and 30 bar. 5. The method according to any one of claims 1 to 4, wherein the 1-chloro-3,3,3-tri fluoropropene in a previous process step Fluorination of 1,1,1,3,3-pentachloropropane (240fa) obtained in the gas phase has been. 6. The method according to any one of claims 1 to 4, wherein the starting product uses a raw 1233zd containing smaller quantities of 1,3,3,3-tetrafluoropropene (1234ze), 1,1-dichloro-3,3,3-trifluoropropane (243fa), 1-Chloro-1,3,3,3-tetrafluoropropane (244fa) and / or 1,1,1,3,3-pentafluoropropane (245fa). 7. The method according to any one of claims 1 to 6, wherein the molar ratio of Hydrofluoric acid to 1233zd, pure or raw, between 2 and 30, preferred between 3 and 15.   8. The method according to any one of claims 1 to 7, in which the reaction in Presence of 0.005 mol to 0.05 mol chlorine per mol 1233zd, pure or crude, carries out. 9. The method according to any one of claims 1 to 8, wherein the catalyst Metal oxide, metal oxyhalide or metal halide, preferably a Metal chloride, metal fluoride or metal chlorofluoride, especially antimony pentachloride, is. 10. The method according to any one of claims 1 to 9, in which 0.005 mol to 0.5 mol, preferably 0.02 mol to 0.25 mol, of catalyst per mole of the organi product (pure or raw 1233zd) is used. 11. A process for the preparation of 1-chloro-3,3,3-trifluoropropene (1233zd), thereby characterized in that a mixture of 1,1,1,3,3-penta in the gas phase chloropropane (240fa) and anhydrous hydrogen fluoride in the presence of a Fluorination catalyst treated. 12. The method according to claim 11, wherein one at a temperature between 140 ° C and 400 ° C, preferably between 180 ° C and 350 ° C, moves. 13. The method according to claim 11 or 12, wherein one under a pressure traversed between atmospheric pressure and 1.5 MPa. 14. The method according to any one of claims 11 to 13, wherein the contact time between 0.5 seconds and 100 seconds, preferably between 2 seconds and 30 seconds. 15. The method according to any one of claims 11 to 14, wherein the HF / 240fa molar ratio is between 5 and 30. 16. The method according to any one of claims 11 to 15, in which one in the presence from 0.1 mol to 5 mol of oxygen or chlorine per 100 mol of 240fa.   17. The method according to any one of claims 11 to 16, in which a Kataly sator based on chromium oxide or a mixed catalyst made of chromium oxide and nickel fluoride used. 18. Process for the preparation of 245fa by fluorination of 240fa in two Work steps, the first process step in the gas phase under Process conditions according to claims 12 to 17 and the second Process step in the liquid phase according to process conditions according to the Claims 2 to 10 is carried out.