EP1497029A1 - Catalyst regeneration with elementary halogen - Google Patents

Catalyst regeneration with elementary halogen

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Publication number
EP1497029A1
EP1497029A1 EP02805322A EP02805322A EP1497029A1 EP 1497029 A1 EP1497029 A1 EP 1497029A1 EP 02805322 A EP02805322 A EP 02805322A EP 02805322 A EP02805322 A EP 02805322A EP 1497029 A1 EP1497029 A1 EP 1497029A1
Authority
EP
European Patent Office
Prior art keywords
halogen
catalyst
chlorine
fluorine
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP02805322A
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German (de)
French (fr)
Inventor
Max Braun
Carsten Brosch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Fluor GmbH
Original Assignee
Solvay Fluor und Derivate GmbH
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Publication date
Application filed by Solvay Fluor und Derivate GmbH filed Critical Solvay Fluor und Derivate GmbH
Publication of EP1497029A1 publication Critical patent/EP1497029A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28—Regeneration or reactivation
    • B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/006—Halides
    • C01G30/007—Halides of binary type SbX3 or SbX5 with X representing a halogen, or mixed of the type SbX3X'2 with X,X' representing different halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for the catalyzed preparation of partially halogenated fluorine-containing organic compounds with regeneration of the catalyst used.
  • fluorine-containing organic compounds can be prepared by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride in the presence of catalysts.
  • U.S. Patent 2,005,710 discloses the preparation of many alkanes containing fluorine, chlorine and optionally hydrogen. Antimony halide catalysts are described as preferred. If pentavalent catalyst is reduced to the trivalent form, it is desirable that free halogen such as chlorine be present during the reaction or added at any time (see column 13, lines 32 to 37 of US-A 2,005,710).
  • This method of regenerating the catalyst in fluorination processes using hydrogen fluoride is described in US Pat. No. 2,510,872 as the prior art to be improved; the process described there provides for the use of antimony pentafluoride, but not as a catalyst but as a fluorinating agent.
  • the object of the present invention is to provide an improved process for the preparation of partially halogenated fluorine-containing organic compounds with regeneration of the catalyst by oxidation with elemental halogen, preferably chlorine. This object is solved by the following invention.
  • the inventive method for the production of partially halogenated fluorine-containing organic compounds by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride and in the presence of catalysts which are regenerated with elemental halogen provides that the regeneration is carried out so that the elementary Halogen does not come into contact with starting materials or intermediates which are undesirably reactive towards halogen.
  • Undesirable reactive are those compounds which react faster with the elemental halogen than the antimony (III) compound to be regenerated, or which form by-products in an undesirable amount.
  • it can be regarded as “undesirably reactive” if more than 10% by weight, preferably more than 5% by weight, in particular more than 2% by weight of the starting compound leads to undesired by-products.
  • a portion of the discharged reaction mixture from the reactor via a loop Preferably, a portion of the discharged reaction mixture from the reactor via a loop.
  • This preferred procedure for the preparation of partially halogenated fluorine-containing organic compounds by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride and in the presence of catalysts which are regenerated with elemental halogen provides that part of the reaction mixture is removed from the reactor halogen is added to the discharged part in order to regenerate the catalyst, and that the thus discharged part treated with the regenerated catalyst is returned to the reactor.
  • Preferred halogens are chlorine and fluorine, especially chlorine.
  • reaction mixture is continuously removed; you can also use semi-continuous reject them or a certain subset at certain times.
  • the preferred catalyst is antimony pentachloride or its fluorination products or HF adducts.
  • the fluorination products have the general formula SbF x Cl 5 _ x , where x means 0 to 5.
  • the process is also advantageous if saturated starting compounds are used. Halogen exchange reactions often take place according to an elimination-addition mechanism, or such a mechanism runs in addition to an S N mechanism. The unsaturated intermediates that result from elimination also react more easily with chlorine to form undesired secondary products. However, this attempted explanation is not intended to limit the invention.
  • the process is particularly preferably used for producing aliphatic fluorocarbon compounds or aliphatic chlorofluorocarbon compounds, in particular those having 1 to 10 carbon atoms.
  • Aliphatic C1-C5-fluorine (chlorine) hydrocarbon compounds are very particularly preferably produced, in particular aliphatic C1-C4-fluorine (chlorine) hydrocarbon compounds.
  • the following are some examples of connections that can be made and their starting connections:
  • CC1 2 F-CHC ⁇ 2 from CC1 2 CC1 2 + HF
  • the process according to the invention is preferably carried out in such a way that a liquid phase is present in the reactor. Pressure and temperature are adjusted accordingly.
  • the pressure in the reactor is preferably in the range from 1 to 15 bar, preferably in the range from 10 to 15 bar.
  • the temperature is preferably in the range from 20 to 200 ° C., in particular in the range from 70 to 150 ° C., very particularly at 90 to 120 ° C.
  • the molar ratio of hydrogen fluoride to catalyst is expediently in the range from 1: 1 to 30: 1, preferably in the range from 8: 1 to 15: 1.
  • the molar ratio of catalyst to organic starting compound is advantageously in the range from 0.1: 1 to 20: 1, preferably in the range from 1: 1 to 3: 1.
  • the procedure is such that 5 to 20 mol% of the catalyst are always removed, likewise in the case of a semi-continuous or batchwise procedure.
  • the advantage of the process is that the chlorine (or halogen) is not introduced directly into the fluorination reactor and can lead to side reactions with starting, intermediate or end products there.
  • the method can be used for any fluorination reaction. It can also be used in fluorination reactions in which aromatic compounds (which are regarded here as "rapidly halogenated") are involved. It is particularly preferably used for the production of saturated or unsaturated aliphatic fluorocarbon compounds or chlorofluorocarbon compounds having 1 to 10, preferably 1 to 5, carbon atoms.
  • aromatic compounds which are regarded here as "rapidly halogenated”
  • It is particularly preferably used for the production of saturated or unsaturated aliphatic fluorocarbon compounds or chlorofluorocarbon compounds having 1 to 10, preferably 1 to 5, carbon atoms.
  • the advantages of the process according to the invention are particularly evident when starting compounds are used which react very easily with elemental halogen, especially chlorine, as is the case, for example, with unsaturated starting compounds (halogenated ethenes, propenes, butenes ).
  • the discharged part is relaxed, for example to a pressure of a maximum of 5 bar or even a maximum of 2 bar or even less.
  • Volatile organic and inorganic compounds and this also includes the starting compound which reacts undesirably with chlorine, are removed from the discharged part in gaseous or vapor form. Only then is the regeneration of the catalyst started. This can also be carried out by isolating the product, for example in a distillation apparatus.
  • the fluorinated product is usually more volatile than the starting compounds. It can be separated from HCl or HF using conventional methods. Existing starting material is then also separated off, especially if the compounds are unsaturated. The remaining "sump" containing the catalyst is then mixed with chlorine (or halogen) and the catalyst is regenerated.
  • Another aspect of the invention relates to the control of the fluorination reaction to more or less fluorinated products. It has been shown that the proportion of Sb '(III), based on the total Sb (V) / Sb (III) system, influences the catalytic properties of the antimony catalyst. The higher the proportion of Sb (V), the greater the effect on the formation of more fluorinated products.
  • the proportion of Sb (III) can be used in the process according to the invention, for. .B. influence by reducing the discharged portion or reducing the addition of chlorine to the added portion so that a predetermined proportion of Sb (III) is present in the reactor. This promotes the formation of low fluorinated products. In order to promote the formation of more fluorinated products, the discharged portion is increased or the chlorine addition is increased.
  • the following examples are intended to illustrate the invention without restricting its scope.
  • Pentachloroethane, antimony pentafluoride and HF were introduced into a continuously mobile autoclave.
  • the molar ratio of HF to SbF 5 was about 12: 1
  • the molar ratio of SbF 5 to the starting material was 5: 1.
  • the autoclave was then brought to a temperature of 100 ° C. and a pressure of 15 bar.
  • a part of the reactor contents (about 15 mol% of the catalyst) was continuously withdrawn from the reactor (autoclave) and transferred to a stripper column.
  • Organic components in particular HCFC-121, HCFC-122 and HFC-123, as well as pentachloroethane
  • the remaining partial stream of the stripper column was mixed with elemental chlorine in countercurrent for the purpose of catalyst regeneration.
  • An advantage of a low reactor temperature is the greatly reduced tendency of Sb (v) to form Sb (III).
  • the perchlorethylene [0.05 ol] was placed in an autoclave equipped with Teflon inliner, and the antimony pentafluoride [0.1 mol] and the hydrogen fluoride [0.88 mol] were slowly added.
  • the autoclave was sealed and stirred in an oil bath preheated to 120 ° C for one hour posed. The perchlorethylene reacted completely.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Catalysts such as antimony halides can be used during fluorination reactions involving hydrogen fluoride. Said catalysts can be reduced during the reaction. Oxidation is usually carried out by introducing elementary halogen, preferably chlorine or fluorine, into the reaction mixture. According to the invention, the elementary halogen does not come into contact with starting or intermediate products which are reactive in relation to halogen. Preferably, part of the reaction mixture is outwardly transferred from the reactor. The outwardly transferred part is mixed with chlorine or fluorine in order to regenerate the catalyst and returned to the reactor.

Description

Katalysator-Regenerierung mit elementarem Halogen Catalyst regeneration with elemental halogen
Beschreibungdescription
Die Erfindung bezieht sich auf ein Verfahren zur katalysierten Herstellung von teilhalogenierten fluorhaltigen organischen Verbindungen unter Regenerierung des eingesetzten Katalysators .The invention relates to a process for the catalyzed preparation of partially halogenated fluorine-containing organic compounds with regeneration of the catalyst used.
Es ist seit langem bekannt, daß fluorhaltige organische Verbindungen durch Halogen-Fluor-Austausch oder Fluorwasserstoff-Anlagerung unter Verwendung von Fluorwasserstoff in Anwesenheit von Katalysatoren hergestellt werden können. Das US-Patent 2,005,710 offenbart die Herstellung vieler Fluor, Chlor und gegebenenfalls Wasserstoff enthaltender Alkane . Antimonhalogenid-Katalysatoren werden als bevorzugt geschildert. Sofern fünfwertiger Katalysator zur dreiwertigen Form reduziert wird, ist es wünschenswert, daß freies Halogen wie Chlor während der Reaktion anwesend ist oder zu beliebiger Zeit zugesetzt wird (siehe Spalte 13, Zeilen 32 bis 37 von US-A 2,005,710). Diese Methode, in Fluorierungsverfahren unter Verwendung von Fluorwasserstoff den Katalysator zu regenerieren, wird im US-Patent 2,510,872 als zu verbessernder Stand der Technik geschildert; das dort beschriebene Verfahren sieht den Einsatz von Antimonpentafluorid vor, aber nicht als Katalysator, sondern als Fluorierungs ittel .It has long been known that fluorine-containing organic compounds can be prepared by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride in the presence of catalysts. U.S. Patent 2,005,710 discloses the preparation of many alkanes containing fluorine, chlorine and optionally hydrogen. Antimony halide catalysts are described as preferred. If pentavalent catalyst is reduced to the trivalent form, it is desirable that free halogen such as chlorine be present during the reaction or added at any time (see column 13, lines 32 to 37 of US-A 2,005,710). This method of regenerating the catalyst in fluorination processes using hydrogen fluoride is described in US Pat. No. 2,510,872 as the prior art to be improved; the process described there provides for the use of antimony pentafluoride, but not as a catalyst but as a fluorinating agent.
Es konnte festgestellt werden, daß die Anwesenheit von elementarem Halogen wie Chlor zum Zwecke der Regenerierung des reduzierten Katalysators im Reaktor von Nachteil ist, wenn organische Verbindungen vorhanden sind, welche mit dem Halogen in unerwünschter Weise, z. B. mit elementarem Chlor unter Chlor-Anlagerung reagieren.It has been found that the presence of elemental halogen such as chlorine for the purpose of regenerating the reduced catalyst in the reactor is disadvantageous when organic compounds are present which are associated with the Halogen in an undesirable manner, e.g. B. react with elemental chlorine with chlorine addition.
Aufgabe der vorliegenden Erfindung ist es, ein verbessertes Verfahren zur Herstellung von teilhalogenierten fluor- haltigen organischen Verbindungen unter Regenerierung des Katalysators durch Oxidation mit elementarem Halogen, vorzugsweise Chlor anzugeben. Diese Aufgabe wird durch die folgende Erfindung gelöst.The object of the present invention is to provide an improved process for the preparation of partially halogenated fluorine-containing organic compounds with regeneration of the catalyst by oxidation with elemental halogen, preferably chlorine. This object is solved by the following invention.
Das erfindungsgemäße Verfahren zur Herstellung von teilhalogenierten fluorhaltigen organischen Verbindungen durch Halogen-Fluor-Austausch oder Fluorwasserstoff-Anlagerung unter Verwendung von Fluorwasserstoff und in Anwesenheit von Katalysatoren, die mit elementarem Halogen regeneriert werden, sieht vor, daß man die Regenerierung so vornimmt, daß das elementare Halogen nicht mit gegenüber Halogen unerwünscht reaktiven Ausgangs- oder Zwischenprodukten in Kontakt kommt .The inventive method for the production of partially halogenated fluorine-containing organic compounds by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride and in the presence of catalysts which are regenerated with elemental halogen, provides that the regeneration is carried out so that the elementary Halogen does not come into contact with starting materials or intermediates which are undesirably reactive towards halogen.
Für den Fachmann ist klar, daß es oft nicht möglich ist, den Kontakt zwischen Halogen und unerwünscht reaktiven Ausgangs- oder Zwischenprodukten vollkommen zu verhindern. Es reicht aus, die Regenerierung so vorzunehmen, daß das Halogen nicht mit wesentlichen Mengen an unerwünscht reaktiven Ausgangs- oder Zwischenprodukten in Kontakt kommt. "Wesentlich" bezeichnet vorzugsweise solche Mengen, die dazu führen, daß mehr als 10 Gew.-%, vorzugsweise mehr als 5 Gew.-%, insbesondere mehr als 2 Gew.-% der Ausgangsverbindung schließlich zu unerwünschten Nebenprodukten umgesetzt werden.It is clear to the person skilled in the art that it is often not possible to completely prevent the contact between halogen and undesirably reactive starting or intermediate products. It is sufficient to carry out the regeneration in such a way that the halogen does not come into contact with substantial amounts of undesirably reactive starting or intermediate products. "Essential" preferably denotes those amounts which lead to the fact that more than 10% by weight, preferably more than 5% by weight, in particular more than 2% by weight, of the starting compound are finally converted to undesired by-products.
"Unerwünscht reaktiv" sind solche Verbindungen, die schneller mit dem elementaren Halogen reagieren als die zu regenerierende Antimon (III) -Verbindung, oder welche Nebenprodukte in unerwünschter Menge bilden. Beispielsweise kann es als "unerwünscht reaktiv" angesehen werden, wenn mehr als 10 Gew.-%, vorzugsweise mehr als 5 Gew.-%, insbesondere mehr als 2 Gew.-% der Ausgangsverbindung zu unerwünschten Nebenprodukten führt ."Undesirable reactive" are those compounds which react faster with the elemental halogen than the antimony (III) compound to be regenerated, or which form by-products in an undesirable amount. For example, it can be regarded as "undesirably reactive" if more than 10% by weight, preferably more than 5% by weight, in particular more than 2% by weight of the starting compound leads to undesired by-products.
Es ist bevorzugt, die Regenerierung so vorzunehmen, daß maximal 10 Gew.-%, vorzugsweise maximal 5 Gew.-% und insbesondere max. 2 Gew.-% der Ausgangsverbindung in unerwünschtes Nebenprodukt umgesetzt wird.It is preferred to carry out the regeneration in such a way that at most 10% by weight, preferably at most 5% by weight and in particular max. 2% by weight of the starting compound is converted into an undesired by-product.
Um die erfindungsgemäße Wirkung zu erzielen, bieten sich verschiedene Möglichkeiten der Verfahrensführung an. Beispielsweise kann man batchweise arbeiten und vor Beginn der Einleitung von Halogen zur Regenerierung mindestens die unerwünscht reaktiven organischen Verbindungen abreagieren lassen oder sie aus dem Reaktor entfernen, beispielsweise durch Abdestillieren oder Dekantieren. Natürlich kann man dabei auch unreaktive Verbindungen, beispielsweise unreaktive Verfahrensprodukte abtrennen. Wenn dann allenfalls noch unwesentliche Mengen an reaktiven Verbindungen im Reaktor sind, kann man das Regenerieren durch Halogeneinleitung beginnen.In order to achieve the effect according to the invention, various options for carrying out the process are available. For example, it is possible to work in batches and, before starting to introduce halogen for regeneration, at least allow the undesirably reactive organic compounds to react or remove them from the reactor, for example by distillation or decanting. Of course, it is also possible to separate unreactive compounds, for example unreactive process products. If there are at most insignificant amounts of reactive compounds in the reactor, regeneration can be started by introducing halogen.
, Bevorzugt schleust man einen Teil der Reaktionsmischung aus dem Reaktor über eine Schleife aus . , Preferably, a portion of the discharged reaction mixture from the reactor via a loop.
Diese bevorzugte Verfahrensweise zur Herstellung von teilhalogenierten fluorhaltigen organischen Verbindungen durch Halogen-Fluor-Austausch oder Fluorwasserstoff-Anlagerung unter Verwendung von Fluorwasserstoff und in Anwesenheit von Katalysatoren, die mit elementarem Halogen regeneriert werden, sieht vor, daß man einen Teil der Reaktionsmischung aus dem Reaktor ausschleust, man den ausgeschleusten Teil mit Halogen versetzt, um den Katalysator zu regenerieren, und daß man den derart behandelten ausgeschleusten Teil mit dem regenerierten Katalysator in den Reaktor zurückführt . Bevorzugte Halogene sind Chlor und Fluor, insbesondere Chlor.This preferred procedure for the preparation of partially halogenated fluorine-containing organic compounds by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride and in the presence of catalysts which are regenerated with elemental halogen provides that part of the reaction mixture is removed from the reactor halogen is added to the discharged part in order to regenerate the catalyst, and that the thus discharged part treated with the regenerated catalyst is returned to the reactor. Preferred halogens are chlorine and fluorine, especially chlorine.
Man kann so vorgehen, daß man kontinuierlich einen Teil der Reaktionsmischung ausschleust; man kann auch halbkontinu- ierlich ausschleusen, oder zu bestimmten Zeitpunkten eine bestimmte Teilmenge.One can proceed in such a way that part of the reaction mixture is continuously removed; you can also use semi-continuous reject them or a certain subset at certain times.
Bevorzugt handelt es sich um ein Herstellungsverfahren, bei welchem ein Brom-Fluor-Austausch oder besonders bevorzugt ein Chlor-Fluor-Austausch vorgesehen ist. Gegebenenfalls kann zusätzlich auch eine HF-Anlagerung vorgesehen sein.It is preferably a production process in which a bromine-fluorine exchange or particularly preferably a chlorine-fluorine exchange is provided. If necessary, an HF attachment can also be provided.
Bevorzugter Katalysator ist Antimonpentachlorid bzw. seine Fluorierungsprodukte oder HF-Addukte. Die Fluorie- rungsprodukte haben die allgemeine Formel SbFxCl5_x, wobei x 0 bis 5 bedeutet.The preferred catalyst is antimony pentachloride or its fluorination products or HF adducts. The fluorination products have the general formula SbF x Cl 5 _ x , where x means 0 to 5.
Das Verfahren ist besonders dann vorteilhaft, wenn die hergestellten teilhalogenierten fluorhaltigen organischen Verbindungen, die Ausgangsverbindungen oder etwaige Zwischenprodukte mit elementarem Chlor in unerwünschter Weise reagieren. Dies gilt besonders dann, wenn Ausgangsverbindungen eingesetzt werden, die ungesättigte Bindungen aufweisen; diese reagieren leicht mit Chlor. Beispiel sind C=C-Doppelbindun- gen . Vorteilhaft ist das Verfahren aber auch, wenn gesättigte Ausgangsverbindungen eingesetzt werden. Halogenaustauschreaktionen erfolgen oft nach einem Eleminations-Additions-Mecha- nismus, oder ein solcher Mechanismus läuft zusätzlich zu einem SN-Mechanismus ab. Auch die bei einer Elemination entstehenden ungesättigten Zwischenprodukte reagieren leichter mit Chlor zu unerwünschten Folgeprodukten. Dieser Erklärungsversuch soll aber die Erfindung nicht einschränken. Besonders bevorzugt wird das Verfahren zur Herstellung aliphatischer Fluorkohlenwasserstoff-Verbindungen oder aliphatischer Fluorchlorkohlenwasserstoff-Verbindungen insbesondere solchen mit 1 bis 10 Kohlenstoffatomen eingesetzt. Ganz besonders bevorzugt stellt man aliphatische Cl-C5-Fluor (chlor) kohlenwasser- stoff-Verbindungen her, insbesondere aliphatische C1-C4- Fluor (chlor) kohlenwasserstoff-Verbindungen. Im folgenden werden einige Beispiele für herstellbare Verbindungen und ihre AusgangsVerbindungen angegeben:The method is particularly advantageous when the partially halogenated fluorine-containing organic compounds, the starting compounds or any intermediates react with elemental chlorine in an undesirable manner. This is especially true when starting compounds are used that have unsaturated bonds; these react easily with chlorine. Examples are C = C double bonds. However, the process is also advantageous if saturated starting compounds are used. Halogen exchange reactions often take place according to an elimination-addition mechanism, or such a mechanism runs in addition to an S N mechanism. The unsaturated intermediates that result from elimination also react more easily with chlorine to form undesired secondary products. However, this attempted explanation is not intended to limit the invention. The process is particularly preferably used for producing aliphatic fluorocarbon compounds or aliphatic chlorofluorocarbon compounds, in particular those having 1 to 10 carbon atoms. Aliphatic C1-C5-fluorine (chlorine) hydrocarbon compounds are very particularly preferably produced, in particular aliphatic C1-C4-fluorine (chlorine) hydrocarbon compounds. The following are some examples of connections that can be made and their starting connections:
CF3CH2CHF2 aus CCI3-CH = CHC1 + 5 HFCF 3 CH 2 CHF 2 from CCI 3 -CH = CHC1 + 5 HF
CF3CH2CH2-CH3 aus CC13-CH2-CC12-CH3 + 5 HFCF 3 CH 2 CH 2 -CH 3 from CC1 3 -CH 2 -CC1 2 -CH 3 + 5 HF
CF2CHCF CH-ι aus CC13~CH2-CC1 = CH2 + 5 HFCF 2 CHCF CH-ι from CC1 3 ~ CH 2 -CC1 = CH 2 + 5 HF
CH2F2 aus CH2C12 + 2HFCH 2 F 2 from CH 2 C1 2 + 2HF
CFC12 -CH2C1 aus CC12 = CHCl + HFCFC1 2 -CH 2 C1 from CC1 2 = CHCl + HF
CC12F-CHCΪ2 aus CC12 = CC12 + HFCC1 2 F-CHCΪ 2 from CC1 2 = CC1 2 + HF
CC1F2-CHC12 aus CC12 = CC12 + 2HFCC1F 2 -CHC1 2 from CC1 2 = CC1 2 + 2HF
CFo ~CHC -2 aus CC12 = CC12 + 3 HFCFo ~ CHC -2 from CC1 2 = CC1 2 + 3 HF
C — CHF aus CC12 = CC12 + 5 HFC - CHF from CC1 2 = CC1 2 + 5 HF
CF3CH2F aus CC12 = CHCl + 4 HFCF 3 CH 2 F from CC1 2 = CHCl + 4 HF
CFC12 - CH3 aus CC12 = CH2 + HFCFC1 2 - CH 3 from CC1 2 = CH 2 + HF
CHF2-CH3 aus CHF = CH2 CHF 2 -CH 3 from CHF = CH 2
CF2C1-CH3 aus CC1 — CH2 CF 2 C1-CH 3 from CC1 - CH 2
CF3-CH3 aus CF2 = CH2 CF3-CH3 from CF 2 = CH 2
CHC1F2 aus CHCI3 + 2 HFCHC1F 2 from CHCI 3 + 2 HF
CHF3 aus CHCI3 + 3 HFCHF 3 from CHCI 3 + 3 HF
Das erfindungsgemäße Verfahren wird vorzugsweise so durchgeführt, daß im Reaktor eine Flüssigphase vorliegt. Entsprechend werden Druck und Temperatur eingeregelt . Bevorzugt liegt der Druck im Reaktor im Bereich von 1 bis 15 bar, vorzugsweise im Bereich von 10 bis 15 bar. Die Temperatur liegt vorzugsweise im Bereich von 20 bis 200 °C, insbesondere im Bereich von 70 bis 150 °C, ganz besonders bei 90 bis 120 °C.The process according to the invention is preferably carried out in such a way that a liquid phase is present in the reactor. Pressure and temperature are adjusted accordingly. The pressure in the reactor is preferably in the range from 1 to 15 bar, preferably in the range from 10 to 15 bar. The temperature is preferably in the range from 20 to 200 ° C., in particular in the range from 70 to 150 ° C., very particularly at 90 to 120 ° C.
Zweckmäßig liegt das Molverhältnis von Fluorwasserstoff zu Katalysator im Bereich von 1:1 bis 30:1, vorzugsweise im Bereich von 8:1 bis 15:1.The molar ratio of hydrogen fluoride to catalyst is expediently in the range from 1: 1 to 30: 1, preferably in the range from 8: 1 to 15: 1.
Das Molverhältnis von Katalysator zur organischen Ausgangsverbindung liegt zweckmäßig im Bereich von 0,1:1 bis 20:1, vorzugsweise im Bereich von 1:1 bis 3:1. Bei kontinuierlicher Ausschleusung geht man so vor, daß immer 5 bis 20 Mol.-% des Katalysators ausgeschleust sind, ebenso bei halbkontinuierlicher oder batchweiser Durchführung.The molar ratio of catalyst to organic starting compound is advantageously in the range from 0.1: 1 to 20: 1, preferably in the range from 1: 1 to 3: 1. In the case of continuous removal, the procedure is such that 5 to 20 mol% of the catalyst are always removed, likewise in the case of a semi-continuous or batchwise procedure.
Vorteil des Verfahrens ist, daß das Chlor (bzw. Halogen) nicht unmittelbar in den Fluorierungsreaktor eingeleitet wird und dort zu Nebenreaktionen mit Ausgangs-, Zwischen- oder Endprodukten führen kann.The advantage of the process is that the chlorine (or halogen) is not introduced directly into the fluorination reactor and can lead to side reactions with starting, intermediate or end products there.
Prinzipiell kann man das Verfahren für beliebige Fluo- rierungsreaktionen anwenden. Es kann auch bei Fluorierungs- reaktionen eingesetzt werden, bei welchem aromatische Verbindungen (die hier als " eilhalogeniert " angesehen werden) beteiligt sind. Besonders bevorzugt setzt man es ein zur Herstellung von gesättigten oder ungesättigten aliphatischen Fluorkohlenwasserstoffverbindungen oder ChlorfluorkohlenwasserstoffVerbindungen mit 1 bis 10, vorzugsweise 1 bis 5 Koh- lenstoffatomen. Die Vorteile des erfindungsgemäßen Verfahrens treten besonders dann zutage, wenn man Ausgangsverbindungen einsetzt, die sehr leicht mit elementarem Halogen, besonders Chlor, reagieren, wie dies beispielsweise bei ungesättigten Ausgangsverbindungen (halogenierte Ethene, Propene, Butene ...) der Fall ist. Hierzu trägt man dafür Sorge, daß im ausgeschleusten Teil während der Chlorzugabe der Gehalt an mit Chlor reagierenden Ausgangs- oder Zwischenverbindungen sehr gering ist, oder daß solche Verbindungen gar nicht enthalten sind. Hierfür bieten sich zwei bevorzugte Maßnahmen an. Zum einen ist es möglich, immer dann einen Teil des Reaktors auszuschleusen, wenn die mit Chlor leicht reagierende Ausgangs oder Zwischenverbindung zu weniger empfindlichen Verbindungen umgesetzt ist. Es handelt sich dann um ein halbkontinuierliches Verfahren, bei welchem intermittierend die unerwünscht mit Chlor reagierende Ausgangsverbindung immer dann zugesetzt wird, wenn die Regenerierung des Katalysators beendet ist, und wobei die Regenerierung des Katalysators immer dann vor- genommen wird, wenn die betreffende Ausgangsverbindung abreagiert ist.In principle, the method can be used for any fluorination reaction. It can also be used in fluorination reactions in which aromatic compounds (which are regarded here as "rapidly halogenated") are involved. It is particularly preferably used for the production of saturated or unsaturated aliphatic fluorocarbon compounds or chlorofluorocarbon compounds having 1 to 10, preferably 1 to 5, carbon atoms. The advantages of the process according to the invention are particularly evident when starting compounds are used which react very easily with elemental halogen, especially chlorine, as is the case, for example, with unsaturated starting compounds (halogenated ethenes, propenes, butenes ...). Care is taken to ensure that the content of starting or intermediate compounds reacting with chlorine is very low in the discharged part during the addition of chlorine, or that such compounds are not present at all. There are two preferred measures for this. On the one hand, it is possible to discharge part of the reactor whenever the starting or intermediate compound, which reacts easily with chlorine, has been converted into less sensitive compounds. It is then a semi-continuous process in which the starting compound which undesirably reacts with chlorine is added intermittently whenever the regeneration of the catalyst has ended, and the regeneration of the catalyst always takes place is taken when the starting compound in question has reacted.
Eine andere Maßnahme sieht vor, daß man den ausgeschleusten Teil entspannt, beispielsweise auf einen Druck von maximal 5 bar oder gar maximal 2 bar oder noch weniger. Flüchtige organische und anorganische Verbindungen, und dazu gehört dann auch die mit Chlor unerwünscht reagierende Ausgangsverbindung, werden gasförmig oder dampfförmig aus dem ausgeschleusten Teil entfernt. Erst dann wird die Regenerierung des Katalysators begonnen. Die kann auch so durchgeführt werden, daß man eine Isolierung des Produkts durchführt, beispielsweise in einer Destillationsapparatur. Das fluorierte Produkt ist üblicherweise leichter flüchtig als die Ausgangsverbindungen. Man kann es von HCl oder HF gemäß üblichen Methoden trennen. Sodann wird auch vorhandenes Ausgangsmaterial abgetrennt, besonders wenn es sich um ungesättigte Verbindungen handelt. Der verbleibende "Sumpf", der den Katalysator enthält, wird dann mit Chlor (bzw. Halogen) versetzt und so der Katalysator regeneriert.Another measure provides that the discharged part is relaxed, for example to a pressure of a maximum of 5 bar or even a maximum of 2 bar or even less. Volatile organic and inorganic compounds, and this also includes the starting compound which reacts undesirably with chlorine, are removed from the discharged part in gaseous or vapor form. Only then is the regeneration of the catalyst started. This can also be carried out by isolating the product, for example in a distillation apparatus. The fluorinated product is usually more volatile than the starting compounds. It can be separated from HCl or HF using conventional methods. Existing starting material is then also separated off, especially if the compounds are unsaturated. The remaining "sump" containing the catalyst is then mixed with chlorine (or halogen) and the catalyst is regenerated.
Ein weiterer Aspekt der Erfindung betrifft die Steuerung der Fluorierungsreaktion zu mehr oder weniger fluorierten Produkten. Es hat sich gezeigt, daß der Anteil an Sb'(III) , bezogen auf das gesamte Sb(V) /Sb (III) -System, Einfluß auf die katalytischen Eigenschaften des Antimon-Katalysators nimmt. Je höher der Anteil an Sb (V) , desto größer die Wirkung bezüglich der Bildung höher fluorierter Produkte. Den Anteil an Sb(III) kann man beim erfindungsgemäßen Verfahren z. .B. dadurch beeinflussen, daß man die ausgeschleuste Teilmenge verringert oder die Chlorzugabe zur angeschleusten Teilmenge verringert, so daß ein vorbestimmter Anteil an Sb(III) im Reaktor vorliegt. Dadurch wird die Bildung geringer fluorierter Produkte gefördert . Um die Bildung höher fluorierter Produkte zu fördern, erhöht man die ausgeschleuste Teilmenge bzw. erhöht den Chlorzusatz. Die folgenden Beispiele sollen die Erfindung weiter erläutern, ohne sie in ihrem Umfang einzuschränken.Another aspect of the invention relates to the control of the fluorination reaction to more or less fluorinated products. It has been shown that the proportion of Sb '(III), based on the total Sb (V) / Sb (III) system, influences the catalytic properties of the antimony catalyst. The higher the proportion of Sb (V), the greater the effect on the formation of more fluorinated products. The proportion of Sb (III) can be used in the process according to the invention, for. .B. influence by reducing the discharged portion or reducing the addition of chlorine to the added portion so that a predetermined proportion of Sb (III) is present in the reactor. This promotes the formation of low fluorinated products. In order to promote the formation of more fluorinated products, the discharged portion is increased or the chlorine addition is increased. The following examples are intended to illustrate the invention without restricting its scope.
Beispiel 1:Example 1:
Herstellung von Dichlortrifluorethan (HCFC-123)Manufacture of dichlorotrifluoroethane (HCFC-123)
In einem kontinuierlich fahrbaren Autoklaven wurde Penta- chlorethan, Antimonpentafluorid und HF eingeleitet. Das Molverhältnis von HF zu SbF5 betrug etwa 12:1, das Molverhältnis von SbF5 zum Edukt betrug 5:1. Der Autoklav wurde dann auf eine Temperatur von 100 °C und einen Druck von 15 bar gebracht. Ein Teil des Reaktorinhalts (etwa 15 Mol.-% des Katalysators) wurde kontinuierlich aus dem Reaktor (Autoklaven) abgezogen und in eine Stripperkolonne überführt. Organische Bestandteile (insbesondere HCFC-121, HCFC-122 und HFC-123, sowie Pentachlorethan) wurden zusammen mit HF und HC1 unter Druckverminderung abgetrennt und in den Autoklaven rückgeführt. Der übrigbleibende Teilstrom der Stripperkolonne wurde im Gegenstrom mit elementarem Chlor zwecks Katalysatorregenerierung versetzt.Pentachloroethane, antimony pentafluoride and HF were introduced into a continuously mobile autoclave. The molar ratio of HF to SbF 5 was about 12: 1, the molar ratio of SbF 5 to the starting material was 5: 1. The autoclave was then brought to a temperature of 100 ° C. and a pressure of 15 bar. A part of the reactor contents (about 15 mol% of the catalyst) was continuously withdrawn from the reactor (autoclave) and transferred to a stripper column. Organic components (in particular HCFC-121, HCFC-122 and HFC-123, as well as pentachloroethane) were separated off together with HF and HC1 under reduced pressure and returned to the autoclave. The remaining partial stream of the stripper column was mixed with elemental chlorine in countercurrent for the purpose of catalyst regeneration.
Ein Vorteil einer niedrigen Reaktortemperatur (90 - 120 °C) ist die stark verringerte Neigung des Sb(v) zur Bildung von Sb(III) .An advantage of a low reactor temperature (90-120 ° C) is the greatly reduced tendency of Sb (v) to form Sb (III).
Beispiel 2;Example 2;
Herstellung von Dichlortrifluorethan mit Chlorierung nach Abreaktion des PerchlorethylensProduction of dichlorotrifluoroethane with chlorination after reaction of the perchlorethylene
Das Perchlorethylen [0,05 ol] wurde in einen mit Teflon- Inliner ausgestatteten Autoklaven vorgelegt und langsam mit dem Antimonpentafluorid [0,1 mol] und dem Fluorwasserstoff [0,88 mol] versetzt. Der Autoklave wurde verschlossen und für eine Stunde unter Rühren in ein auf 120 °C vorgeheiztes Ölbad gestellt. Dabei setzte sich das Perchlorethylen vollständig um.The perchlorethylene [0.05 ol] was placed in an autoclave equipped with Teflon inliner, and the antimony pentafluoride [0.1 mol] and the hydrogen fluoride [0.88 mol] were slowly added. The autoclave was sealed and stirred in an oil bath preheated to 120 ° C for one hour posed. The perchlorethylene reacted completely.
Nachdem der Autoklave auf Raumtemperatur abgekühlt war, wurde die Gasphase abgespannt. Es wurde nun 5,4 g Chlorgas [0,08 Mol, 80 Mol-% bezogen auf Antimon] in den Autoklaven gefüllt (Druck: 4,9 bar) . Nach 5 Minuten unter Rühren war der Druck auf 3,9 bar abgefallen. Der Druck blieb weitere 3 Stunden stabil. Nun wurde der Autoklave in Eis abgekühlt, die Gasphase abgespannt und danach geöffnet. Der Ansatz wurde in einer Eis/Weinsäuremischung hydrolisiert . Die Organik wurde von der wäßrigen Phase getrennt und beide wurden analysiert.After the autoclave had cooled to room temperature, the gas phase was released. 5.4 g of chlorine gas [0.08 mol, 80 mol% based on antimony] were then introduced into the autoclave (pressure: 4.9 bar). After 5 minutes with stirring, the pressure had dropped to 3.9 bar. The pressure remained stable for another 3 hours. The autoclave was then cooled in ice, the gas phase removed and then opened. The mixture was hydrolyzed in an ice / tartaric acid mixture. The organics were separated from the aqueous phase and both were analyzed.
Analyse der Organik: 00,01 area % 124a Kat.-Analyse: 55,93 m % SbF5 Analysis of the organic matter: 00.01 area% 124a Cat.analysis: 55.93 m% SbF 5
57,15 area % 123 34,27 % HF57.15 area% 123 34.27% HF
00,72 area % 113 09,80 m % HCI00.72 area% 113 09.80 m% HCI
41,97 area % 122 es war kein SbF3 nachweisbar41.97 area% 122 no SbF 3 was detectable
00,15 area % sonst.00.15 area% otherwise.
Isomeren 99,87 area % 123Isomers 99.87 area% 123
00,13 area % 123a00.13 area% 123a
Umsatz Perchlorethylen: 100 %, Selektivität zu 123, 122, 121:99,13 %Perchlorethylene conversion: 100%, selectivity to 123, 122, 121: 99.13%
Das Beispiel belegt die Vorteilhaftigkeit der Vorgehensweise, erst nach Abreaktion des Perchlorethylens die Aufchlorierung vorzunehmen. Es zeigt auch, daß die gesättigten Endprodukte nicht "unerwünschte reaktiv" sind. The example demonstrates the advantageousness of the procedure of only performing the chlorination after the perchlorethylene has reacted. It also shows that the saturated end products are not "undesirably reactive".

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von teilhalogenierten fluorhaltigen organischen Verbindungen durch Halogen-Fluor- Austausch oder Fluorwasserstoffanlagerung unter Verwendung von Fluorwasserstoff und in Anwesenheit von Katalysatoren, die mit elementarem Halogen, vorzugsweise Chlor, regeneriert werden, wobei man die Regenerierung so vornimmt, dass das e- lementar Halogen nicht mit gegenüber Halogen unerwünscht reaktiven Ausgangs- oder Zwischenprodukten in Kontakt kommt.1. Process for the preparation of partially halogenated fluorine-containing organic compounds by halogen-fluorine exchange or hydrogen fluoride addition using hydrogen fluoride and in the presence of catalysts which are regenerated with elemental halogen, preferably chlorine, the regeneration being carried out in such a way that the e- Elementary halogen does not come into contact with starting materials or intermediates which are undesirably reactive towards halogen.
2. Verfahren nach Anspruch 1, wobei man die Regenerierung so vornimmt, dass das elementar Halogen nicht mit gegenüber Halogen unerwünscht reaktiven Ausgangs- oder Zwischenprodukten in Kontakt kommt, wobei man einen Teil der Reaktionsmischung aus dem Reaktor ausschleust, man den ausgeschleusten Teil mit Halogen, vorzugsweise Chlor versetzt, um den Katalysator zu regenerieren, und man den ausgeschleusten Teil mit regeneriertem Katalysator in den Reaktor rückführt.2. The method according to claim 1, wherein the regeneration is carried out in such a way that the elemental halogen does not come into contact with starting materials or intermediates which are undesirably reactive towards halogen, part of the reaction mixture being discharged from the reactor, the part discharged being removed with halogen, preferably chlorine is added in order to regenerate the catalyst, and the part which has been removed is returned to the reactor with regenerated catalyst.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es sich um ein Herstellungsverfahren handelt, welches den Brom-Fluor-Austausch, vorzugsweise den Chlor-Fluor-Austausch gegebenenfalls mit zusätzlicher HF-Anlagerung vorsieht.3. The method according to claim 1, characterized in that it is a manufacturing process which provides the bromine-fluorine exchange, preferably the chlorine-fluorine exchange, optionally with additional HF addition.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Katalysator aus Antimonpentachlorid und/oder seinen Fluorierungsprodukten bzw. HF-Addukten handelt.4. The method according to claim 1, characterized in that the catalyst is made of antimony pentachloride and / or its fluorination products or HF adducts.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es die Herstellung aliphatischer Fluorkohlenwasserstoffverbindungen oder aliphatischer Fluorchlorkohlenwasserstoffverbindungen vorsieht, vorzugsweise mit 1 bis 10 Kohlenstoff- ato en . 5. The method according to claim 1, characterized in that it provides for the production of aliphatic fluorocarbon compounds or aliphatic chlorofluorocarbon compounds, preferably with 1 to 10 carbon atoms.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass man aliphatische Cl-C5-Fluor (chlor) kohlenwasserstoff- verbindungen herstellt.6. The method according to claim 5, characterized in that producing aliphatic Cl-C5-fluorine (chlorine) hydrocarbon compounds.
7. Verfahren nach Anspruch 6,. dadurch gekennzeichnet, dass man aliphatische Cl-C4-Fluor (chlor) kohlenwasserstoff- verbindungen herstellt.7. The method according to claim 6,. characterized in that aliphatic Cl-C4-fluorine (chlorine) hydrocarbon compounds are produced.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass es die Herstellung von Fluorethanen oder Chlorfluoretha- nen aus Chlorethenen oder Chlorfluorethenen vorsieht.8. The method according to claim 1, characterized in that it provides for the production of fluoroethanes or chlorofluoroethanes from chloroethenes or chlorofluoroethenes.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass im Reaktor ein Druck im Bereich von 1 bis 15 bar, vorzugsweise im Bereich von 10 bis 15 bar herrscht.9. The method according to claim 1, characterized in that there is a pressure in the reactor in the range from 1 to 15 bar, preferably in the range from 10 to 15 bar.
10. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass im Reaktor eine Temperatur im Bereich von 20 bis 200 °C, vorzugsweise 70 bis 150 °C herrscht.10. The method according to claim 1, characterized in that there is a temperature in the reactor in the range of 20 to 200 ° C, preferably 70 to 150 ° C.
11. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der ausgeschleuste Teil auf einen Druck von maximal 5 bar entspannt wird, um organische oder anorganische flüchtige Bestandteile abzutrennen.11. The method according to claim 1, characterized in that the discharged part is depressurized to a maximum pressure of 5 bar in order to separate organic or inorganic volatile constituents.
12. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der ausgeschleuste Teil der Reaktionsmischung im wesentlichen frei ist von organischen Verbindungen mit Doppelbindung.12. The method according to claim 1, characterized in that the discharged part of the reaction mixture is essentially free of organic compounds with a double bond.
13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Molverhältnis von Fluorwasserstoff zu Katalysator im Bereich von 1:1 bis 30:1, vorzugsweise im Bereich von 8:1 bis 15 : 1 liegt .13. The method according to claim 1, characterized in that the molar ratio of hydrogen fluoride to catalyst is in the range from 1: 1 to 30: 1, preferably in the range from 8: 1 to 15: 1.
14. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Molverhältnis von Katalysator zur organischen Aus- gangsverbindung im Bereich von 0,1:1 bis 20:1, vorzugsweise im Bereich von 1:1 bis 3:1 liegt.14. The method according to claim 1, characterized in that the molar ratio of catalyst to organic Aus gang connection in the range of 0.1: 1 to 20: 1, preferably in the range of 1: 1 to 3: 1.
15. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass 5 bis 20 Mol.-% der Katalysatormenge sich in den zur Ausschleusung dienenden Bauteilen befinden.15. The method according to claim 1, characterized in that 5 to 20 mol .-% of the amount of catalyst are in the components serving to discharge.
16. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man den Fluorierungsgrad der Verfahrensprodukte über die Regenerierung des Sb(III) steuert, wobei der Fluorierungsgrad um so höher ist, je vollständiger die Regenerierung des Sb(III) ist. 16. The method according to claim 1, characterized in that the degree of fluorination of the products of the process is controlled via the regeneration of the Sb (III), the degree of fluorination being higher the more complete the regeneration of the Sb (III) is.
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