New process and reactor for liquid phase fluorination with hydrogen fluoride

Abstract

The invention relates to an improved process for the manufacture of a fluorinated organic compound, wherein the process comprises a fluorination reaction of an organic precursor compound having at least one chlorine substituent and / or at least one double bond, and said organic precursor compound is reacted in liquid phase in HF (hydrogen fluoride) serving as solvent and fluorinating agent in the presence of a fluorinating catalyst, and wherein the fluorination reaction is performed in liquid phase in a SiC block chemical reactor, and wherein the reaction mixture is withdrawn from SiC block chemical reactor, and wherein the process comprises optionally isolating and / or purifying the targeted fluorinated organic compound.

Description

[0001] New Process and Reactor for Liquid Phase Fluorination with Hydrogen Fluoride

[0002] FIELD OF THE INVENTION

[0003] The invention relates to a new process and a new reactor as well as the use of the reactor for liquid phase fluorination of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst.

[0004] BACKGROUND OF THE INVENTION

[0005] Gas phase fluorination processes have a number of disadvantages.

[0006] As of today, even if the manufactured products comprising fluorinated organic compounds are environmentally friendly, all catalytic large industrial scale fluorinations are forced to be done in gas phase at high temperatures (> 250°C), because the reactivity of liquid phase fluorination catalysts is either insufficient or the so-called fluorination catalyst cannot be considered as “a catalyst” from a scientific point of view, because it is just a fluorinating reagent. For example, this also applies to the manufacture of fluorinated organic compounds, e.g., such like the manufacture of HCFC-134a (1 ,1 ,1 ,2-tetrafluorethane) as well as of today the manufacture of 1234yf (2,3,3,3-tetrafluoropropene) and 1234ze (1 ,1 ,1 ,3-tetrafluoropropene),

[0007] Another drawback of gas phase fluorination processes is the polymerization of olefinic precursors or of olefinic intermediates as undesired side-chain reaction.

[0008] Most of the existing gas phase fluorinations use Cr2Os-based and / or AhOs-based perfluorinated gas phase catalysts. In general, a chemical process in gas phase, on the one side requires a lot of evaporation energy to transfer all reacting compounds into the gas phase, and on the other side requires a lot of condensation energy to condense and separate products and product mixtures. Compared to gas phase, the product carbon footprint (PCF) in liquid phase can be diminished down to 25%

[0009] Fluorinations with anhydrous HF is the most efficient and economic route to make C-F- bonds (carbon-fluorine bonds). Fluorinated organic compounds, some of them containing many C-F-bonds, are essential in many fields for our life, for example, such like the application in life science (Agro- and Pharma active ingredients), new refrigerants with no ODP (Ozone Depletion Potential) and no GWP (Global Warming Potential), SFe replacement products, heat transfer fluids, membranes, fluorinated plastics, conducting salts and battery electrolyte additives. In Ullmans Encylopedia published in 2016, Siegemund and Kirsch et al give an excellent overview (https: / / doi.org / 10.1002 / 14356007.a1 1_349.pub2). In the following, hydrogen fluoride or HF normally means “anhydrous hydrogen fluoride” or “anhydrous HF”, if not stated otherwise, with the term “anhydrous” being defined herein further below. A disadvantage of lower- temperature and non-corrosive liquid phase fluorinations is the insufficient lifetime of the fluorinating catalysts used (e.g., Lewis acids such like AIF3, NiFs, TiF4, ZnF2, and SnCk). During the fluorinating reaction, especially such involving chlorine / fluorine exchange reactions, in steady state the catalysts may exist in a partial fluorinated / chlorinated form, but for simplification, only the fully fluorinated representatives or forms of catalyst are mentioned here. It is also known that only TaFs, NbFs and SbFs in excess HF have the ability to form so-called super-acids which are needed for an industrially suitable catalytic nucleophilic chlorine / fluorine exchange reaction. Further, regarding corrosiveness it is known, for example, in case of the production process of difluorochloromethane (HCFC-22) by liquid phase fluorination of chloroform (CHCh) in HF with Sb as the most common fluorinating catalyst (with a Ch-feed for maintaining catalyst activity), corrosion only plays a minor role, because the super-acid state is never reached. Furthermore, it is known that in case of antimony (Sb), the trifluoride SbFs has only very low fluorination reactivity while the pentafluoride SbFs, especially in super-acid state as H2F+SbFe' has very high nucleophilic reactivity. A drawback of such super-acids (i.e., here the metal catalyst with additional HF as reagent and solvent) as fluorination catalyst, however, is their known strong corrosiveness versus metals. Even Hastelloy high grade stainless steels do not resist once the catalyst is in such super-acid state. Any corrosiveness, especially in case of SbFs catalyzed reactions, leads to formation of much less active or even inactive SbFs due to degradation of the active SbFs.

[0010] It is also known that reactions in microreactors (e.g., in a Chemtrix microreactor) enhance reactivity and selectivity and thereby negatively enhance the product carbon footprint (PCF) rate. For example, in fluorination reactions in a microreactor, like in the production of CF2CI- CHCI2 (HCFC-122) and CF3-CHCI2 (HCFC-123) which is described in US10633310, the residence time can be diminished to 10 % vs. fluorination reactions in a CSTR (Continuously Stirred Tank Reactor). However, for example, the width of the channels out of SiC in the Chemtrix microreactor are too narrow (e.g., only about 4 mm) for the reaction to be operated continuously, as there are always small particles, either from little SbFs clogging due to very low solubility of Sb in oxidation state III (like it is used in high Sb concentrated catalyst mixtures) and besides that, the high viscosity of SbFs in HF in presence of organic starting material and / or organic fluorinated product.

[0011] The results of producing the refrigerant difluoromethane (HFC-32) in liquid phase in a flow-system (channel size also only 4 mm) and using a non pre-fluorinated Sb catalyst (based on SbCh as starting catalyst material) are disclosed in Chinese Journal of Chemical Engineering 28 (2020) 1860-1865. Although, cross-checking of the flow-system process in own laboratory indicated formation of HFC-32, nevertheless, neither residence time nor the operation mode of the flow-system process as such would allow industrial production in large scale. As HFC-32 (difluoromethane, also called difluoromethylene) is applied in 1 :1 admixture with pentafluoroethane (HFC-125) in the commercialized refrigerant HFC-410A an efficient and environmentally beneficial process to manufacture HFC-32 is highly desirable.

[0012] OBJECTS OF THE INVENTION

[0013] It is an object of the present invention to overcome the disadvantages of the prior art processes and to provide a highly efficient process for the manufacture of fluorinated organic compounds in liquid phase, and to also provide a new reactor, for efficiently performing said liquid phase fluorination reactions of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst.

[0014] Furthermore, it is an object of the present invention to provide a highly efficient process for a fluorination reaction of an organic precursor compound having at least one chlorine substituent and / or at least one double bond.

[0015] Furthermore, it is an object of the present invention to provide a highly efficient process for the manufacture of fluorinated organic compounds, wherein the process is a liquid phase fluorination, and preferably a continuous liquid phase fluorination, of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst, and wherein the process tolerates high viscosity of the reaction medium and / or presence of solids in the reaction medium and / or a slurry of fluorination catalyst.

[0016] In particular, it is also an object of the present invention to provide said highly efficient liquid phase fluorination process for the manufacture of fluorinated organic compounds, for example, which are selected from the group of C1-C10 partially or fully fluorinated alkanes and alkenes including partially or fully fluorinated C1-C10 alkanes and alkenes, which are bearing aromatic and / or NO2 groups in the molecule.

[0017] Such compounds are used in electronics, heat transfer fluids, refrigerants, firefighting agents etc. or just as key raw materials for downstream products in life science (Agro / Pharma) like disclosed for the case of HCFC-122 and HCFC-123 in W02024 / 075010 or fluorinated raw materials for difluoromethyl substituted pyrazoles like disclosed in W02024 / 150100. Another example is the fluorination of 1 ,1 ,1 ,3,3-pentachloropropane (240fa) to 1 ,1 ,1 ,3,3-pentafluoropropane (245fa) in liquid phase with Sb catalyst, which is already described in example 9 by Central Glass published in year 1996 in EP0729932 and JP3456605 but yet did not succeed in industrial scale due to too low catalyst concentration, formation of tars and usage of a not corrosion resistant stainless steel (316L). Also, olefinic intermediates can be assumed which contribute on top of the corrosion to deactivation of the catalyst.

[0018] It is also an object of the present invention to provide a new reactor for liquid phase fluorination, and preferably a continuous liquid phase fluorination, of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst, wherein the reactor is designed for a highly efficient process for the manufacture of fluorinated organic compounds by a liquid phase fluorination, and preferably by continuous (vs. gasphase energy saving) liquid phase fluorination, of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst, and wherein the process tolerates high viscosity of the reaction medium and / or presence of solids in the reaction medium and / or even a slurry of fluorination catalyst.

[0019] The main reaction in the SiC block reactor is chlorine / fluorine exchange on alkanes by HCI elimination optionally forming a double bond in the corresponding intermediate alkene followed by HF addition to the intermediate double bond. Therefore, the fluorinating reaction in SiC block reactor can advantageously also be applied to olefinic compounds with less reactive double bonds. An example of such an olefinic compound is PCE (perchloroethylene), which is very stable (therefore, formerly PCE has long been used dry cleaning). A notably further advantage of using the SiC block reactor in fluorinating reaction is that the (adjustable) diameter size of the drilled reaction channels allows for high catalyst concentrations to be used. Thus, in SiC block reactor the fluorinating reaction can easily also performed with a reaction medium having a relatively high viscosity or that even is a slurry, because such a reaction medium can be pumped through the drilled reaction channels while heat transfer characteristics and flow / residence time characteristics mimic a reaction performance of a micro reactor. For sake of clarity, said advantages of using a SiC block reactor for a fluorinating reaction do not limit to a relatively high viscosity or slurry reaction medium, but a reaction medium with lower viscosity or even as solution can be applied to the SiC block reactor as well.

[0020] It is also an object of the invention to provide a novel organic compound as precursor for the described fluorination process.

[0021] It is also an object of the invention to provide a novel partially or fully fluorinated compound, which can be produced via the process according to the invention.

[0022] SUMMARY OF THE INVENTION

[0023] The objects are solved by the process and / or the organic precursor compound and / or the partially or fully fluorinated compound and / or the reactor and / or the use of the reactor as defined in the claims, and as described herein after in summary and in detail.

[0024] In one aspect, the invention relates to an improved process for the manufacture of a fluorinated organic compound in liquid phase in a reactor comprising at least one SiC block (“Silicon carbide block”) with specific dimensions of channels, and the inventions also relates to a new reactor comprising at least one SiC block with specific dimensions of channels (herein after “SiC block reactor”), for efficiently performing said liquid phase fluorination reactions of organic compounds with hydrogen fluoride (HF) as solvent and the fluorinating agent and in the presence of a fluorinating catalyst. Said specific SiC block reactor is a reactor comprising a so-called SiC block, which provides two types of tubes or channels respectively. One type of channels is vertically arranged and serves as channels (tubes or pipes) for the reaction mixture, these reaction channels having an internal diameter in the range from about 6 mm to about 25 mm, and the other type of channels is horizontally arranged.

[0025] A single SiC block contains more than one vertically arranged and more than one horizontally arranged channel. A single SiC block thus contains a multitude of vertical and a multitude of horizontal channels.

[0026] The vertical reaction tubes or channels, respectively, collectively are serving as reaction chamber for passing through the reaction mixture and thus are for the product manufacturing process.

[0027] The horizontal channels collectively are serving as heating channels for heating the reaction mixture, when performing the liquid phase fluorination of the present invention.

[0028] While the dimensions of the reaction channels (tubes) are defined as before, the diameter of heating channels is flexible and can be adapted, accordingly, e.g., to the need of a circulating heating liquid, respectively. The given channel (tube) dimensions are found optimal for processing viscous and / or solid particles containing reaction mixtures, and slurry reaction mixtures, while at the same time providing heat transfer and temperature control during the liquid phase fluorination.

[0029] In another aspect, the invention relates to a new use of at least one SiC block (“Silicon carbide block”) with specific dimensions of channels for performing a chemical reaction, preferably for performing a catalyzed fluorinating reaction with HF (hydrogen fluoride) as fluorinating reagent.

[0030] In another aspect, the invention relates to the use of at least one SiC block heat exchanger as chemical reactor (“SiC block reactor”) for fluorination reactions in liquid phase, with above given channel dimensions. In general, SiC blocks are known in the prior art, but hitherto they have not been used as a chemical reactor, neither in general nor in context of fluorination reactions.

[0031] For example, conventional Silicon carbide block heat exchangers (“SiC block heat exchanger”) are known and commercially available e.g. by companies like GAP Neumann in Germany (https: / / www.gab-neumann.com / Blockw%C3%A4rmetauscher-SiC) and Sunshine Graphite in China (http: / / www.sunshine-graphite.com / ), and such SiC block is illustrated in Fig. 1 herein. Such known and conventionally used silicon carbide block heat exchangers are designed for heating, cooling, evaporation, condensation and absorption of highly corrosive and / or oxidizing chemicals. This design, e.g., as is illustrated in Fig. 1 herein (showing the SiC block reactor part only, and without stainless steel housing), is the most versatile design for silicon carbide heat exchangers. The block is drilled axially and radially with parallel product and service channels. Heat is transferred via heat conduction through the material remaining between the rows of holes, which separate the media used from each other. Silicon carbide blocks are cylindrical; they are installed as a block column together with head and base pieces in a steel casing. It goes without saying, due to their different function as reaction and heating channels, that the vertical and horizontal channels are not connected with each other.

[0032] By the use of such a SiC block as a chemical reactor, especially with above given channel (tube) dimensions, the present invention provides a highly efficient process for performing liquid phase fluorination reactions of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst.

[0033] Therefore, in still another aspect, the invention is also directed to a SiC block chemical reactor (“SiC block reactor”), well suitable for fluorination reactions in liquid phase, the SiC block comprising two types of tubes or channels respectively as defined above.

[0034] The process according to the invention is a fluorination reaction of an organic precursor compound having at least one chlorine substituent and / or at least one double bond.

[0035] One main reaction in the SiC block reactor is chlorine / fluorine exchange on alkanes by HCI elimination optionally forming a double bond in the corresponding intermediate alkene followed by HF addition to the intermediate double bond. Therefore, the fluorinating reaction in SiC block reactor can advantageously also be applied to olefinic compounds with less reactive double bonds. An example for such an olefinic compound is PCE (perchloroethylene), which is very stable (therefore, formerly PCE has long been used for dry cleaning). A notably further advantage of using the SiC block reactor in fluorinating reaction is that the (adjustable) diameter size of the drilled reaction channels allows for high catalyst concentrations to be used. Thus, in SiC block reactor the fluorinating reaction can easily also performed with a reaction medium having a relatively high viscosity or that even is a slurry, because such a reaction medium can be pumped through the drilled reaction channels while heat transfer characteristics and flow / residence time characteristics mimic a reaction performance of a micro reactor. For sake of clarity, said advantages of using a SiC block reactor for a fluorinating reaction do not limit to a relatively high viscosity or slurry reaction medium, but a reaction medium with lower viscosity or even as solution can be applied to the SiC block reactor as well.

[0036] In another aspect, the invention relates to a novel organic precursor compound that can be fluorinated with the process according to the present invention.

[0037] In another aspect, the invention relates to a novel organic fluorinated compound that can be manufactured with the process according to the present invention.

[0038] DETAILED DESCRIPTION OF THE INVENTION

[0039] A preferred design of a SiC block chemical reactor (“SiC block reactor”) according to the present invention, well suitable for fluorination reactions in liquid phase, the SiC block comprising two types of tubes or channels respectively, is illustrated in Fig. 1 , simplified showing the vertically arranged channels for the reaction mixture.

[0040] Herein, in the SiC block chemical reactor one type of channels are upright-down going channels and are called “vertically arranged channels” or “vertical channels” (vertical arrangement related to top or bottom), and the other type of channels are from side to side going channels and are called “horizontally arranged channels” or “horizontal channels” (horizontal arrangement related to top or bottom). The vertical channels are for the product manufacturing process, the horizontal channels for heating (if used as reactor as in case of the present invention).

[0041] Thus, one type of channels is vertically arranged and serves as channels (tubes or pipes) for the reaction mixture, these reaction channels having independently from each other an internal diameter in the range from about 6 mm to about 25 mm, preferably from about 8 mm to about 16 mm.

[0042] More preferably all of the vertically arranged channels are having the same internal diameter in the range of from about 8 mm to about 16 mm.

[0043] Preferably one SiC block reactor contains at least three vertically arranged channels, more preferably from 3 to 50 vertically arranged channels with the given diameters.

[0044] The length of a single vertical channel in one SiC block is preferably from about 50 to 500 mm, more preferably from 200 to 300 mm, for example 250 mm.

[0045] The needed length of the reaction channels resulting in the right volume for a given residence time could also be obtained by the combination of two or more SiC block reactors in series. Turbulent reaction conditions are a preferred option but not a must for the chemistry.

[0046] Preferably two or more SiC blocks are combined in one SiC block reactor.

[0047] Preferably the SiC block chemical reactor used in the process according to the invention contains at least two, more preferably 5 to 15 SiC blocks, for example up to 12 SiC blocks. These blocks are preferably arranged for example on top of each other yielding in a combined (vertical) length of the reaction channels.

[0048] Preferably the combined length of the reaction channels in case of more than one SiC block is in the range from about 0.2 m to about 4 m, more preferably from about 1 m to 2 m; even more preferably in the range of from about 1 .3 m to 1 .70 m. The other type of channels is horizontally arranged.

[0049] Alternatively, the SiC block chemical reactor used in the process according to the invention contains only one SiC block. This alternative is especially suitable for production on a smaller scale. For industrial applications it is thus less preferred.

[0050] While the dimensions of the vertical reaction channels are defined as before, the diameter of the horizontal heating channels is flexible and can be adapted to the characteristics of the heating media. Normally and preferably the internal diameter of the heating channels is in the range of 5 to 15 mm, preferably 10 mm. The length of a single heating channel in one SiC block is preferably from about 60 to 500 mm, more preferably from about 300 to 400 mm, for example 350 mm.

[0051] The principle of the SiC block chemical reactor (“SiC block reactor”) according to the present invention and as shown here in simplified Fig. 2 can be described as follows. The horizontal drillings (not shown in Fig. 2) are for passing through a heating fluid, like oil, and the vertical drillings for the product stream, which starts from the bottom by letting the raw materials through the “starting material inlet” and ends at the “product mixture outlet”. The reaction channels (tubes or pipes) having an internal diameter in the range as described above, in exemplary designs may have an internal diameter of 16 mm, of 14 mm or 1 1 mm. If the flow of the reaction mixture (“product flow”) is low (e.g., a laminar flow), a narrower drilling diameter of the given range is chosen as compared to a turbulent feed (e.g., a turbulent flow of the reaction mixture or “a turbulent product flow”) where larger diameters of the given range are applicable. The reactor channel volume shown in simplified Fig. 2 is for example 6 liter and an example for large industrial scale. The needed reaction channel volume for needed residence time obviously also can be reached by combining several smaller reactors in series. At the outlet, namely “product mixture outlet” (flange of screw), there is a pressure valve keeping 15 bar absolute. The reactor given in simplified Fig. 2 and having a 6-liter volume of total reaction channel is suitable for industrial scale fluorination in liquid phase.

[0052] The SiC block chemical reactor (“SiC block reactor”) can be used as a single reactor, as well as a multitude of reactors, e.g., to adjust or scale-up the reaction volume for needed residence time. A multitude of SiC block reactors can be arranged in array system. The SiC block chemical reactor (“SiC block reactor”) can also be used as a multitude of reactors in series, e.g., to adjust the residence time of the reaction mixture. A multitude of SiC block reactors combined in series in addition can also be arranged in array system.

[0053] In a further aspect, the invention relates to an improved process for the manufacture of fluorinated organic compounds in liquid phase in a reactor comprising at least one SiC block (“Silicon carbide block”) with herein specified dimensions of channels, for efficiently performing said liquid phase fluorination reactions of organic compounds with hydrogen fluoride (HF) as the fluorinating agent and in the presence of a fluorinating catalyst.

[0054] Preferably a proviso of the present invention is that the organic compound is not one of 3, 3-dichoro-1 ,1 ,1 -trichloropropane (240fa), 3, 3-difluoro-1 , 1 ,1 -trifluoropropane (245fa) and / or that the targeted fluorinated organic compound is not 1 ,1 ,1 ,3-tetrafluoropropene (1234ze).

[0055] In particular, it is also an aspect of the present invention to provide said highly efficient liquid phase fluorination process for the manufacture of fluorinated organic compounds, for example which are selected from the group consisting of partially or fully fluorinated C1-C10 alkanes and partially or fully fluorinated C1-C10 alkenes, wherein these C1-C10 alkanes and C1-C10 alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

[0056] The NO2 groups are preferably substituents on the aromatic group. In this case these C1- C10 alkanes and C1-C10 alkenes carry aromatic groups and NO2 groups in the molecule, whereas the NO2 groups are substituents on the aromatic group.

[0057] The fluorinating process to obtain the fluorinated target compounds according to the present invention may comprise chlorine-fluorine exchange and / or hydrogen-fluorine exchange and / or the addition of fluorine and hydrogen to a C=C-double bond.

[0058] Thus, the precursor for the process according to the invention is preferably an organic precursor compound that is selected from the group consisting of chlorinated and optionally partially fluorinated C1-C10 alkanes and optionally chlorinated and optionally partially fluorinated C1-C10 alkenes, wherein the alkanes and alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

[0059] Thus, the organic precursor compound for the process according to the invention is preferably an organic precursor compound that is selected from the group consisting of C1- C10 alkanes and C1-C10 alkenes, wherein the alkanes are chlorinated and optionally partially fluorinated and wherein the alkenes are optionally chlorinated and optionally partially fluorinated, wherein these C1-C10 alkanes and C1-C10 alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

[0060] The carbon atoms of the aromatic groups are not part of the number of carbon atoms in the defined C1-C10 alkane or alkene, respectively. These numbers from 1 to 10 relate to the alkane or alkene part only.

[0061] Preferably the aromatic group is a benzene ring.

[0062] The organic precursor compound is thus preferably either a chlorinated alkane or a chlorinated and partially fluorinated alkane or an alkene or a chlorinated alkene or a partially fluorinated alkene or a partially fluorinated and chlorinated alkene.

[0063] Preferably the organic precursor compound is selected from the group consisting of perchloroethylene (PCE, CCl2=CCl2), trichloroethylene (TRI, CHCI=CCl2), CCIF2CHCI2 (HCFC-122), 1 ,1 ,1 ,2,2-Pentachloroethane (HCC 120), dichloromethane (CH2CI2), chloroform (CHCI3), 1 ,1 ,1 ,3,3-pentachloropropane (HCC-240fa), 1 ,1 ,2,3- tetrachloropropene (HCC-1230xa), 2,3,3,3-tetrachloropropene (HCC-1230xf), 3,3,3- trichloropropene (HCC-1240zf), 1 ,1 ,1 ,2,3-pentachloropropane (HCC 240db), 1 ,1 ,3- trichloropropene (HCC 1240za), 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb), 1 , 1 ,1 , 3,3- pentachlorobutane (HCC 360), a,a,a-trichlorotoluene (Benzotrichloride), 1- perchloroisopropyl 3-trichloromethyl benzene, 1 -perchloroisopropyl 3-trichloromethyl 4- nitro benzene and heptachloro isopropyl m-trichloromethyl benzene (HCiPCM).

[0064] Surprisingly also novel organic precursor compounds for the inventive process were found as well as novel fluorinated compounds could be manufactured via the process according to the invention.

[0065] The novel organic precursor compounds are shown in the formulas (I) and (II):

[0066] In another aspect, the invention relates to a novel organic precursor compound that can be or is fluorinated in the process according to the invention and is selected from the group of compounds according to the following formula (I) and (II) as shown above.

[0067] In another aspect, the invention relates to a novel organic compound according to formula (lb), that is the downstream product of formula (I):

[0068] The fluorinated compounds that could be manufactured via the process according to the invention are shown in formula (III) and in formula (IV):

[0069] The compound according to formula (III) is a novel compound. The compound according to formula (IV) is a potential downstream product of the compound according to formula (III).

[0070] The compound according to formula (III) has a high relevance for the chemical industry as it can be used to produce the corresponding aniline, namely the compound according to formula (IV).

[0071] The reaction from compound (III) to compound (IV) is not part of the invention as many routes to nitrobenzenes and anilines out of corresponding benzene precursors are very well known and applied, see for example PATAI's Chemistry of Functional Groups in 2009 by John Wiley & Sons, Ltd., DOI: 10.1002 / 9780470682531 ,pat0391). But the most convenient and cheapest reaction is according to the Bechamp-Reaction with Fe / HCI but preferred only for large scale due to handling and ferric oxide side product reasons.

[0072] Preferably the compound according to formula (IV) is manufactured by the process according to the present invention.

[0073] Preferably the targeted fluorinated organic compound is selected from the group consisting of (HCFC-122), (HCFC-123), (HCFC-123a), 1 -perfluoroisopropyl 3-trifluoromethyl benzene and 1-perfluoroisopropyl-3-trifluoromethyl-4-nitro benzene.

[0074] Also, (HFC-32), 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa) is a favorable targeted fluorinated organic compound.

[0075] Throughout the whole present disclosure including the figures compounds such as HCFC-122 are also shortly named “122”. Also, “(HCFC-122)” stands for HCFC-122. These alternative spellings apply analogously to all other compounds with such known numbered names in the art.

[0076] It needs to be mentioned that for chlorine-fluorine exchange reactions, for multi carbon compounds a catalyst (especially Sb based) has two functions: a) accelerating HCI-elimination out of a chlorinated and even partial fluorinated compound b) promoting the nucleophilic fluorine / chlorine exchange.

[0077] Especially in the case of a multi carbon compound with at least one chlorine atom in exposition to a hydrogen atom the reaction with HF will lead to the elimination of HCI and the addition of HF.

[0078] The fluorine-chlorine exchange is either nucleophilic or moving mechanistically alternatively and in parallel over an addition elimination mechanism creating olefinic intermediate compounds.

[0079] The fluorinating catalyst used in the present invention is preferably a metal-based Lewis acid catalyst.

[0080] As fluorination catalyst, TiCk, SbCIs, SnCk, TaCIs, SbCh, or AlCh, (including their partial or fully fluorinated derivatives) alone or in combination are mentioned already in patent publication US8648221 B2.

[0081] It now was found that all catalysts in the procedure as described in patent publication US8648221 B2 got deactivated in that liquid phase process after very short time (continuous) or limited cycles (2-3 in batch process). This is not practicable in industrial scale. That is why as of today without this invention, e.g. the synthesis of fluorinated compounds in industrial scale is done in gas phase with high energy consumption. The deactivation might be due to formation of mainly fully fluorinated positions at the metal which means TiF4, SnF4, TaFs, SbFs, or AIF3 which are much lower or even not soluble in anhydrous HF (hydrogen fluoride), and therefore these fully fluorinated materials concentrate as precipitated product at lower phases, and besides low fluorination activity, this enrichment in lower phases even as precipitates will block pumps, valves and stirrers and will lead to enhanced abrasion of equipment which can lead to dangerous leakages and shut downs.

[0082] A potential theoretical solution for this problem might be the application of a gas phase process like also based on Sb as described in Journal of Molecular Catalysis A 233 (2005) 99-104, but obtained yields are too low for industrial application and as in a gas phase process high temperatures are needed (up to 350°C are described). High energy consumption would be another environmental drawback.

[0083] The present invention relates to an improved fluorinating process with HF (hydrogen fluoride) using a fluorinating catalyst, preferably a metal-based Lewis acid catalyst.

[0084] In Lewis acid catalysis of the fluorination reaction of the present invention, a metalbased Lewis acid acts as an electron pair acceptor to increase the reactivity of a substrate. Common Lewis acid catalysts can be used that are based on main group metals such as aluminum, boron, silicon, and tin, as well as many early (titanium, zirconium) and late (iron, copper, zinc) d-block metals. The complexation has partial charge-transfer character and makes the lone-pair donor effectively more electronegative, activating the substrate toward nucleophilic attack, heterolytic bond cleavage, or cycloaddition with 1 ,3-dienes and 1 ,3-dipoles. Today, metal-based Lewis acid catalyst based on Sb (antimony) are very common and in use in the field of fluorinating compounds.

[0085] The counter-ion in the metal-based Lewis acid catalyst is chlorine or fluorine, or a combination of chlorine or fluorine. Hence, the metal-based Lewis acid catalyst used in the liquid phase fluorination process of the present invention can be a metal-chloride Lewis acid catalyst, a metal-fluoride Lewis acid catalyst, or a combination thereof.

[0086] Examples of metal-chloride Lewis acid catalysts are TiCk and SnCk, even FeCh, NiCh, TaCIs, and AICI3, or SbCh and SbCIs or a mixture of SbCh / SbCIs. During fluorination the metal-chloride Lewis acid catalysts are converted to the fluorides or to mixed chlorides / fluorides.

[0087] However, fully fluorinated metal-chloride Lewis acid catalysts are avoided (except the catalyst is a mixed Sb oxidation state, e.g., Sb(l I l) / Sb(V)) because these may cause deactivation due to formation of mainly fully fluorinated positions at the metal which means, for example, TiF4, SnF4, TaFs, SbFs, or AIF3, which are much lower or even not soluble in anhydrous HF (hydrogen fluoride), and therefore these fully fluorinated catalyst materials concentrate as precipitate in lower phases and may lead to reactor system blockages.

[0088] The catalyst in the fluorination is more preferably an Sb (antimony) based Lewis acid catalyst, and in addition provides applicability of the liquid phase fluorinating process in industrial scale.

[0089] In the liquid phase fluorinating process step of the present invention any metal-based Lewis acid catalyst based on other metal than Sb (antimony) can be used. In principle, in the liquid phase fluorination of the present invention, instead of Sb (antimony) catalyst, also other Lewis acids like TiHak, SnHak etc. can be used. The term “Hal” stands for Halide.

[0090] The metal-based Lewis acid catalyst is preferably selected from the group consisting of TiCk, SnCk, FeCh, NiCh, TaCIs, AICI3, SbCh, SbCIs, a mixture of SbCh / SbCIs, the partially fluorinated versions of each of the chlorides and a combination of any of the aforementioned chlorides and partially fluorinated versions thereof.

[0091] However, using Sb (antimony) catalyst in the liquid phase fluorination reaction of the invention is preferred.

[0092] The metal-based Lewis acid catalyst based on Sb (antimony) can exist in two different oxidation states, i.e., the Sb(lll) oxidation state and the Sb(V) oxidation state or as a mixed Sb(l ll) / Sb(V) oxidation state; the Sb(lll) oxidation state Lewis acid catalyst, the mixed Sb(l ll) / Sb(V) oxidation state Lewis acid catalyst, and as well metal-based Lewis acid catalysts based on other metal (e.g., Ti, Sn, Fe, Ni) than Sb are weaker than the stronger Sb(V) oxidation state Lewis acid catalyst.

[0093] The liquid phase fluorination reaction is a pure nucleophilic CI / F-exchange when using highly fluorinated Sb(V) catalyst and excess HF (giving H2F+SbFe')-

[0094] In the liquid phase fluorinating process of the present invention, an Sb (antimony) based Lewis acid catalyst can be employed, wherein in the fluorinating process the Sb (antimony) based Lewis acid catalyst is in oxidation state mixture (Sb(V) / Sb(l II) or wherein the Sb (antimony) based Lewis acid catalyst is in oxidation state Sb(V). Thus, in the fluorinating process of the invention the Sb (antimony) based Lewis acid catalyst can be used in different oxidation state in the liquid phase fluorination reaction, which is very much advantageous to steer reactivity, and in addition provides applicability in industrial scale.

[0095] Therefore, the catalyst activity level necessary for an industrial scale process can be easily maintained at the required level, allows avoiding catalyst degradation, and is highly efficiently performable and even scalable to industrial scale.

[0096] The fluorination properties can for example be weakened by balancing a lower catalyst concentration, higher Sb(lll) content and a shorter residence time as well as the reaction temperature. This must not be too high, as Sb(V) for example thermally splits off halogens at least at 100 °C (and without a reaction partner) and produces Sb(lll). Preferably in the liquid phase fluorinating process of the present invention as metal-based Lewis acid catalyst an Sb (antimony) catalyst is employed, wherein the oxidation state Sb(V) is preferred.

[0097] In the fluorinating reaction the metal-based Lewis acid catalyst is preferably SbCIs (e.g., Sb (antimony) Lewis acid catalyst with oxidation state Sb(V).

[0098] A more preferred metal-based Lewis acid catalyst is a pre-fluorinated Sb (antimony) based Lewis acid catalyst SbFs-nCIn, in which n is an integer from 1 to 4.

[0099] The reaction pressure the process steps of the present invention is set to a pressure in a range known in the technical art to be applied in fluorinating reactions

[0100] The reaction temperature in the liquid phase and metal-based Lewis acid catalyzed fluorinating reaction of the compounds with, preferably anhydrous, HF (hydrogen fluoride) as fluorinating agent of the present invention is controlled to be less than 110°C (maximum reaction temperature), and is starting (minimum reaction temperature) from about ambient temperature (e.g., 20°C to 25°C, or e.g. 20°C, or e.g. 25°C). For example, the fluorination according to the present invention can be performed at (“soft”) reaction temperatures, which is in the range from about ambient temperature (e.g., 20°C to 25°C, or e.g. 20°C, or e.g. 25°C) up to about 100°C; or in the range from about ambient temperature (e.g., 25°C) up to about 80°C. The reaction temperature is correlated with the residence time in the process. For example, at temperatures of about ambient temperature (e.g., 25°C) the fluorinating reaction takes a longer time period (e.g., up to about 12 h; e.g., if fluorination overnight is desired, e.g. for energy-cost saving) with the drawback that advantageous turbulent conditions cannot be reached. For example, at temperatures of about 90°C the fluorinating reaction takes a short time period (e.g., less than about 1 h, often residence time is only several minutes; e.g., if production time saving is desired). Accordingly, in the process of the invention a (“higher”) reaction temperature in the range from about 25°C up to about 1 10 °C is applied; preferably, the (“higher”) reaction temperature is in the range from about greater than 80 °C up to about 110 °C, more preferably in the range from about 85 °C up to about 110 °C, from about 85 °C up to about 105 °C, or from about 87 °C up to about 103 °C.

[0101] Furthermore, it shall be considered that thermal deactivation of catalyst component Sb(V) was found to occur significantly at temperatures higher than 110°C. At these temperatures higher than 110 °C catalyst activities needed for industrial scale production cannot be kept any more, due to said catalyst degradation.

[0102] Avoiding corrosion by selecting suitable equipment and suitable material of construction is another aspect of the present invention linked to Sb Lewis acid catalysts to avoid deactivation of Sb(V) to Sb(lll); and also and even more important in the nucleophilic Cl / F- exchange. This aspect to avoid corrosion is also solved by the process and proposed reactor equipment for performing the present invention. As material of construction for the reactor housing 1 .4571 high grade stainless steel is fine for most metal-based Lewis acid catalysts, except for some, e.g. based on Sb (antimony) and Bi (Bismuth). As Sb in oxidation state V is very corrosive also against all Hastelloy steels the reactor is preferably coated with PTFE (polytetrafluoroethylene) and due to low heat transfer of plastic coatings, the heat is introduced over a loop having heat exchanger constructed out of SiC if Lewis acid catalyst with oxidation state Sb(V) is used.

[0103] Due to the low pressure, some HF is joining the gaseous HCI stream leaving the boilers on each of the two reactor columns. This gaseous HCI stream containing some HF is collected and can be subjected to a high pressure distillation at 15 bar in another column made out of 1 .4571 high grade stainless steel to separate off HCI in pure form at the top boiler with a transition (reflux) temperature of -20°C in a purity which fits for commercialization.

[0104] The problems to be solved by performing the reactions of the present invention in a reactor with tubes and / or channels is a) to avoid blockage by some precipitated particles which always can happen when using fluorinated metal Lewis acid catalysts, and especially in antimony based systems where higher catalyst concentrations and higher concentration of Sb in oxidation state III increases the probability of precipitates.

[0105] Last but not least, corrosion is another very big challenge with Sb-based Lewis acid catalysts, and here especially in the oxidation state Sb(V) in presence of excess HF, which forms a so called superacid (H2F+SbHale')- The technical solution for material of construction is SiC. But as SiC tubes and / or SiC channels have limited pressure resistance (e.g., as of today known in the state of the art up to 6 bars absol. only) the reaction chemistry in SiC tubes and / or SiC channels manufactured for heat exchangers does also not fit at all due to the higher needed pressures.

[0106] Fortunately, now it was found by the invention that if so-called SiC blocks, e.g., from company GAB Neumann GmbH, which are usually only used so far as heat exchanger, are used in the reactions of the present invention in a kind of SiC tube and / or SiC channel reactor then pressures up to 20 bar are technically feasible. The dimensions of the SiC block and the reaction and heating channels, preferably are adapted to the fluorinating reaction needs, as described in context of the present invention.

[0107] In the said at least one SiC block, the channels are drilled into the SiC block so that the final SiC tubes and / or SiC channels can be used as pressure resistant reactor as in case of the present invention.

[0108] In the said at least one SiC block of the invention, as described in the claims and herein above, there are two types of tubes or channels, respectively, one type is vertically arranged, the other type is horizontally arranged. The vertical channels are for the product manufacturing process, the horizontal channels for heating (if used as reactor as in case of the present invention) or for cooling (if used as heat exchanger).

[0109] In the SiC block process of the present invention, the HF tank is used in combination also as storage tank (pressure) for the catalyst; optionally a separate tank can be installed only keeping the catalyst, but a solution of catalyst in HF is advantageous to keep all catalyst dissolved in liquid phase.

[0110] Sb is preferably used as metal in the catalyst for fluorination reaction of the invention.

[0111] In some reactions performed in a SiC block reactor at 15 bar, the catalyst mixture of 50% Sb(lll) and 50% Sb(V) is used. Said catalyst mixture on the one side is active enough to consume any intermediate olefins but is also deactivated enough to stop over reaction as long as mainly the HCI-elimination / HF-addition reaction proceeds.

[0112] Some reactions in the SiC block reactor are performed at 12 bar, e.g., in a pure nucleophilic CI / F-exchange using highly fluorinated Sb(V) with excess HF (giving H2F+SbFe') which is reacted with the compound(s) CsCIs-nFn.

[0113] The process according to the invention also comprises that the reaction mixture is continuously withdrawn from SiC block chemical reactor.

[0114] The process comprises optionally isolating and / or purifying the targeted fluorinated organic compound.

[0115] Final distillation in a pressure column may be applied to give pure target fluorinated compound. The final distillation can be skipped if in the settler (phase separator) the temperature is kept at 0°C or lower so that all or at least most of the formed HCI acid has moved to the HF / catalyst phase (upper phase), and the target fluorinated compound is obtained as lower phase, which contains only traces of HCI and HF acid and which HCI and HF traces are acceptable for subsequent reaction step of the elimination of HF.

[0116] The HF (hydrogen fluoride) used in the reaction of the present invention is preferably anhydrous (if not expressively stated otherwise), i.e., the terms “HF” or “hydrogen fluoride” each mean “anhydrous HF” or “anhydrous hydrogen fluoride” (if not expressively stated otherwise). A substance is “anhydrous” if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is most preferred and important that water-free reagents and techniques are used. In practice, however, it is very difficult to achieve perfect dryness; anhydrous substances will gradually absorb water (humidity) from the atmosphere so they must be stored carefully. The term “waterfree” is used synonymously to the term “anhydrous”.

[0117] “Anhydrous hydrogen fluoride” (“anhydrous HF”) can be prepared by converting the mineral fluorspar (CaF2) typically in a rotary kiln with H2SO4 to HF and CaSC . As H2SO4 is a drying agent anyway, the produced anhydrous hydrogen fluoride might have only traces of moisture and only resulting from external contamination, e.g., occurring in storage tank, in connection / disconnection of pipes, and from moisture traces resulting from inert gas(es) and / or solvent(s) potentially used in the processing and / or application of anhydrous hydrogen fluoride.

[0118] In the process of the present invention traces of water (H2O) are tolerated of even up to about 100 ppm. Such traces of water can even contribute to an advantageous increase in the conductivity of the hydrogen fluoride (HF) used in the process. However, such traces of water must be counter-balanced against the disadvantage of too high traces water (H2O) in the process, i.e., potential corrosion and possibly increased consumption of reaction material(s). Therefore, the term “anhydrous” “water-free” or “essentially water-free”, or similar terms, in the context of the present invention denote a water content (traces) of at maximum about 100 ppm (< 100 ppm), preferably of at maximum about 50 ppm (< 50 ppm), more preferably of at maximum about 40 ppm (< 40 ppm) or 30 ppm (< 30 ppm), and even more preferably of at maximum about 20 ppm (< 20 ppm).

[0119] Accordingly, the term “anhydrous hydrogen fluoride” (“anhydrous HF”) means an essentially water-free hydrogen fluoride with traces of water of at maximum about 100 ppm (< 100 ± 5 ppm), preferably of of at maximum about 50 ppm (< 50 ± 5 ppm), more preferably of at maximum about 40 ppm (< 40 ± 5 ppm) or 30 ppm (< 30 ± 5 ppm), and even more preferably of at maximum about 20 ppm (< 20 ± 5 ppm). In particular, the term “anhydrous hydrogen fluoride” (“anhydrous HF”) “essentially water-free hydrogen fluoride” (or similar terms, e.g., “anhydrous HF”, “water-free HF” or “water-free hydrogen fluoride”) thus preferably means “anhydrous hydrogen fluoride for industrial use”, and especially that the hydrogen fluoride (HF) typically contains at maximum approximately 20 ppm of water (20 ± 1 ppm), preferably at maximum approximately 15 ppm of water (15 ± 1 ppm), and more preferably at maximum approximately 10 ppm (10 ± 1 ppm), of water traces.

[0120] DRAWINGS

[0121] Figure 1 :

[0122] Illustration of the SiC part of so-called SiC blocks, i.e., without exterior housing which usually is high grade stainless steel (not shown). Those blocks can be found in general under the source: https: / / www.aab-neumann.com / SiC-block-heat-exchangers.

[0123] Fig. 1 shows also the schematic design of said SiC block as chemical reactor, showing raw material stream in (starting reaction mixture) into the SiC block from the bottom part, passing the reaction mixture in vertical direction (not shown) through the SiC block reaction channels (tubes), and collecting from the SiC block reaction channels (tubes) the reaction product stream out at top part of the SiC block. In horizontal direction the heating medium stream (e.g., oil or steam) into and out of the SiC block heating channels is schematically illustrated.

[0124] Figure 2:

[0125] Scheme of a SiC-block chemical reactor design according to the invention (horizontal drillings or heating channels are not shown), showing a SiC-block reactor module with vertically drilled reaction channels (tubes or pipes respectively) with an exemplary length of 1.5 m. Further exemplary parameters are: diameter of reaction channels = 14 mm, pressure resistance = 20 bar, operating pressure = 15 bar, and total reactor volume comprised of interior spaces of all reaction channels = 6 liter. The bottom and top part of the SiC-block reactor module each independently from each other, either being of SiC material or PTFE coated material (PTFE = polytetrafluoroethylene), Fig. 2 shows also an inlet, e.g., as a connection flange or screw connection, for raw materials stream (starting reaction mixture) into the SiC block at bottom part, and an outlet, e.g., as a connection flange or screw connection, for the reaction product stream at top part of the SiC block, wherein said inlet at the bottom and said outlet at the top, independently from each other, can be arranged at any location of the perimeter of the SiC-block reactor.

[0126] Figure 3:

[0127] Reaction scheme of the fluorination process according to the invention by using an inventive SiC-block reactor as illustrated in Fig. 2, for the fluorination of compound HCFC-122 in the presence of an Sb-catalyst to obtain compounds HCFC-123 (main product) and HCFC-123a (minor to zero) in admixture.

[0128] Figure 4

[0129] Reaction scheme of the fluorination process according to the invention by using an inventive SiC-block reactor as illustrated in Fig. 2, for the fluorination of Perchloroethylene (PCE) to CCIF2CHCI2 (HCFC-122).

[0130] Figure 5:

[0131] Reaction scheme of the fluorination process according to the invention by using an inventive SiC-block reactor as illustrated in Fig. 2, for the fluorination of compound dichloromethane (CH2CI2) in the presence of a Sb-catalyst to obtain compound HFC-32 (difluoromethane).

[0132] Particular Aspects of the Invention:

[0133] In a first aspect the invention pertains to a process for the manufacture of a fluorinated organic compound, wherein the process comprises a fluorination reaction of an organic precursor compound having at least one chlorine substituent and / or at least one double bond, and said organic precursor compound is reacted in liguid phase in HF (hydrogen fluoride), preferably in liguid phase in anhydrous HF (hydrogen fluoride), serving as solvent and fluorinating agent in the presence of a fluorinating catalyst, preferably a metal-based Lewis acid catalyst, and wherein the fluorination reaction is performed in liguid phase in a SiC block chemical reactor comprising at least one SiC block which provides two types of channels, wherein one type of channel is vertically arranged having an internal diameter from about 6 mm to about 25 mm, and this type of channel is serving as reaction chamber for passing through the reaction mixture, and the other type of channel is horizontally arranged for passing through a heating medium for heating the reaction mixture to a reaction temperature during the liguid phase fluorination, and wherein the reaction mixture is withdrawn from SiC block chemical reactor, and wherein the process comprises optionally isolating and / or purifying the targeted fluorinated organic compound. In a second aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to the first aspect of the invention, wherein the vertical channels independently from each other have an internal diameter in the range of from about 8 mm to about 16 mm, and more preferably all of them have the same internal diameter in the range of from about 8 mm to about 16 mm.

[0134] In a third aspect the invention pertains to a process for the the manufacture of a fluorinated organic compound according to any of the previous aspects, wherein the length of a single vertical channel in one SiC block is preferably from about 50 to 500 mm, more preferably from 200 to 300 mm.

[0135] In a fourth aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any of the previous aspects, with proviso that the organic precursor compound is not one of 3,3-dichoro-1 ,1 ,1-trichloropropane (240fa), 3,3-difluoro- 1 ,1 ,1 -trifluoropropane (245fa) and / or with the proviso that the targeted fluorinated organic compound is not 1 ,1 ,1 ,3-tetrafluoropropene (1234ze).

[0136] In a fifth aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any one of the previous aspects, wherein the organic precursor compound is selected from the group consisting of chlorinated and optionally partially fluorinated C1-C10 alkanes and optionally chlorinated and optionally partially fluorinated C1-C10 alkenes, wherein the alkanes and alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

[0137] In a sixth aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any of the previous aspects, wherein the organic precursor compound is selected from the group consisting of perchloroethylene (PCE, CCl2=CCl2), trichloroethylene (TRI, CHCI=CCI2), CCIF2CHCI2 (HCFC-122), 1 ,1 , 1 ,2, 2- Pentachloroethane (HCC 120), dichloromethane (CH2CI2), chloroform (CHCI3), 1 , 1 ,1 , 3,3- pentachloropropane (HCC-240fa), 1 ,1 ,2,3-tetrachloropropene (HCC-1230xa), 2, 3,3,3- tetrachloropropene (HCC-1230xf), 3,3,3-trichloropropene (HCC-1240zf), 1 , 1 ,1 , 2,3- pentachloropropane (HCC 240db), 1 ,1 ,3-trichloropropene (HCC 1240za), 1 , 1 ,1 ,3- tetrachloropropane (HCC-250fb), 1 ,1 ,1 ,3,3-pentachlorobutane (HCC 360), a,a,a- trichlorotoluene (Benzotrichloride), 1 -perchloroisopropyl 3-trichloromethyl benzene, 1- perchloroisopropyl 3-trichloromethyl 4-nitro benzene and heptachloro isopropyl m- trichloromethyl benzene (HCiPCM).

[0138] In a seventh aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any of the previous aspects, wherein the targeted fluorinated organic compound is selected from the group consisting of of partially or fully fluorinated C1-C10 alkanes and partially or fully fluorinated C1-C10 alkenes, wherein these C1-C10 alkanes and C1-C10 alkenes can further carry aromatic groups and / or NO2 groups in the molecule. In an eighth aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any of the previous aspects, wherein the targeted fluorinated organic compound is selected from the group consisting of (HCFC-122), (HCFC-123), (HCFC-123a), (HFC-32), 1 -perfluoroisopropyl 3-trifluoromethyl benzene and 1 -perfluoroisopropyl-3-trifluoromethyl-4-nitro benzene.

[0139] In another aspect the invention pertains to a process for the manufacture of a compound as defined herein above according to any of the previous aspects, comprising a metal-based Lewis acid catalyzed fluorinating reaction with anhydrous HF (hydrogen fluoride) as fluorinating agent, wherein in the fluorinating reaction the metal-based Lewis acid catalyst is selected from the group consisting of TiCk, SnCk, FeCh, NiCh, TaCIs, AlCh, SbCh, SbCIs, a mixture of SbCh / SbCIs, the partially fluorinated versions of each of the chlorides and a combination of any of the aforementioned chlorides and partially fluorinated versions thereof.

[0140] In still another aspect the invention pertains to a process for the manufacture of a compound as defined herein above, comprising a metal-based Lewis acid catalyzed fluorinating reaction with anhydrous HF (hydrogen fluoride) as fluorinating agent, wherein in the fluorinating reaction the metal-based Lewis acid catalyst is SbCIs (e.g., Sb (antimony) Lewis acid catalyst with oxidation state Sb(V) or the pre-fluorinated version thereof SbFs- nCIn.

[0141] A preferred metal-based Lewis acid catalyst is a pre-fluorinated Sb (antimony) based Lewis acid catalyst SbFs-nCIn.

[0142] In another aspect the invention pertains to a process for the manufacture of a fluorinated organic compound according to any of the previous aspects, wherein the metal-based Lewis acid catalyst contains Sb as metal, wherein Sb(V) is preferred.

[0143] In another aspect the invention pertains to a novel organic precursor compound that can be fluorinated in the process according to any of the previous aspects and that is selected from the group of compounds according to the following formula (I) and (II): In another aspect the invention pertains to a compound according to formula (III): whereas the compound according to formula (III) is preferably manufactured by a process according to any of above listed aspects.

[0144] In another aspect the invention pertains to the use of a SiC block as a reactor for performing a chemical reaction, preferably for performing a catalyzed fluorinating reaction with HF (hydrogen fluoride) as fluorinating agent, wherein the SiC block chemical reactor is comprising at least one SiC block which provides two types of channels, wherein one channel type is vertically arranged and has an internal diameter from about 6 mm to about 25 mm, and this type is serving as reaction chamber for passing through the reaction mixture, and the other channel type is horizontally arranged and serves as heating channels for passing through a heating medium for heating the reaction mixture to a reaction temperature.

[0145] In another aspect the invention pertains to a SiC block chemical reactor comprising at least one SiC block which provides two types of channels, wherein one type of channel is vertically arranged having an internal diameter from about 6 mm to about 25 mm, and this type of channel is serving as reaction chamber for passing through the reaction mixture, and the other type of channel is horizontally arranged for passing through a heating medium for heating the reaction mixture to a reaction temperature during the liquid phase fluorination, and wherein the reaction mixture is withdrawn from SiC block chemical reactor, and wherein the process comprises optionally isolating and / or purifying the targeted fluorinated organic compound.

[0146] In the SiC block according to the use and the aspect pertaining to the SiC block chemical reactor the vertical channels preferably have independently from each other an internal diameter in the range of from about 8 mm to about 16 mm, and more preferably all of them have the same internal diameter in the range of from about 8 mm to about 16 mm.

[0147] In the SiC block according to the use and the aspect pertaining to the SiC block chemical reactor the length of a single vertical channel in one SiC block is preferably from about 50 to 500 mm, more preferably from 200 to 300 mm.

[0148] Particular Example Fluorinations of the Invention: As commercial SiC tubes as of today resist only to pressures up to 5 bar, but a chlorine / fluorine exchange reaction like for HCFC-122 and HCFC-123 in liquid phase happen at reactor pressures of around 15 bar, the pressure resistance of a SiC block reactor with channels drilled into a SiC block provide the needed pressure resistance up to 40 bar. This type of reactors are hand designed e.g. by companies like GAP Neumann in Germany (https: / / www.gab-neumann.com / ) and Sunshine Graphite in China (http: / / www.sunshine-graphite.com / ). The block reactor is housed into a stainless steel mantle with flange connectors also out of SiC. The inlet and outlets are PTFE (or SiC) coated. While in US10633310 the Sb concentration is limited to 10 mol % and the reaction is permanently interrupted by clogging, with the use of a SiC block reactor according to the present invention the Sb catalyst can be concentrated up to 80 % and operated at soft temperatures between 70 and 110°C, whereas 90 °C was experienced as most convenient temperature providing high conversion, high selectivity and quite short residence time compared to a CSTR. In US10633310 the residence time is given 5 minutes and with the diluted 10% Sb catalyst (such dilution needed to avoid clogging), besides that, turbulent reaction conditions cannot be reached.

[0149] In the present invention, the channel drilling diameter is preferably from about 8 to about 16 mm. The length of the reactor is chosen that the residence time is around or smaller than 10 minutes depending on the reactivity of the substrate, in most cases the residence time is 5 minutes and the Sb catalyst slurry concentration can be up to 80 % (viscosity gets quite high), but a concentration of around 40 to 60 mass % is preferred related calculated as SbFs.

[0150] It needs to be mentioned that for chlorine-fluorine exchange reactions, for all multi carbon compounds a catalyst (especially Sb based) has two functions: a) accelerating HCI-elimination out of a chlorinated and even partial fluorinated compound; b) nucleophilic fluorine / chlorine exchange.

[0151] Subsequently, some examples of fluorination reactions in context of the invention are given as further illustration: excess HF CI C=CCI - ► CF CI-CHCI +2 HCI excess HF excess HF excess HF

[0152] (9) (

[0153] In all formulas SbCInFs-n in the present disclosure the index “n” represents an integer from 1 to 4.

[0154] In case of PCE (an olefin) as starting material, catalyst mainly enables the HCI elimination step. For fluorinations of substrates with functional groups (e.g. Keto groups), the catalyst can be applied in sharply diluted solutions as reaction accelerator, as in higher concentrations the catalyst might also act as Friedel Crafts catalyst.

[0155] EXAMPLES

[0156] The following examples illustrate the SiC block chemical reactor of the present invention, and its use for fluorination reactions in the presence of a Lewis acid catalyst, and also illustrate the fluorination process according to the invention by the manufacture of representative fluorinated organic compounds.

[0157] Example 1 :

[0158] Principle of a SiC apparatus: The SiC block chemical reactor of the present invention. Reference is made to Figure 1 , which describes the SiC part of so-called SiC blocks, i.e., without exterior housing which usually is high grade stainless steel (not shown),

[0159] Fig. 1 shows also the schematic design of said SiC block as chemical reactor, showing raw material stream in (starting reaction mixture) into the SiC block from the bottom part, passing the reaction mixture in vertical direction (not shown) through the SiC block reaction channels (tubes), and collecting from the SiC block reaction channels (tubes) the reaction product stream out at top part of the SiC block. In horizontal direction the heating medium stream (e.g., oil or steam) into and out of the SiC block heating channels is schematically illustrated.

[0160] The principle of the SiC block chemical reactor (“SiC block reactor”) according to the present invention and used herein in the examples can be described as follows and as shown schematically in Figure 2.

[0161] Fig. 2 shows the scheme of a SiC-block chemical reactor design according to the invention (horizontal drillings or heating channels are not shown), showing a SiC-block reactor module with vertically drilled reaction channels (tubes or pipes respectively) with an exemplary length of 1.5 m. Further exemplary parameters are: diameter of reaction channels = 14 mm, pressure resistance = 20 bar, operating pressure = 15 bar, and total reactor volume comprised of interior spaces of all reaction channels = 6 liter. The bottom and top part of the SiC-block reactor module each independently from each other, either being of SiC material or PTFE coated material (PTFE = polytetrafluoroethylene), Fig. 2 shows also an inlet, e.g., as a connection flange or screw connection, for raw materials stream (starting reaction mixture) into the SiC block at bottom part, and an outlet, e.g., as a connection flange or screw connection, for the reaction product stream at top part of the SiC block, wherein said inlet at the bottom and said outlet at the top, independently from each other, can be arranged at any location of the perimeter of the SiC-block reactor.

[0162] The horizontal drillings (not shown in Fig. 2) are for passing through a heating fluid, for example oil, the vertical drillings for the product stream, i.e., the reaction channels (tubes) having an internal diameter in the range of from about 6 mm to about 25 mm, preferably from about 8 mm to about 16 mm. The length of a single vertical channel in one SiC block is preferably from about 50 to 500 mm, more preferably from 200 to 300 mm, for example 250 mm. Preferably two or more SiC blocks are combined.

[0163] Preferably the combined length of the reaction channels in case of more than one SiC block is in the range from about 0.2 m to about 4 m, more preferably from about 1 m to 2 m; even more preferably in the range of from about 1 .3 m to 1 .70 m. The other type of channels is horizontally arranged.

[0164] If the flow of the reaction mixture (“product flow”) is low (e.g., a laminar flow), a narrower drilling diameter of the given range is chosen as compared to a turbulent feed (e.g., a turbulent flow of the reaction mixture or “a turbulent product flow”) where larger diameters of the given range are applicable. The reactor channel volume shown in simplified Fig. 2 is an example for large industrial scale.

[0165] The needed reaction channel volume obviously also can be reached by combining several smaller reactors in series, up to 12 blocks (as of today) can be in one stainless steel housing. At the outlet there is a pressure valve keeping 15 bar absolute. The reactor given in simplified Fig. 2 and having a 6 Liter volume of total reaction channel is suitable for continuous industrial scale fluorination in liquid phase.

[0166] Example 2:

[0167] Fluorination of CCIF2CHCI2 (HCFC-122) to CF3-CHCI2 (HCFC-123) and CF2CI-CHFCI (HCFC-123a).

[0168] Reference is made to Figure 3.

[0169] Instead of “HCFC-122” this is also shortly abbreviated with “122”. This applies a nalogously to_HCFC-123 and HCFC-123a as well as for the rest of the present disclosure including other figures.

[0170] Pre-fluorination of catalyst:

[0171] Preparation of catalyst was done single time by using SbCIs which was treated in a batch PTFE lined autoclave with 10 eq. waterfree HF at 80°C for 1 h. The formed HCI was purged whenever the pressure has reached 20 bar. After cooling down and release to atmospheric pressure, the so-formed SbFs-nCIn was transferred into a SbFs-nCIn tank together with 20 mass % (mass percent) HF as catalyst for the reaction.

[0172] Fluorination in SiC block reactor:

[0173] A SiC block reactor with reaction channel volume 500 ml was heated to 95°C and the SbFs- nCIn feed was started with 100 ml / min. Right thereafter, the HCFC-122 feed was started as well with 50 ml / min. After filling of the settler (V=10 I) to 90 % and phase separation, catalyst phase was started to be fed back into the SbFs-nCIn tank so that the level in the settler remained constant. Fresh HF is fed before the catalyst pump to get additional advantage by reducing viscosity over dilution. The HCFC-123 (and HCFC-123a) phase mainly contained HCFC-123 (no HCFC-123a) and some HF and was transferred into a pressure distillation column made out of high grade stainless streel 1 .4571 as all corrosive materials remain in the rector cycle. The conversion of HCFC-122 to HCFC-123 was almost quantitative, and the obtained isolated yield of HCFC-123 after distillation was 97 %. If after 12 h of operation, a drop of activity is observed, the HCFC-122 feed was stopped and some CI2 was fed into the catalyst tank directly until the catalyst does not absorb anymore CI2 gas (not shown in the scheme of Fig. 3).

[0174] Example 3:

[0175] Fluorination of Perchloroethylene (PCE) to CCIF2CHCI2 (HCFC-122).

[0176] Reference is made to Figure 4.

[0177] Pre-fluorination of catalyst: Preparation of catalyst was done single time by using SbCh which was treated in a batch PTFE lined autoclave with 10 eq. waterfree HF at 80°C for 1 h. The formed HCI was purged whenever the pressure has reached 20 bar. After cooling down and release to atmospheric pressure, the so-formed SbFs-nCIn was transferred into the SbFs-nCIn tank together with 60 mass % HF as catalyst for the reaction.

[0178] Fluorination in SiC block reactor:

[0179] A SiC block reactor with reaction channel volume 500 ml was heated to 90°C and the SbFs- nCIn feed was started with 200 ml / min. Right thereafter, the PCE feed was started as well with 20 ml / min. After filling of the settler (V=10 I) to 90 % and phase separation, catalyst phase was started to be fed back into the SbFs-nCIn tank so that the level in the settler remained constant. The organic phase contained some small amount of unconverted PCE, HCFC-122, already some HCFC-123, some traces of R113 as side product and little amounts of HF. This organic phase mixture was transferred into a pressure distillation column made out of high grade stainless streel 1.4571 for PCE / HCFC-122 separation (if pure HCFC-122 is the target; if HCFC-123 is the target molecule, the distillation can be skipped, if no / very low amount of PCE is present) and directly used for next step fluorination to 123). The conversion of PCE to HCFC-122 / HCFC-123 was 89 %, the obtained isolated yield HCFC-122 after distillation in this trial was 95 %. It was observed that by reducing the residence time, the PCE conversion went little more down to 70% but R113 was not formed any more. The formation of R113 also can be tracked and taken as indicator for some deactivation of Sb in oxidation state V to oxidation state III.

[0180] Example 4:

[0181] Fluorination of CH2CI2 to HFC-32.

[0182] Reference is made to Figure 5.

[0183] A SiC block reactor with reaction channel volume 500 ml was heated to 100°C and the SbFs-nCIn feed was started with 100 ml / min. Right thereafter, the dichloromethane (CH2CI2) feed was started as well with 60 ml / min. After start of the reaction the formed HCI together with the product HFC-32 and some HF were leaving over a cyclone into a pressure distillation consisting out of three distillation columns to separate the mentioned compounds over the top condensers. The liquid phase of the cyclone was fed back into the SbFs-nCIn tank. Fresh HF was fed in light excess of stoichiometric amount to the dichloromethane before the catalyst pump, in order to achieve additional advantage by reducing somewhat viscosity over dilution. The conversion of CH2CI2 to the product HFC-32 was quantitative, the obtained isolated yield of HFC-32 after distillation was 98 %.

[0184] Example 5

[0185] The process of this exemplary embodiment is shown schematically in the reaction scheme above and comprises the steps 5a) and 5b).

[0186] 5a) Photochlorination of m-Cymene (3-lsopropyltoluene) to Heptachloro isopropyl m- trichloromethyl benzene (HCiPCM):

[0187] Apparatus for lab set up: 150 ml outside double wall (for cooling) Photoreactor for gas liquid reactions made out of Pyrex glass (which filters off all wavelength < 290 nm) with reflux condenser on the top (cooling 15°C), equipped with a TQ 718 Hg medium pressure lamp (Heraeus) and gas inlet over a fritted glas disc at the bottom.

[0188] 100g / 115 ml (0,745 mol) m-Cymene from Aldrich (product number 255289) were filled into the reactor together with an inert solvent, in this example 40 ml CF2CICFCI2 (Freon 113) were used, the lamp was switched on and after 2 minutes a CI2 gas stream out of a chlorine gas cylinder with 50 g / minute was fed over the fritted glass disc into the reactor. The typical green yellow color of the chlorine gas disappeared immediately and HCI gas started to leave the apparatus over the reflux condenser which shows that the chlorination is proceeding. Over the time, the green yellow color disappeared more and more slowly so that the reaction was stopped after 423 g (~80%) of the stochiometric CI2 was fed. GC MS showed mainly presence of the desired product besides some only partial chlorinated compounds which were NOT removed before next step. No nucleus chlorinated representatives could be detected.

[0189] 5b) Fluorination in SiC Block Reactor:

[0190] The heptachloroisopropyl m-trichloromethyl benzene (HCiPCM) solution out of several trials as described previously were directly used in a fluorination reaction apparatus according to example 1 (instead of 122). Fresh prepared perfluorinated catalyst with 20 mass % HF was fed together with 2,1 mol fresh HF / min (42g / min) HF into the reactor heated to 95°C. Right after, the heptachloro isopropyl m-trichloromethyl benzene (HCiPCM) feed was added with 100g / min. The residence time was adapted in total to 5-6 min for allowing all chlorinated positions to be fluorinated. A very strong HCI evolution was observed which was purged over the cyclone before the material entered the settler. The organic phase of the settler was transferred to a storage tank, washed with water, neutralized and distilled at atmospheric pressure. After some pre run of Freon 1 13 from photochlorination step, at a transition temperature of 131 ,2 °C, the product perfluoro-m- cymene (1-(perfluoropropan-2-yl)-4-(trifluoromethyl)benzene or (heptafluoro isopropyl m- trifluoromethyl) benzene)) was isolated with 98,8 % purity (GC analysis on 50 meter CP SIL 8 column). The yield based on starting material m-cymene was 82 %.

[0191] Example 6

[0192] This is not part of the invention as many routes to nitrobenzenes and anilines out of corresponding benzene precursors are very well known and applied. For a review about anilines, see PATAI's Chemistry of Functional Groups in 2009 by John Wiley & Sons, Ltd., DOI: 10.1002 / 9780470682531 ,pat0391). But the most convenient and cheapest reaction is according to the Bechamp-Reaction with Fe / HCI but preferred only for large scale due to handling and ferric oxide side product reasons. The nitration to HFiPTFNOB was done according to the scholar standard procedure with HNO3 / H2SO4 in almost quantitative yield and is not described here.

[0193] Reduction of 1 -Heptafluoroisopropyl 3-trifluoromthyl 4-nitrobenzene (HFiPTFNOB) to 1 -Heptafluoroisopropyl 3-trifluoromethyl 4-amino benzene (HFiPTFNH2B):

[0194] 10 g (0,0278 mol) of 1 -Heptafluoroisopropyl 3-trifluoromthyl 4-nitrobenzene (HFiPTFNOB) is dissolved in 50 ml EtOH together with 0,11 g (0,001 mol) Pd in a 100 ml glass flask, saturated with H2 over a dip pipe and afterwards equipped with a H2 filled 1 I ballon while stirring. After 5 h, the Pd was filtered off. GC-MS analysis showed presence of quantitative 1 -Heptafluoroisopropyl 3-trifluoromthyl 4-amino benzene (HFiPTFNH2B).

Claims

Claims:

1. A process for the manufacture of a fluorinated organic compound, wherein the process comprises a fluorination reaction of an organic precursor compound having at least one chlorine substituent and / or at least one double bond, and said organic precursor compound is reacted in liquid phase in HF (hydrogen fluoride), preferably in liquid phase in anhydrous HF (hydrogen fluoride), serving as solvent and fluorinating agent in the presence of a fluorinating catalyst, preferably a metal-based Lewis acid catalyst, and wherein the fluorination reaction is performed in liquid phase in a SiC block chemical reactor comprising at least one SiC block which provides two types of channels, wherein one type of channel is vertically arranged having an internal diameter from about 6 mm to about 25 mm, and this type of channel is serving as reaction chamber for passing through the reaction mixture, and the other type of channel is horizontally arranged for passing through a heating medium for heating the reaction mixture to a reaction temperature during the liquid phase fluorination, and wherein the reaction mixture is withdrawn from SiC block chemical reactor, and wherein the process comprises optionally isolating and / or purifying the targeted fluorinated organic compound.

2. A process for the manufacture of a fluorinated organic compound according to claim 1 , wherein the vertical channels independently from each other have an internal diameter in the range of from about 8 mm to about 16 mm, and more preferably all of them have the same internal diameter in the range of from about 8 mm to about 16 mm.

3. A process for the manufacture of a fluorinated organic compound according to claim 1 or 2, wherein the length of a single vertical channel in one SiC block is preferably from about 50 to 500 mm, more preferably from 200 to 300 mm.

4. A process for the manufacture of a fluorinated organic compound according to any of the preceding claims, with proviso that the organic precursor compound is not one of 3, 3-dichoro-1 ,1 ,1 -trichloropropane (240fa), 3,3-difluoro-1 ,1 ,1 -trifluoropropane (245fa) and / or with the proviso that the targeted fluorinated organic compound is not 1 ,1 ,1 ,3-tetrafluoropropene (1234ze).

5. A process for the manufacture of a fluorinated organic compound according to any one of claims 1 to 3, wherein the organic precursor compound is selected from the group consisting of chlorinated and optionally partially fluorinated C1-C10 alkanes and optionally chlorinated and optionally partially fluorinated C1-C10 alkenes, wherein the alkanes and alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

6. A process for the manufacture of a fluorinated organic compound according to claim 5, wherein the organic precursor compound is selected from the group consisting ofperchloroethylene (PCE, CCl2=CCl2), trichloroethylene (TRI, CHCI=CCl2), CCIF2CHCI2 (HCFC-122), 1 ,1 ,1 ,2,2-Pentachloroethane (HCC 120), dichloromethane (CH2CI2), chloroform (CHCh), 1 ,1 ,1 ,3,3-pentachloropropane (HCC- 240fa), 1 ,1 ,2,3-tetrachloropropene (HCC-1230xa), 2,3,3,3-tetrachloropropene (HCC-1230xf), 3,3,3-trichloropropene (HCC-1240zf), 1 ,1 ,1 ,2,3-pentachloropropane (HCC 240db), 1 ,1 ,3-trichloropropene (HCC 1240za), 1 ,1 ,1 ,3-tetrachloropropane (HCC-250fb), 1 ,1 ,1 ,3,3-pentachlorobutane (HCC 360), a,a,a-trichlorotoluene (Benzotrichloride), 1 -perchloroisopropyl 3-trichloromethyl benzene, 1- perchloroisopropyl 3-trichloromethyl 4-nitro benzene and heptachloro isopropyl m- trichloromethyl benzene.

7. A process for the manufacture of a fluorinated organic compound according to any one of the claims 1 to 3, wherein the targeted fluorinated organic compound is selected from the group consisting of partially or fully fluorinated C1-C10 alkanes and partially or fully fluorinated C1-C10 alkenes, wherein these C1-C10 alkanes and C1-C10 alkenes can further carry aromatic groups and / or NO2 groups in the molecule.

8. A process for the manufacture of a fluorinated organic compound according to claim7, wherein the targeted fluorinated organic compound is selected from the group consisting of (HCFC-122), (HCFC-123), (HCFC-123a), (HFC-32), 1 - perfluoroisopropyl 3-trifluoromethyl benzene and 1-perfluoroisopropyl-3- trifluoromethyl-4-nitro benzene.

9. A process for the manufacture of a fluorinated organic compound according to any of the preceding claims, wherein the metal-based Lewis acid catalyst contains Sb as metal, wherein Sb(V) is preferred.

10. A novel organic precursor compound that can be fluorinated in the process according to any of the preceding claims and that is selected from the group of compounds according to the following formula (I) and (II):11 . A compound according to formula (III):whereas the compound according to formula (III) is preferably manufactured by a process according to any of the preceding claims.

12. Use of a SiC block as a reactor for performing a chemical reaction, preferably for performing a catalyzed fluorinating reaction with HF as fluorinating agent, wherein the SiC block chemical reactor is comprising at least one SiC block which provides two types of channels, wherein one channel type is vertically arranged and has an internal diameter from about 6 mm to about 25 mm, and this type is serving as reaction chamber for passing through the reaction mixture, and the other channel type is horizontally arranged and serves as heating channels for passing through a heating medium for heating the reaction mixture to a reaction temperature.

13. A SiC block chemical reactor comprising at least one SiC block which provides two types of channels, wherein one type of channel is vertically arranged having an internal diameter from about 6 mm to about 25 mm, and this type of channel is serving as reaction chamber for passing through the reaction mixture, and the other type of channel is horizontally arranged for passing through a heating medium for heating the reaction mixture to a reaction temperature during the liquid phase fluorination, and wherein the reaction mixture is withdrawn from SiC block chemical reactor, and wherein the process comprises optionally isolating and / or purifying the targeted fluorinated organic compound.

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