WO2013023964A1 - Method of fluorination of a metal halide in an aqueous medium - Google Patents

Method of fluorination of a metal halide in an aqueous medium Download PDF

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Publication number
WO2013023964A1
WO2013023964A1 PCT/EP2012/065465 EP2012065465W WO2013023964A1 WO 2013023964 A1 WO2013023964 A1 WO 2013023964A1 EP 2012065465 W EP2012065465 W EP 2012065465W WO 2013023964 A1 WO2013023964 A1 WO 2013023964A1
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Prior art keywords
metal
process according
metal halide
fluorination process
fluorination
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PCT/EP2012/065465
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French (fr)
Inventor
Olivier Buisine
Julien TOURNAYRE
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Rhodia Operations
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Priority to CN201280044082.9A priority Critical patent/CN103781725A/en
Priority to IN1632DEN2014 priority patent/IN2014DN01632A/en
Publication of WO2013023964A1 publication Critical patent/WO2013023964A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B9/00—General methods of preparing halides
    • C01B9/08—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/02—Fluorides

Definitions

  • the present invention relates to the field of the fluorination of metal cation salts and halide anions, especially chloride anions, for the conversion of said salts into metal fluorides.
  • the present invention very advantageously has an application for the treatment of aqueous effluents containing halogenated anionic species.
  • the first step consists of reacting potassium chloride KCl with HF hydrofluoric acid in an anhydrous medium to lead to intermediate production potassium bifluoride KHF 2 , which is subjected in a second step to a high temperature thermolysis step (T> 300 ° C) to obtain potassium fluoride KF (FR 698921).
  • the hydrofluoric acid which is coproduced during the thermolysis step is isolated from potassium fluoride by distillation.
  • the regeneration of alkali metal fluorides is further described in Inorgic Fluorine Chemistry, JS Thrasher and S. Strauss, ACS Symposium Series 555, 1994, p237.
  • metal fluoride implements processes that are particularly delicate and difficult to use on an industrial scale because it requires an anhydrous reaction environment (anhydrous HF) and to operate at high temperature.
  • anhydrous reaction environment anhydrous HF
  • the present invention proposes the implementation of an innovative alternative method.
  • the subject of the present invention is a process for the fluorination of at least one metal halide MX in which M is a metal chosen from alkali metals and alkaline earth metals and X is a halogen chosen from chlorine, bromine and iodine. , said method comprising reacting, in the presence of water, at least said metal halide with hydrofluoric acid.
  • said fluorination process leads to the production of an MF metal fluoride where M is a metal selected from alkali metals and alkaline earth metals and a HX hydracid where X is a halogen selected from chlorine , bromine and iodine.
  • the fluorination reaction according to the process of the invention is written: MX + HF ⁇ MF + HX (reaction 1).
  • the HX hydracid is present in aqueous solution.
  • the metal fluoride MF has a high solubility in water, for example greater than 100 g / l, preferably greater than 500 g / l and even more preferably greater than 900 g / l at 25 °. vs.
  • said metal M is chosen from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium.
  • said metal M is chosen from lithium, sodium and potassium.
  • the halogen X present in the metal halide MX used for carrying out the fluorination process according to the invention is preferably chosen from chlorine and bromine. More preferably, the halogen X is chlorine.
  • the metal halides targeted by the invention are all commercial products.
  • the metal halide MX used for carrying out the process according to the invention is potassium chloride KCl.
  • the hydrofluoric acid used for carrying out the process according to the invention is used in anhydrous form (pure hydrogen fluoride) or in aqueous solution.
  • an aqueous solution containing at least 30% by weight of hydrogen fluoride is advantageously used.
  • Aqueous solutions containing up to 70% by weight of hydrogen fluoride are particularly preferred.
  • the aqueous reaction mixture comprises a mixture of metal halides.
  • aqueous reaction mixture is meant the mixture comprising at least one metal halide MX, at least hydrofluoric acid and at least water.
  • said reaction mixture comprises said metal halide MX and a metal fluoride M'F in which the metal M ', chosen from the alkali and alkaline earth metals as defined above in the present description, is identical or different to the metal M present in said metal halide MX.
  • the reaction mixture may also comprise a mixture of metal halides MX, as defined above, varying from one another by the nature of the metal M and / or the halogen X, for example it may be 'a mixture of an alkali or alkaline earth metal chloride and an alkali or alkaline earth metal bromide.
  • the mass ratio first metal halide / second metal halide is preferably greater than 0.1, very preferably greater than 0.2 and even more preferably greater than 0.3.
  • the aqueous reaction mixture comprises mineral species other than the said metal halide (s) , for example oxygenated mineral species such as carbonates or oxides.
  • the aqueous reaction mixture comprises at least one acid other than hydrofluoric acid, particularly a strong acid such as hydrochloric acid.
  • the said metal halide (s) MX and hydrofluoric acid are advantageously used in a proportion such that 0.5 to 5, preferably 0.9 to 3, more preferably 1 to 2.5, molar equivalents of fluoride anions per halogen atom X is (are) used.
  • the fluoride anions taken into account for calculating the number of molar equivalent (s) of fluoride anions are those present only in hydrofluoric acid.
  • the element (s) X taken into account for the calculation of the number of molar equivalents of fluoride anions per halogen atom X is (are) that present in the said (s) ( s) metal halide (s) MX, where X is a halogen selected from chlorine, bromine and iodine.
  • X is a halogen selected from chlorine, bromine and iodine.
  • the fluorination process according to the invention is carried out in the presence of water.
  • the amount of water present in the aqueous reaction mixture comprising at least hydrofluoric acid and at least said metal halide MX represents from 1 to 90% of its weight.
  • said quantity of water present in said mixture aqueous reaction is such that the molar ratio (s) metal (s) MX / water is between 0.01 and 1, preferably between 0.02 and 0.5 and even more preferably between 0.2 and 0 5.
  • a mixture of metal halides as described above in the present description, only the metal halides MX where X is a halogen chosen from chlorine, bromine and iodine are to be taken into account for the calculation of said halide. molar ratio.
  • demineralized water will be used for carrying out the process according to the invention.
  • the aqueous reaction mixture advantageously has an acidic pH, that is to say less than 7.
  • the fluorination reaction itself, carried out between at least said metal halide MX and hydrofluoric acid, is preferably carried out at room temperature. a temperature of between 50 and 160 ° C.
  • the duration of this fluorination reaction is between 1 and 20 hours, preferably between 3 and 15 hours, very preferably between 3 and 10 hours.
  • the fluorination process is advantageously carried out in a device equipped with a boiler in which the fluorination reaction between hydrofluoric acid and at least said metal halide MX takes place, of a distillation column in which circulating the formed hydracid vapor HX and a hydrogen acid vapor absorption system HX placed at the head of said column.
  • the boiler is the chamber in which the fluorination reaction in aqueous medium is carried out between the hydrofluoric acid and at least said metal halide MX according to the operating conditions described above: the said halide (s) MX-metal (s) and hydrofluoric acid are advantageously used in a proportion such as 0.5 to 5, preferably 0.9 to 3, more preferably 1 to 2.5, molar equivalents of fluoride anions per halogen atom X is (are) implemented.
  • the amount of water present in the boiler is such that the metal halide / water molar ratio is between 0.01 and 1, preferably between 0.02 and 0.5 and even more preferably between 0.2 and 0. 5.
  • the said metal halide (s) and hydrofluoric acid are preferably introduced separately into the boiler. They are introduced either in the pure state or in aqueous solution.
  • the water is introduced in admixture with the said metal halide (s) and / or with the hydrofluoric acid and / or alone, that is to say in the absence of any a species that can interfere with the fluorination reaction. It goes without saying that water is added separately when the said metal halide (s) and hydrofluoric acid are introduced in the pure state.
  • the reaction carried out in the boiler is advantageously carried out at a temperature of between 50 and 160 ° C.
  • the system providing heating within the boiler is ensured in a conventional manner, for example by a double jacket or a thermosiphon.
  • the fluorination reaction is carried out at atmospheric pressure or under reduced pressure, preferably at atmospheric pressure.
  • the boiler is drained so as to recover an aqueous solution of MF metal fluoride having a molar ratio X / F preferably less than 0.3, very preferably less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05, where X is selected from chlorine, bromine and iodine.
  • the distillation zone generally comprises at least one column provided with at least one distillation intern chosen from the group consisting of trays, bulk packings and structured packings. Said column advantageously comprises from the head to the foot of 2 to 35 theoretical trays without counting the boiler or the absorption system.
  • the distillation is carried out at atmospheric pressure or under a reduced pressure. At the top of the column, for example, the pressure is between 0.9 bar and 1.5 bar (0.09-0.15 MPa).
  • the temperature at the top of the column is advantageously between 20 and 130 ° C. and the temperature at the bottom of the column is advantageously between 20 and 120 ° C.
  • the distillation column present in the device preferably used for the implementation of the process according to the invention is surmounted by at least one system for absorbing the vapors of hydracid HX, in which the said hydracid vapors are brought into contact. with a fluid, preferably water, very preferably demineralised water.
  • a fluid preferably water, very preferably demineralised water.
  • the fluid, preferably water, introduced into the absorption system is such that the acid content is between 5% by weight and the saturated solution, ie 37% for hydrochloric acid for example.
  • the fluid, preferably water is introduced into the absorption system continuously so that the vapors are fully condensed.
  • Said absorption system is advantageously chosen from the following systems: a tube or bundle of tubes supplied co-currently with or without a static mixer which can be immersed in a shell in which a cooling fluid circulates, a tube or bundle of tubes supplied with counter-current said static falling film can be immersed in a calender in which circulates a cooling fluid, a packed column or trays can be traversed by sheets of tubes in which circulates a cooling fluid, a Venturi device, a stirred tank that can be equipped with a double jacket, half-shells or internal coil where a cooling fluid circulates and which can be provided with a gas injection torus, a bubble column which can be crossed by a sheet of tubes in which a fluid circulates cooling, a spraying column.
  • the absorption system is an absorber operating co-current, in particular a tube or tube bundle co-current fed with or without static mixer can be immersed in a calender in which a cooling fluid circulates.
  • Said absorption system is cooled by a cooling system such that the temperature within said absorption system is preferably between 10 and 70 ° C.
  • the temperature of the aqueous solution comprising the hydracid exiting said absorption system is between 20 and 90 ° C.
  • the cooling of the absorption system is provided by any cooling system used in the distillation field and known to those skilled in the art.
  • the cooling of the absorption system is provided by the technology own system or by a heat exchanger on an external loop. In particular, it may be a heat transfer fluid, preferably water, circulating in a double outer envelope to said absorption system.
  • the distillation carried out is a reactive distillation.
  • the equilibrium of reaction 1 above, thermodynamically shifted in the direction leading to the production of MF and HF, is shifted to the desired production of said metal fluoride by the distillation of HX hydracid.
  • the hydracid After absorption into the water within the absorption system, preferably in an absorber operating cocurrently, the hydracid is present in aqueous solution which is partially demoted to the top of the distillation column while the other part is recovered.
  • the flow rate of the aqueous solution of hydracid introduced at the top of the column is less than the total flow rate of hydracid vapors circulating at the top of the column.
  • the continuous introduction of a fluid, preferably water, into the absorption system leads to a perfect separation of the hydrofluoric acid from the hydracid HX formed: the aqueous solution containing the hydracid is very advantageously free of hydrofluoric acid.
  • the method according to the invention implemented in the device described above leads to the production of a part of an aqueous solution in which the hydracid is present and secondly of an aqueous solution of metallic fluoride.
  • a molar ratio X / F preferably less than 0.3, very preferably less than 0.2 and even more preferably less than 0.1, where X is selected from chlorine, bromine and iodine.
  • FIG. 1 represents a distillation column device for implementing the fluorination process according to the invention.
  • the boiler (1) In the boiler (1) are separately introduced the metal halide MX by the line (2), the hydrofluoric acid by the line (3) and optionally water through the line (4).
  • the boiler is equipped with a heating system (6) to enable the fluorination reaction to be carried out at a temperature between 50 and 160 ° C.
  • the column (5) contains elements allowing gas / liquid contacting, for example trays or packing. At the bottom of the column, the least volatile fraction of the products formed, namely metallic fluoride, is recovered in the boiler (1). The entire mixture thus obtained is heated and evaporated in the exchanger (6) - in an outer loop in the diagram. The steam is reintroduced into the boiler by the line (8) and then goes up in the column (5).
  • the hydrofluoric vapor HX is sent via line (9) into an absorber operating in cocurrent (10).
  • the absorber is a bundle of co-current fed tubes immersed in a calender. Demineralized water and hydrofluoric vapor HX are respectively introduced by the lines (1 1) and (9) at the head of the absorber (10).
  • the cooling system of the absorber (10) is provided by circulating a cooling fluid, preferably water, within a double jacket external to said absorber (10) and into which said cooling fluid is injected. for example water, via line (12) at a temperature of between 10 and 70 ° C.
  • the cooling of the absorber results in a heating of the cooling fluid which is discharged, heated, by the line (13).
  • the liquid aqueous solution withdrawn at the bottom of the absorber (10) is introduced into a flask (14) provided with a vent (15) allowing the pressure regulation of the installation.
  • the liquid phase formed of an aqueous solution of hydracid extracted from the flask (14) is returned continuously, for a part, by the line (16) at the top of the distillation column (5) while the other part constitutes the liquid distillate which is evacuated by the line (17).
  • the aqueous solution of metal fluoride is recovered via line (7) after opening of the valve (18).
  • the process according to the invention is advantageously carried out in a device capable of resisting corrosion of the reaction medium.
  • the device is made of one or more corrosion resistant material (s).
  • the material constituting the boiler and the distillation column is chosen from graphite materials, silicon carbide and fluoropolymers.
  • fluoropolymers PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), FEP (hexafluoropropylene tetrafluoroethylene copolymer) and PFA (perfluoroalkyl resins) are particularly suitable. It would not be outside the scope of the invention to use a material of equivalent nature.
  • the distillation column may be made, throughout its length, of a single material resistant to corrosion or a succession of sections, each of them being made of a different material.
  • the absorption system is for example made of a material chosen from graphite materials, fluorinated polymers, PPHD (high density polypropylene), HDPE (high density polyethylene), vitreous steel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten alloys sold under the trade names HASTELLOY ® or nickel, chromium alloys , iron, manganese additivés of copper and / or molybdenum marketed under the name INCONEL ® and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718.
  • the fluorination process according to the invention is a process that is simple to implement, operating under mild conditions in an aqueous medium. It leads to the co-production of an aqueous solution of HX hydracid and an aqueous solution of MF metal fluoride.
  • the aqueous solution of HX hydracid is advantageously promoted as a raw material in the chemical industry.
  • One of the advantages of implementing the method of the invention according to the boiler / distillation column / absorption system device is the possibility of obtaining an aqueous solution of HX hydracid, for example an aqueous solution of HCl at the desired concentration, depending on the amount of water introduced into the absorption system.
  • the aqueous solution of metal fluoride MF can be directly used for applications involving the use of an aqueous solution based on salts of metal cations M and fluoride anions or it can be spray dried or concentrated by evaporation of the water.
  • Said aqueous solution of metal fluoride MF has a molar ratio X / F preferably less than 0.3, very preferably less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05, where X is selected from chlorine, bromine and iodine.
  • the process according to the invention is particularly preferred for carrying out the fluorination reaction of potassium chloride with hydrofluoric acid in an aqueous medium. This results in the co-production of an aqueous solution of hydrochloric acid and an aqueous solution of potassium fluoride.
  • the fluorination process of the invention is based on a simple and environmentally friendly technology provided that the products obtained are present in aqueous solution, which is inexpensive in terms of energy, in particular with regard to the existing technology which requires a step thermolysis.
  • the fluorination process according to the invention is advantageously applied for the treatment of aqueous flux containing at least one metal halide MX as defined above in the present description.
  • the fluorination process according to the invention is perfectly suitable for the treatment of aqueous effluents containing said halide metal, alone or mixed with other mineral species, for example with other metal halides, such as metal fluorides, or with oxygenated mineral species such as carbonates or oxides.
  • Said metal halide MX is especially present in effluents produced by the implementation of a halogen / fluorine exchange reaction between a halogenated substrate and a salt providing a fluoride anion.
  • Said halogenated substrate comprises at least one halogen atom different from fluorine.
  • said halogenated substrate has the following formula: HCX 1 X 2 - COOR- ⁇ , with
  • X 1 and X 2 which may be identical or different, represent a chlorine, bromine or fluorine atom with the proviso that at least one of the atoms X 1 , X 2 is a chlorine or bromine atom,
  • a hydrocarbon group substituted or unsubstituted, which may be an alkyl or cycloalkyl group,
  • Example 1 (invention)
  • the device used in this example is equipped with a double-shelled 200 ml PTFE boiler-reactor surmounted by a PTFE distillation column (height 200 mm, diameter 30 mm) filled with a PTFE packing of 12 theoretical stages, said column being itself surmounted by a gas absorber operating against the current.
  • Said absorber is a column, of PTFE, 30 mm in diameter and 200 mm in height, filled with Rashig-type rings and supplied with counter-current, the gas (namely the vapors of HCl in this example) arriving in bottom of the column (playing the role of absorber) and water (stream 1 1) arriving from above.
  • the absorber is provided with an outer double jacket in which water circulates to ensure cooling within the absorber.
  • the entire device is placed at atmospheric pressure.
  • the temperature of the outer jacket to the boiler is increased to 160 ° C for a period of 12 hours.
  • the absorber of gas is fed at the top by a flow of water permuted, continuously, corresponding to a total amount of 89 g during the experiment over a period of 12 hours (flow 1 1).
  • the temperature at the top of the distillation column rises gradually to 104 ° C.
  • the absorber is cooled by water circulating in a jacket at a temperature of 15 ° C.
  • the temperature of the aqueous phase in which HCl is present is equal to 25 ° C.
  • stream 16 Part of the aqueous stream comprising HCl, at the outlet of the absorber, is re-introduced into the distillation column (stream 16): the total amount of aqueous solution re-introduced into the distillation column during the experiment is equal to 302 g over a period of 12 hours.
  • the remainder of the stream (stream No. 17) is collected and the total collected is 1 12 g containing 333 g / l of chloride and 9.1 g / l of protons.

Abstract

The invention describes a method of fluorination of at least one metal halide MX where M is a metal selected from the alkali metals and the alkaline earth metals and X is a halogen selected from chlorine, bromine and iodine, said method comprising the reaction, in the presence of water, of at least said metal halide with hydrofluoric acid. Said fluorination method is implemented in a device provided with a boiler in which the fluorination reaction takes place between the hydrofluoric acid and at least said metal halide MX, a distillation column in which circulate the hydracid vapours HX formed, and a system for absorbing the hydracid vapours HX positioned at the head of said column.

Description

PROCEDE DE FLUORATION D'UN HALOGENURE METALLIQUE EN MILIEU AQUEUX  PROCESS FOR THE FLUORATION OF A METAL HALIDE IN AQUEOUS MEDIUM
La présente invention se rapporte au domaine de la fluoration de sels de cations métalliques et d'anions halogénures, notamment d'anions chlorures, pour la transformation desdits sels en fluorures métalliques. La présente invention trouve très avantageusement une application pour le traitement d'effluents aqueux contenant des espèces anioniques halogénées. The present invention relates to the field of the fluorination of metal cation salts and halide anions, especially chloride anions, for the conversion of said salts into metal fluorides. The present invention very advantageously has an application for the treatment of aqueous effluents containing halogenated anionic species.
Etat de la technique antérieure La fluoration d'halogénures métalliques pour obtenir les fluorures métalliques correspondants a déjà été largement décrite dans la littérature. En particulier, il est connu d'obtenir du fluorure de potassium KF par un mécanisme réactionnel en deux étapes : la première étape consiste à faire réagir du chlorure de potassium KCI avec de l'acide fluorhydrique HF en milieu anhydre pour conduire à la production intermédiaire de bifluorure de potassium KHF2, lequel est soumis dans une seconde étape à une étape de thermolyse à haute température (T > 300°C) pour obtenir du fluorure de potassium KF (FR 698921 ). L'acide fluorhydrique qui est coproduit au cours de l'étape de thermolyse est isolé du fluorure de potassium par distillation. La régénération des fluorures métalliques alcalins est par ailleurs décrite dans l'ouvrage Inorgic Fluorine Chemistry, J. S. Thrasher et S. Strauss, ACS symposium Séries 555, 1994, p237. STATE OF THE PRIOR ART The fluorination of metal halides to obtain the corresponding metal fluorides has already been widely described in the literature. In particular, it is known to obtain KF potassium fluoride by a two-step reaction mechanism: the first step consists of reacting potassium chloride KCl with HF hydrofluoric acid in an anhydrous medium to lead to intermediate production potassium bifluoride KHF 2 , which is subjected in a second step to a high temperature thermolysis step (T> 300 ° C) to obtain potassium fluoride KF (FR 698921). The hydrofluoric acid which is coproduced during the thermolysis step is isolated from potassium fluoride by distillation. The regeneration of alkali metal fluorides is further described in Inorgic Fluorine Chemistry, JS Thrasher and S. Strauss, ACS Symposium Series 555, 1994, p237.
Jusqu'à présent, la production de fluorures métalliques met en œuvre des procédés particulièrement délicats et difficiles à utiliser à l'échelle industrielle car il nécessite un environnement réactionnel anhydre (HF anhydre) et d'opérer à haute température.  Until now, the production of metal fluoride implements processes that are particularly delicate and difficult to use on an industrial scale because it requires an anhydrous reaction environment (anhydrous HF) and to operate at high temperature.
De plus, les effluents contenant des halogénures métalliques issus de procédés mettant en œuvre des fluorures métalliques causent des problèmes environnementaux nécessitant le traitement subséquent desdits effluents. In addition, the effluents containing metal halides from processes using metal fluorides cause environmental problems requiring the subsequent treatment of said effluents.
Aussi pour s'affranchir des contraintes techniques imposées par l'environnement anhydre de la réaction de production de fluorures métalliques à partir d'HF et pour éviter le traitement subséquent d'effluents issus de procédés utilisant des fluorures métalliques, la présente invention propose la mise en œuvre d'un procédé alternatif innovant.  Also to overcome the technical constraints imposed by the anhydrous environment of the reaction of production of metal fluorides from HF and to avoid the subsequent treatment of effluents from processes using metal fluorides, the present invention proposes the implementation of an innovative alternative method.
Description de l'invention Description of the invention
La présente invention a pour objet un procédé de fluoration d'au moins un halogénure métallique MX où M est un métal choisi parmi les métaux alcalins et les métaux alcalino- terreux et X est un halogène choisi parmi le chlore, le brome et l'iode, ledit procédé comprenant la réaction, en présence d'eau, d'au moins dudit halogénure métallique avec de l'acide fluorhydrique. The subject of the present invention is a process for the fluorination of at least one metal halide MX in which M is a metal chosen from alkali metals and alkaline earth metals and X is a halogen chosen from chlorine, bromine and iodine. , said method comprising reacting, in the presence of water, at least said metal halide with hydrofluoric acid.
Selon l'invention, ledit procédé de fluoration conduit à la production d'un fluorure métallique MF où M est un métal choisi parmi les métaux alcalins et les métaux alcalino-terreux et d'un hydracide HX où X est un halogène choisi parmi le chlore, le brome et l'iode. La réaction de fluoration selon le procédé de l'invention s'écrit : MX + HF→ MF + HX (réaction 1 ). De manière avantageuse, l'hydracide HX se trouve présent en solution aqueuse. Selon l'invention, le fluorure métallique MF présente une solubilité élevée dans l'eau, par exemple supérieure à 100 g/l, de préférence supérieure à 500 g/l et de manière encore plus préférée supérieure à 900 g/l à 25°C.  According to the invention, said fluorination process leads to the production of an MF metal fluoride where M is a metal selected from alkali metals and alkaline earth metals and a HX hydracid where X is a halogen selected from chlorine , bromine and iodine. The fluorination reaction according to the process of the invention is written: MX + HF → MF + HX (reaction 1). Advantageously, the HX hydracid is present in aqueous solution. According to the invention, the metal fluoride MF has a high solubility in water, for example greater than 100 g / l, preferably greater than 500 g / l and even more preferably greater than 900 g / l at 25 °. vs.
Conformément à l'invention ledit métal M est choisi parmi le lithium, le sodium, le potassium, le rubidium, le césium, le magnésium, le calcium, le strontium et le baryum. De manière préférée, ledit métal M est choisi parmi le lithium, le sodium et le potassium.  According to the invention, said metal M is chosen from lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium. Preferably, said metal M is chosen from lithium, sodium and potassium.
L'halogène X présent dans l'halogénure métallique MX utilisé pour la mise en œuvre du procédé de fluoration selon l'invention est préférentiellement choisi parmi le chlore et le brome. De manière plus préférée, l'halogène X est le chlore. Les halogénures métalliques visés par l'invention sont tous des produits commercialisés. De manière avantageuse, l'halogénure métallique MX utilisé pour la mise en œuvre du procédé selon l'invention est le chlorure de potassium KCI. The halogen X present in the metal halide MX used for carrying out the fluorination process according to the invention is preferably chosen from chlorine and bromine. More preferably, the halogen X is chlorine. The metal halides targeted by the invention are all commercial products. Advantageously, the metal halide MX used for carrying out the process according to the invention is potassium chloride KCl.
L'acide fluorhydrique utilisé pour la mise en œuvre du procédé selon l'invention est utilisé sous forme anhydre (fluorure d'hydrogène pur) ou en solution aqueuse. On utilise par exemple avantageusement une solution aqueuse contenant au moins 30% poids de fluorure d'hydrogène. Des solutions aqueuses contenant jusqu'à 70% poids de fluorure d'hydrogène sont en particulier préférées. The hydrofluoric acid used for carrying out the process according to the invention is used in anhydrous form (pure hydrogen fluoride) or in aqueous solution. For example, an aqueous solution containing at least 30% by weight of hydrogen fluoride is advantageously used. Aqueous solutions containing up to 70% by weight of hydrogen fluoride are particularly preferred.
Selon un mode avantageux de mise en œuvre du procédé selon l'invention, le mélange réactionnel aqueux comprend un mélange d'halogénures métalliques. Par mélange réactionnel aqueux, on entend le mélange comprenant au moins un halogénure métallique MX, au moins de l'acide fluorhydrique et au moins de l'eau. Par exemple, ledit mélange réactionnel comprend ledit halogénure métallique MX et un fluorure métallique M'F dans lequel le métal M', choisi parmi les métaux alcalins et alcalino-terreux tels que définis ci- dessus dans la présente description, est identique ou différent au métal M présent dans ledit halogénure métallique MX. Le mélange réactionnel peut encore comprendre un mélange d'halogénures métalliques MX, selon la définition donnée ci-dessus, variant les uns des autres par la nature du métal M et/ou de l'halogène X, par exemple il peut s'agir d'un mélange d'un chlorure d'un métal alcalin ou alcalino-terreux et d'un bromure d'un métal alcalin ou alcalino-terreux. En présence d'un mélange d'halogénures métalliques comprenant un premier halogénure métallique MX tel que décrit ci-dessus et un deuxième halogénure métallique choisi parmi un fluorure métallique et un second halogénure métallique MX variant du premier par la nature du métal M et/ou de l'halogène X, le rapport massique premier halogénure métallique/deuxième halogénure métallique est préférentiellement supérieur à 0,1 , très préférentiellement supérieur à 0,2 et de manière encore plus préférée supérieur à 0,3. Selon un autre mode avantageux de mise en œuvre du procédé selon l'invention, indépendant ou non de celui décrit précédemment, le mélange réactionnel aqueux comprend des espèces minérales autres que le(s)dit(s) halogénure(s) métallique(s), par exemple des espèces minérales oxygénées tels que les carbonates ou les oxydes. Selon un autre mode avantageux de mise en œuvre du procédé selon l'invention, indépendant ou non de ceux décrits précédemment, le mélange réactionnel aqueux comprend au moins un acide autre que l'acide fluorhydrique, particulièrement un acide fort tel que l'acide chlorhydrique. Conformément au procédé de l'invention, le(s)dit(s) halogénure(s) métallique(s) MX et l'acide fluorhydrique sont avantageusement utilisés dans une proportion telle que 0,5 à 5, de préférence 0,9 à 3, de manière plus préférée de 1 à 2,5, équivalents molaires d'anions fluorures par atome d'halogène X est(sont) mis en œuvre. Les anions fluorures pris en compte pour le calcul du nombre d'équivalent(s) molaire(s) d'anions fluorures sont ceux présents uniquement dans l'acide fluorhydrique. Le(s) élément(s) X pris en compte pour le calcul du nombre d'équivalents molaires d'anions fluorures par atome d'halogène X est(sont) celui(ceux) présent(s) dans le(s)dit(s) halogénure(s) métallique(s) MX, où X est un halogène choisi parmi le chlore, le brome et l'iode. En présence d'un mélange d'halogénures métalliques tel que décrit plus haut dans la présente description, seuls les halogènes X présents dans les halogénures métalliques MX où X est un halogène choisi parmi le chlore, le brome et l'iode sont à prendre en compte pour ledit calcul. According to an advantageous embodiment of the process according to the invention, the aqueous reaction mixture comprises a mixture of metal halides. By aqueous reaction mixture is meant the mixture comprising at least one metal halide MX, at least hydrofluoric acid and at least water. For example, said reaction mixture comprises said metal halide MX and a metal fluoride M'F in which the metal M ', chosen from the alkali and alkaline earth metals as defined above in the present description, is identical or different to the metal M present in said metal halide MX. The reaction mixture may also comprise a mixture of metal halides MX, as defined above, varying from one another by the nature of the metal M and / or the halogen X, for example it may be 'a mixture of an alkali or alkaline earth metal chloride and an alkali or alkaline earth metal bromide. In the presence of a mixture of metal halides comprising a first metal halide MX as described above and a second metal halide selected from a metal fluoride and a second metal halide MX varying from the first by the nature of the metal M and / or of the halogen X, the mass ratio first metal halide / second metal halide is preferably greater than 0.1, very preferably greater than 0.2 and even more preferably greater than 0.3. According to another advantageous embodiment of the process according to the invention, independent or not of that described above, the aqueous reaction mixture comprises mineral species other than the said metal halide (s) , for example oxygenated mineral species such as carbonates or oxides. According to another advantageous embodiment of the process according to the invention, independent or not of those described above, the aqueous reaction mixture comprises at least one acid other than hydrofluoric acid, particularly a strong acid such as hydrochloric acid. . According to the process of the invention, the said metal halide (s) MX and hydrofluoric acid are advantageously used in a proportion such that 0.5 to 5, preferably 0.9 to 3, more preferably 1 to 2.5, molar equivalents of fluoride anions per halogen atom X is (are) used. The fluoride anions taken into account for calculating the number of molar equivalent (s) of fluoride anions are those present only in hydrofluoric acid. The element (s) X taken into account for the calculation of the number of molar equivalents of fluoride anions per halogen atom X is (are) that present in the said (s) ( s) metal halide (s) MX, where X is a halogen selected from chlorine, bromine and iodine. In the presence of a mixture of metal halides as described above in the present description, only the halogens X present in the metal halides MX where X is a halogen chosen from chlorine, bromine and iodine are to be taken into account. account for said calculation.
Le procédé de fluoration selon l'invention est mis en œuvre en présence d'eau. La quantité d'eau présente dans le mélange réactionnel aqueux comprenant au moins l'acide fluorhydrique et au moins ledit halogénure métallique MX représente de 1 à 90% de son poids. De manière avantageuse, ladite quantité d'eau présente dans ledit mélange réactionnel aqueux est telle que le rapport molaire halogénure(s) métallique(s) MX/eau est compris entre 0,01 et 1 , de préférence entre 0,02 et 0,5 et de manière encore plus préférée entre 0,2 et 0,5. En présence d'un mélange d'halogénures métalliques tel que décrit plus haut dans la présente description, seuls les halogénures métalliques MX où X est un halogène choisi parmi le chlore, le brome et l'iode sont à prendre en compte pour le calcul dudit rapport molaire. De manière préférée, on utilisera de l'eau déminéralisée pour la mise en œuvre du procédé selon l'invention. Le mélange réactionnel aqueux présente avantageusement un pH acide, c'est-à-dire inférieur à 7. La réaction de fluoration en elle-même, réalisée entre au moins ledit halogénure métallique MX et l'acide fluorhydrique, est préférentiellement mise en œuvre à une température comprise entre 50 et 160°C. De préférence, la durée de cette réaction de fluoration est comprise entre 1 et 20 heures, préférentiellement entre 3 et 15 heures, très préférentiellement entre 3 et 10 heures. The fluorination process according to the invention is carried out in the presence of water. The amount of water present in the aqueous reaction mixture comprising at least hydrofluoric acid and at least said metal halide MX represents from 1 to 90% of its weight. Advantageously, said quantity of water present in said mixture aqueous reaction is such that the molar ratio (s) metal (s) MX / water is between 0.01 and 1, preferably between 0.02 and 0.5 and even more preferably between 0.2 and 0 5. In the presence of a mixture of metal halides as described above in the present description, only the metal halides MX where X is a halogen chosen from chlorine, bromine and iodine are to be taken into account for the calculation of said halide. molar ratio. Preferably, demineralized water will be used for carrying out the process according to the invention. The aqueous reaction mixture advantageously has an acidic pH, that is to say less than 7. The fluorination reaction itself, carried out between at least said metal halide MX and hydrofluoric acid, is preferably carried out at room temperature. a temperature of between 50 and 160 ° C. Preferably, the duration of this fluorination reaction is between 1 and 20 hours, preferably between 3 and 15 hours, very preferably between 3 and 10 hours.
Conformément à l'invention, le procédé de fluoration est avantageusement mis en œuvre dans un dispositif équipé d'un bouilleur où se produit la réaction de fluoration entre l'acide fluorhydrique et au moins ledit halogénure métallique MX, d'une colonne de distillation où circulent les vapeurs d'hydracide HX formé et d'un système d'absorption des vapeurs d'hydracide HX placé en tête de ladite colonne. According to the invention, the fluorination process is advantageously carried out in a device equipped with a boiler in which the fluorination reaction between hydrofluoric acid and at least said metal halide MX takes place, of a distillation column in which circulating the formed hydracid vapor HX and a hydrogen acid vapor absorption system HX placed at the head of said column.
Le bouilleur est l'enceinte dans laquelle est réalisée la réaction de fluoration en milieu aqueux entre l'acide fluorhydrique et au moins ledit halogénure métallique MX selon les conditions opératoires décrites ci-dessus : le(s)dit(s) halogénure(s) métallique(s) MX et l'acide fluorhydrique sont avantageusement utilisés dans une proportion telle que 0,5 à 5, de préférence 0,9 à 3, de manière plus préférée de 1 à 2,5, équivalents molaires d'anions fluorure par atome d'halogène X est(sont) mis en œuvre. La quantité d'eau présente dans le bouilleur est telle que le rapport molaire halogénures métalliques/eau est compris entre 0,01 et 1 , de préférence entre 0,02 et 0,5 et de manière encore plus préférée entre 0,2 et 0,5. Le(s)dit(s) halogénure(s) métallique(s) et l'acide fluorhydrique sont préférentiellement introduits séparément dans le bouilleur. Ils sont introduits soit à l'état pur soit en solution aqueuse. L'eau est introduite en mélange avec le(s)dit(s) halogénure(s) métallique(s) et/ou avec l'acide fluorhydrique et/ou seule, c'est-à-dire en l'absence de toute espèce pouvant interférer sur la réaction de fluoration. Il va de soi que de l'eau est ajoutée séparément lorsque le(s)dit(s) halogénure(s) métallique(s) et l'acide fluorhydrique sont introduits à l'état pur. La réaction réalisée dans le bouilleur est avantageusement effectuée à une température comprise entre 50 et 160°C. Le système assurant le chauffage au sein du bouilleur est assurée de façon classique, par exemple par une double enveloppe ou un thermosiphon. La réaction de fluoration est effectuée à pression atmosphérique ou sous pression réduite, préférentiellement à pression atmosphérique. En fin de réaction, le bouilleur est vidangé de manière à récupérer une solution aqueuse de fluorure métallique MF présentant un rapport molaire X/F préférentiellement inférieur à 0,3, très préférentiellement inférieur à 0,2, plus préférentiellement inférieur à 0,1 , et encore plus préférentiellement inférieur à 0,05, où X est choisi parmi le chlore, le brome et l'iode. The boiler is the chamber in which the fluorination reaction in aqueous medium is carried out between the hydrofluoric acid and at least said metal halide MX according to the operating conditions described above: the said halide (s) MX-metal (s) and hydrofluoric acid are advantageously used in a proportion such as 0.5 to 5, preferably 0.9 to 3, more preferably 1 to 2.5, molar equivalents of fluoride anions per halogen atom X is (are) implemented. The amount of water present in the boiler is such that the metal halide / water molar ratio is between 0.01 and 1, preferably between 0.02 and 0.5 and even more preferably between 0.2 and 0. 5. The said metal halide (s) and hydrofluoric acid are preferably introduced separately into the boiler. They are introduced either in the pure state or in aqueous solution. The water is introduced in admixture with the said metal halide (s) and / or with the hydrofluoric acid and / or alone, that is to say in the absence of any a species that can interfere with the fluorination reaction. It goes without saying that water is added separately when the said metal halide (s) and hydrofluoric acid are introduced in the pure state. The reaction carried out in the boiler is advantageously carried out at a temperature of between 50 and 160 ° C. The system providing heating within the boiler is ensured in a conventional manner, for example by a double jacket or a thermosiphon. The fluorination reaction is carried out at atmospheric pressure or under reduced pressure, preferably at atmospheric pressure. At the end of the reaction, the boiler is drained so as to recover an aqueous solution of MF metal fluoride having a molar ratio X / F preferably less than 0.3, very preferably less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05, where X is selected from chlorine, bromine and iodine.
Le chauffage du mélange réactionnel dans le bouilleur conduit à la formation de vapeurs d'hydracides HX récupérées en tête de colonne de distillation. La zone de distillation comprend généralement au moins une colonne munie d'au moins un interne de distillation choisi dans le groupe formé par les plateaux, les garnissages en vrac et les garnissages structurés. Ladite colonne comporte avantageusement de la tête vers le pied de 2 à 35 plateaux théoriques sans compter le bouilleur ni le système d'absorption. La distillation est réalisée à pression atmosphérique ou sous une pression réduite. En tête de colonne, par exemple, la pression est comprise entre 0,9 bar et 1 ,5 bar (0,09-0,15 MPa). La température en tête de colonne est avantageusement comprise entre 20 et 130°C et la température en fond de colonne est avantageusement comprise entre 20 et 120°C.  Heating the reaction mixture in the boiler leads to the formation of hydrous acid HX vapor recovered at the top of the distillation column. The distillation zone generally comprises at least one column provided with at least one distillation intern chosen from the group consisting of trays, bulk packings and structured packings. Said column advantageously comprises from the head to the foot of 2 to 35 theoretical trays without counting the boiler or the absorption system. The distillation is carried out at atmospheric pressure or under a reduced pressure. At the top of the column, for example, the pressure is between 0.9 bar and 1.5 bar (0.09-0.15 MPa). The temperature at the top of the column is advantageously between 20 and 130 ° C. and the temperature at the bottom of the column is advantageously between 20 and 120 ° C.
La colonne de distillation présente dans le dispositif préférentiellement utilisé pour la mise en œuvre du procédé selon l'invention est surmontée d'au moins un système d'absorption des vapeurs d'hydracide HX, dans lequel lesdites vapeurs d'hydracide sont mises en contact avec un fluide, préférentiellement de l'eau, très préférentiellement de l'eau déminéralisée. Le fluide, préférentiellement l'eau, introduit(e) dans le système d'absorption est tel que le titre en acide est compris entre 5% massique et la solution saturée, soit 37% pour l'acide chlorhydrique par exemple. Le fluide, préférentiellement l'eau, est introduit dans le système d'absorption en continu de sorte que les vapeurs soient entièrement condensées. Ledit système d'absorption est avantageusement choisi parmi les systèmes suivants : un tube ou faisceau de tubes alimenté à co-courant avec ou sans mélangeur statique pouvant être plongé dans une calandre où circule un fluide de refroidissement, un tube ou faisceau de tubes alimenté à contre-courant dit à film tombant statique pouvant être plongé dans une calandre où circule un fluide de refroidissement, une colonne avec garnissage ou plateaux pouvant être traversée par des nappes de tubes où circule un fluide de refroidissement, un dispositif Venturi, une cuve agitée pouvant être équipée de double enveloppe, de demi- coquilles ou de serpentin interne où circule un fluide de refroidissement et pouvant être pourvue d'un tore d'injection de gaz, une colonne à bulles pouvant être traversée par une nappe de tubes où circule un fluide de refroidissement, une colonne à pulvérisation. Ces différents systèmes sont bien connus de l'Homme du métier en tant que tel. De manière préférée, le système d'absorption est un absorbeur fonctionnant à co-courant, notamment un tube ou faisceau de tubes alimenté à co-courant avec ou sans mélangeur statique pouvant être plongé dans une calandre où circule un fluide de refroidissement. Ledit système d'absorption est refroidi par un système de refroidissement tel que la température au sein dudit système d'absorption est préférentiellement comprise entre 10 et 70°C. La température de la solution aqueuse comprenant l'hydracide sortant dudit système d'absorption est comprise entre 20 et 90°C. Le refroidissement du système d'absorption est assuré par tout système de refroidissement utilisé dans le domaine de la distillation et connu de l'Homme du métier. Le refroidissement du système d'absorption est assuré grâce à la technologie propre audit système ou par un échangeur de chaleur sur une boucle externe. En particulier, il peut s'agir d'un fluide caloporteur, préférentiellement de l'eau, circulant dans une double enveloppe extérieure audit système d'absorption. The distillation column present in the device preferably used for the implementation of the process according to the invention is surmounted by at least one system for absorbing the vapors of hydracid HX, in which the said hydracid vapors are brought into contact. with a fluid, preferably water, very preferably demineralised water. The fluid, preferably water, introduced into the absorption system is such that the acid content is between 5% by weight and the saturated solution, ie 37% for hydrochloric acid for example. The fluid, preferably water, is introduced into the absorption system continuously so that the vapors are fully condensed. Said absorption system is advantageously chosen from the following systems: a tube or bundle of tubes supplied co-currently with or without a static mixer which can be immersed in a shell in which a cooling fluid circulates, a tube or bundle of tubes supplied with counter-current said static falling film can be immersed in a calender in which circulates a cooling fluid, a packed column or trays can be traversed by sheets of tubes in which circulates a cooling fluid, a Venturi device, a stirred tank that can be equipped with a double jacket, half-shells or internal coil where a cooling fluid circulates and which can be provided with a gas injection torus, a bubble column which can be crossed by a sheet of tubes in which a fluid circulates cooling, a spraying column. These different systems are well known to those skilled in the art as such. So preferred, the absorption system is an absorber operating co-current, in particular a tube or tube bundle co-current fed with or without static mixer can be immersed in a calender in which a cooling fluid circulates. Said absorption system is cooled by a cooling system such that the temperature within said absorption system is preferably between 10 and 70 ° C. The temperature of the aqueous solution comprising the hydracid exiting said absorption system is between 20 and 90 ° C. The cooling of the absorption system is provided by any cooling system used in the distillation field and known to those skilled in the art. The cooling of the absorption system is provided by the technology own system or by a heat exchanger on an external loop. In particular, it may be a heat transfer fluid, preferably water, circulating in a double outer envelope to said absorption system.
Selon le procédé de l'invention, la distillation opérée est une distillation réactive. L'équilibre de la réaction 1 ci-dessus, thermodynamiquement déplacé vers le sens conduisant à la production de MF et HF, est déplacé vers la production désirée dudit fluorure métallique par la distillation de l'hydracide HX.  According to the process of the invention, the distillation carried out is a reactive distillation. The equilibrium of reaction 1 above, thermodynamically shifted in the direction leading to the production of MF and HF, is shifted to the desired production of said metal fluoride by the distillation of HX hydracid.
Après absorption dans l'eau au sein du système d'absorption, préférentiellement au sein d'un absorbeur fonctionnant à co-courant, l'hydracide se trouve présent en solution aqueuse laquelle est en partie rétrogradée en tête de colonne de distillation tandis que l'autre partie est récupérée. Le débit de la solution aqueuse d'hydracide introduite en tête de colonne est inférieur au débit total de vapeurs d'hydracide circulant en tête de colonne. Selon l'invention, l'introduction en continu d'un fluide, préférentiellement d'eau, dans le système d'absorption conduit à une parfaite séparation de l'acide fluorhydrique de l'hydracide HX formé: la solution aqueuse contenant l'hydracide est très avantageusement dépourvue d'acide fluorhydrique.  After absorption into the water within the absorption system, preferably in an absorber operating cocurrently, the hydracid is present in aqueous solution which is partially demoted to the top of the distillation column while the other part is recovered. The flow rate of the aqueous solution of hydracid introduced at the top of the column is less than the total flow rate of hydracid vapors circulating at the top of the column. According to the invention, the continuous introduction of a fluid, preferably water, into the absorption system leads to a perfect separation of the hydrofluoric acid from the hydracid HX formed: the aqueous solution containing the hydracid is very advantageously free of hydrofluoric acid.
Le procédé selon l'invention mis en œuvre dans le dispositif décrit ci-dessus conduit à la production d'une part d'une solution aqueuse dans laquelle se trouve présent l'hydracide et d'autre part d'une solution aqueuse de fluorure métallique présentant un rapport molaire X/F préférentiellement inférieur à 0,3, très préférentiellement inférieur à 0,2 et encore plus préférentiellement inférieur à 0,1 , où X est choisi parmi le chlore, le brome et l'iode.  The method according to the invention implemented in the device described above leads to the production of a part of an aqueous solution in which the hydracid is present and secondly of an aqueous solution of metallic fluoride. having a molar ratio X / F preferably less than 0.3, very preferably less than 0.2 and even more preferably less than 0.1, where X is selected from chlorine, bromine and iodine.
La figure 1 représente un dispositif de colonne à distiller pour la mise en œuvre du procédé de fluoration selon l'invention.  FIG. 1 represents a distillation column device for implementing the fluorination process according to the invention.
Dans le bouilleur (1 ) sont introduits séparément l'halogénure métallique MX par la ligne (2), l'acide fluorhydrique par la ligne (3) et éventuellement de l'eau par la ligne (4). Le bouilleur est équipé d'un système de chauffage (6) pour permettre de réaliser la réaction de fluoration à une température comprise entre 50 et 160°C. La colonne (5) contient des éléments permettant la mise en contact gaz / liquide, par exemple des plateaux ou du garnissage. En pied de colonne, la fraction la moins volatile des produits formés, à savoir le fluorure métallique, est récupérée dans le bouilleur (1 ). L'ensemble du mélange ainsi obtenu est chauffé et évaporé dans l'échangeur (6) - en boucle externe sur le schéma. La vapeur est réintroduite dans le bouilleur par la ligne (8) puis monte dans la colonne (5). En tête de colonne, la vapeur d'hydracide HX est envoyée par la ligne (9) dans un absorbeur fonctionnant à co-courant (10). Sur la figure 1 , l'absorbeur est un faisceau de tubes alimenté à co-courant plongé dans une calandre. De l'eau déminéralisée et la vapeur d'hydracide HX sont respectivement introduites par les lignes (1 1 ) et (9) en tête de l'absorbeur (10). Le système de refroidissement de l'absorbeur (10) est assuré par circulation d'un fluide de refroidissement, préférentiellement de l'eau, au sein d'une double enveloppe externe audit absorbeur (10) et dans laquelle est injectée ledit fluide de refroidissement, par exemple de l'eau, par la ligne (12) à une température comprise entre 10 et 70 °C. Le refroidissement de l'absorbeur se traduit par un échauffement du fluide de refroidissement lequel est évacué, réchauffé, par la ligne (13). La solution aqueuse liquide soutirée en queue de l'absorbeur (10) est introduite dans un ballon (14) pourvu d'un évent (15) permettant la régulation en pression de l'installation. La phase liquide formée d'une solution aqueuse d'hydracide extraite du ballon (14) est renvoyée en continu, pour une partie, par la ligne (16), en tête de colonne de distillation (5) tandis que l'autre partie constitue le distillât liquide qui est évacué par la ligne (17). En fin de réaction, la solution aqueuse de fluorure métallique est récupérée par la ligne (7) après ouverture de la vanne (18). In the boiler (1) are separately introduced the metal halide MX by the line (2), the hydrofluoric acid by the line (3) and optionally water through the line (4). The boiler is equipped with a heating system (6) to enable the fluorination reaction to be carried out at a temperature between 50 and 160 ° C. The column (5) contains elements allowing gas / liquid contacting, for example trays or packing. At the bottom of the column, the least volatile fraction of the products formed, namely metallic fluoride, is recovered in the boiler (1). The entire mixture thus obtained is heated and evaporated in the exchanger (6) - in an outer loop in the diagram. The steam is reintroduced into the boiler by the line (8) and then goes up in the column (5). At the top of the column, the hydrofluoric vapor HX is sent via line (9) into an absorber operating in cocurrent (10). In Figure 1, the absorber is a bundle of co-current fed tubes immersed in a calender. Demineralized water and hydrofluoric vapor HX are respectively introduced by the lines (1 1) and (9) at the head of the absorber (10). The cooling system of the absorber (10) is provided by circulating a cooling fluid, preferably water, within a double jacket external to said absorber (10) and into which said cooling fluid is injected. for example water, via line (12) at a temperature of between 10 and 70 ° C. The cooling of the absorber results in a heating of the cooling fluid which is discharged, heated, by the line (13). The liquid aqueous solution withdrawn at the bottom of the absorber (10) is introduced into a flask (14) provided with a vent (15) allowing the pressure regulation of the installation. The liquid phase formed of an aqueous solution of hydracid extracted from the flask (14) is returned continuously, for a part, by the line (16) at the top of the distillation column (5) while the other part constitutes the liquid distillate which is evacuated by the line (17). At the end of the reaction, the aqueous solution of metal fluoride is recovered via line (7) after opening of the valve (18).
Le procédé selon l'invention est avantageusement conduit dans un dispositif susceptible de résister à la corrosion du milieu réactionnel. Le dispositif est réalisé en un ou plusieurs matériau(x) résistant à la corrosion. De manière préférée, le matériau constituant le bouilleur et la colonne de distillation est choisi parmi les matériaux graphites, le carbure de silicium et les polymères fluorés. Parmi les polymères fluorés, le PTFE (polytétrafluoroéthylène), le PVDF (polyfluorure de vinylidène), le FEP (copolymère d'hexafluoropropylène et de tétrafluoroéthylène) et le PFA (résines perfluoroalkyles) sont particulièrement adaptés. On ne sortirait pas du cadre de l'invention à utiliser un matériau de nature équivalente. La colonne de distillation peut être réalisée, sur toute sa longueur, d'un seul matériau résistant à la corrosion ou d'une succession de tronçons, chacun d'eux étant réalisé en un matériau différent. Le système d'absorption est par exemple réalisé en un matériau choisi parmi les matériaux graphites, les polymères fluorés, le PPHD (polypropylène haute densité), le PEHD (polyéthylène haute densité), l'acier vitrifié, les alliages à base de molybdène, chrome, cobalt, fer, cuivre, manganèse, titane, zirconium, aluminium, carbone et tungstène vendus sous les marques HASTELLOY® ou les alliages de nickel, chrome, fer, manganèse additivés de cuivre et/ou molybdène commercialisés sous la dénomination INCONEL® et plus particulièrement les alliages HASTELLOY C 276 ou INCONEL 600, 625 ou 718. The process according to the invention is advantageously carried out in a device capable of resisting corrosion of the reaction medium. The device is made of one or more corrosion resistant material (s). Preferably, the material constituting the boiler and the distillation column is chosen from graphite materials, silicon carbide and fluoropolymers. Of the fluoropolymers, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), FEP (hexafluoropropylene tetrafluoroethylene copolymer) and PFA (perfluoroalkyl resins) are particularly suitable. It would not be outside the scope of the invention to use a material of equivalent nature. The distillation column may be made, throughout its length, of a single material resistant to corrosion or a succession of sections, each of them being made of a different material. The absorption system is for example made of a material chosen from graphite materials, fluorinated polymers, PPHD (high density polypropylene), HDPE (high density polyethylene), vitreous steel, molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten alloys sold under the trade names HASTELLOY ® or nickel, chromium alloys , iron, manganese additivés of copper and / or molybdenum marketed under the name INCONEL ® and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718.
Le procédé de fluoration selon l'invention est un procédé simple à mettre en œuvre, opérant dans des conditions douces en milieu aqueux. Il conduit à la coproduction d'une solution aqueuse d'hydracide HX et d'une solution aqueuse de fluorure métallique MF. La solution aqueuse d'hydracide HX est avantageusement valorisée comme matière première dans l'industrie chimique. Un des avantages de la mise en œuvre du procédé de l'invention selon le dispositif bouilleur/colonne de distillation/système d'absorption réside dans la possibilité d'obtenir une solution aqueuse d'hydracide HX, par exemple une solution aqueuse d'HCI, à la concentration souhaitée, en fonction de la quantité d'eau introduite dans le système d'absorption. La solution aqueuse de fluorure métallique MF peut être directement employée pour des applications impliquant l'emploi d'une solution aqueuse à base de sels de cations métalliques M et d'anions fluorures ou elle peut être séchée par atomisation ou concentrée par évaporation de l'eau. Ladite solution aqueuse de fluorure métallique est obtenue avec une pureté optimale, c'est-à-dire présentant un taux résiduel d'halogène X (X = Cl, Br ou I) faible. Ladite solution aqueuse de fluorure métallique MF présente un rapport molaire X/F préférentiellement inférieur à 0,3, très préférentiellement inférieur à 0,2, plus préférentiellement inférieur à 0,1 , et encore plus préférentiellement inférieur à 0,05, où X est choisi parmi le chlore, le brome et l'iode. Le procédé selon l'invention est particulièrement préféré pour la mise en œuvre de la réaction de fluoration du chlorure de potassium avec l'acide fluorhydrique en milieu aqueux. Il en résulte la coproduction d'une solution aqueuse d'acide chlorhydrique et d'une solution aqueuse de fluorure de potassium. Le procédé de fluoration de l'invention repose sur une technologie simple, respectueuse de l'environnement dès lors que les produits obtenus se trouvent présents en solution aqueuse, peu coûteuse en terme énergétique, en particulier au regard de la technologie existante qui nécessite une étape de thermolyse. The fluorination process according to the invention is a process that is simple to implement, operating under mild conditions in an aqueous medium. It leads to the co-production of an aqueous solution of HX hydracid and an aqueous solution of MF metal fluoride. The aqueous solution of HX hydracid is advantageously promoted as a raw material in the chemical industry. One of the advantages of implementing the method of the invention according to the boiler / distillation column / absorption system device is the possibility of obtaining an aqueous solution of HX hydracid, for example an aqueous solution of HCl at the desired concentration, depending on the amount of water introduced into the absorption system. The aqueous solution of metal fluoride MF can be directly used for applications involving the use of an aqueous solution based on salts of metal cations M and fluoride anions or it can be spray dried or concentrated by evaporation of the water. Said aqueous solution of metal fluoride is obtained with optimum purity, that is to say having a low residual level of halogen X (X = Cl, Br or I). Said aqueous solution of metal fluoride MF has a molar ratio X / F preferably less than 0.3, very preferably less than 0.2, more preferably less than 0.1, and even more preferably less than 0.05, where X is selected from chlorine, bromine and iodine. The process according to the invention is particularly preferred for carrying out the fluorination reaction of potassium chloride with hydrofluoric acid in an aqueous medium. This results in the co-production of an aqueous solution of hydrochloric acid and an aqueous solution of potassium fluoride. The fluorination process of the invention is based on a simple and environmentally friendly technology provided that the products obtained are present in aqueous solution, which is inexpensive in terms of energy, in particular with regard to the existing technology which requires a step thermolysis.
Le procédé de fluoration selon l'invention est avantageusement appliqué pour le traitement de flux aqueux contenant au moins un halogénure métallique MX tel que défini plus haut dans la présente description. Le procédé de fluoration selon l'invention est parfaitement adapté pour le traitement d'effluents aqueux contenant ledit halogénure métallique, seul ou en mélange avec d'autres espèces minérales, par exemple avec d'autres halogénures métalliques, tels que des fluorures métalliques, ou encore avec des espèces minérales oxygénées tels que les carbonates ou les oxydes. Ledit halogénure métallique MX est notamment présent dans des effluents produits par la mise en œuvre d'une réaction d'échange halogène/fluor entre un substrat halogéné et un sel apportant un anion fluorure. Ledit substrat halogéné comprend au moins un atome d'halogène différent du fluor. Par exemple ledit substrat halogéné présente la formule suivante : HCX1X2 - COOR-ι , avec The fluorination process according to the invention is advantageously applied for the treatment of aqueous flux containing at least one metal halide MX as defined above in the present description. The fluorination process according to the invention is perfectly suitable for the treatment of aqueous effluents containing said halide metal, alone or mixed with other mineral species, for example with other metal halides, such as metal fluorides, or with oxygenated mineral species such as carbonates or oxides. Said metal halide MX is especially present in effluents produced by the implementation of a halogen / fluorine exchange reaction between a halogenated substrate and a salt providing a fluoride anion. Said halogenated substrate comprises at least one halogen atom different from fluorine. For example, said halogenated substrate has the following formula: HCX 1 X 2 - COOR-ι, with
- Xi et X2, identiques ou différents, représentent un atome de chlore, de brome ou de fluor avec la condition qu'au moins l'un des atomes X-i , X2 est un atome de chlore ou de brome, - X 1 and X 2 , which may be identical or different, represent a chlorine, bromine or fluorine atom with the proviso that at least one of the atoms X 1 , X 2 is a chlorine or bromine atom,
- Ri représente :  Ri represents:
. un atome d'hydrogène,  . a hydrogen atom,
. un groupe hydrocarboné, substitué ou non, qui peut être un groupe alkyle ou cycloalkyle,  . a hydrocarbon group, substituted or unsubstituted, which may be an alkyl or cycloalkyl group,
. un cation métallique  . a metal cation
L'invention est illustrée au moyen des exemples suivants. Exemple 1 (invention) : The invention is illustrated by means of the following examples. Example 1 (invention)
Le dispositif utilisé dans cet exemple est équipé d'un réacteur-bouilleur en PTFE de 200 ml à double enveloppe surmonté d'une colonne à distiller en PTFE (hauteur de 200 mm, diamètre de 30 mm) remplie d'un garnissage en PTFE de 12 étages théoriques, ladite colonne étant elle-même surmonté d'un absorbeur de gaz fonctionnant à contre courant. Ledit absorbeur est une colonne, en PTFE, de 30 mm de diamètre et de 200 mm de hauteur, remplie d'anneaux de type Rashig et alimentée à contre-courant, le gaz (à savoir les vapeurs de HCI dans cet exemple) arrivant en bas de la colonne (jouant le rôle d'absorbeur) et l'eau (flux 1 1 ) arrivant par le haut. L'absorbeur est muni d'une double enveloppe externe dans laquelle circule de l'eau pour assurer le refroidissement au sein de l'absorbeur. L'ensemble du dispositif est placé à pression atmosphérique. The device used in this example is equipped with a double-shelled 200 ml PTFE boiler-reactor surmounted by a PTFE distillation column (height 200 mm, diameter 30 mm) filled with a PTFE packing of 12 theoretical stages, said column being itself surmounted by a gas absorber operating against the current. Said absorber is a column, of PTFE, 30 mm in diameter and 200 mm in height, filled with Rashig-type rings and supplied with counter-current, the gas (namely the vapors of HCl in this example) arriving in bottom of the column (playing the role of absorber) and water (stream 1 1) arriving from above. The absorber is provided with an outer double jacket in which water circulates to ensure cooling within the absorber. The entire device is placed at atmospheric pressure.
On introduit dans le réacteur 103,7 g de KCI (1 ,38 mol) et 300 g d'une solution de HF 40% (6 mol). Le pH du mélange réactionnel est voisin de 1 . 103.7 g of KCl (1.38 mol) and 300 g of a solution of 40% HF (6 mol) are introduced into the reactor. The pH of the reaction mixture is close to 1.
La température de la double enveloppe externe au bouilleur est portée à 160°C pour une durée de 12 heures. Lorsque la température du bouilleur est égale à 1 13°C, l'absorbeur de gaz est alimenté en tête par un débit d'eau permutée, en continu, correspondant à une quantité totale de 89 g au cours de l'expérience sur une durée de 12 heures (flux 1 1 ). La température en tête de colonne de distillation monte progressivement jusqu'à 104°C. L'absorbeur est refroidi par de l'eau circulant dans une double enveloppe à une température égale à 15°C. La température de la phase aqueuse où se trouve présent HCI (flux entrant dans le ballon 14) est égale à 25°C. The temperature of the outer jacket to the boiler is increased to 160 ° C for a period of 12 hours. When the temperature of the boiler is equal to 13 ° C, the absorber of gas is fed at the top by a flow of water permuted, continuously, corresponding to a total amount of 89 g during the experiment over a period of 12 hours (flow 1 1). The temperature at the top of the distillation column rises gradually to 104 ° C. The absorber is cooled by water circulating in a jacket at a temperature of 15 ° C. The temperature of the aqueous phase in which HCl is present (flow entering the flask 14) is equal to 25 ° C.
Une partie du flux aqueux comprenant HCI, en sortie de l'absorbeur, est ré-introduite dans la colonne à distiller (flux 16) : la quantité totale de solution aqueuse ré-introduite dans la colonne à distiller au cours de l'expérience est égale à 302 g sur une durée de 12 h. En fin de réaction, le reste du flux (flux n°17) est récolté et le total recueilli est de 1 12 g titrant 333 g/l de chlorure et 9,1 g/l de protons.  Part of the aqueous stream comprising HCl, at the outlet of the absorber, is re-introduced into the distillation column (stream 16): the total amount of aqueous solution re-introduced into the distillation column during the experiment is equal to 302 g over a period of 12 hours. At the end of the reaction, the remainder of the stream (stream No. 17) is collected and the total collected is 1 12 g containing 333 g / l of chloride and 9.1 g / l of protons.
Après 12 heures de réaction, le réacteur est vidangé. On obtient 331 g d'une solution aqueuse de fluorure de potassium (flux 7) qui se solidifie lors de son retour à température ambiante. Une analyse par chromatographie ionique du produit final constituant le flux 7 indique la présence de 5,1 mol de fluorures (29,3 % p/p), 1 ,38 mol de potassium (16,2 % p/p) et 0,4 mmol de chlorures (4,4 % p/p). Le rapport molaire Cl/F dans ledit produit final est égal à 0,07. After 12 hours of reaction, the reactor is drained. 331 g of an aqueous solution of potassium fluoride (stream 7) are obtained which solidifies when it returns to ambient temperature. Ion chromatographic analysis of the final product constituting stream 7 indicates the presence of 5.1 mol of fluorides (29.3% w / w), 1.38 mol of potassium (16.2% w / w) and 0, 4 mmol of chlorides (4.4% w / w). The molar ratio Cl / F in said final product is equal to 0.07.

Claims

REVENDICATIONS
1. Procédé de fluoration d'au moins un halogénure métallique MX où M est un métal choisi parmi les métaux alcalins et les métaux alcalino-terreux et X est un halogène choisi parmi le chlore, le brome et l'iode, ledit procédé étant mis en œuvre dans un dispositif équipé d'un bouilleur où se produit une réaction de fluoration, en présence d'eau, entre de l'acide fluorhydrique et au moins ledit halogénure métallique MX, d'une colonne de distillation où circulent des vapeurs d'hydracide HX formé et d'un système d'absorption des vapeurs d'hydracide HX placé en tête de ladite colonne. A method of fluorinating at least one metal halide MX where M is a metal selected from alkali metals and alkaline earth metals and X is a halogen selected from chlorine, bromine and iodine, said process being carried out implemented in a device equipped with a boiler where a fluorination reaction occurs, in the presence of water, between hydrofluoric acid and at least said metal halide MX, a distillation column where circulating vapors HX hydracid formed and a hydrogen acid vapor absorption system HX placed at the head of said column.
2. Procédé de fluoration selon la revendication 1 dans lequel ledit métal M est choisi parmi le lithium, le sodium et le potassium. 2. fluorination process according to claim 1 wherein said metal M is selected from lithium, sodium and potassium.
3. Procédé de fluoration selon la revendication 1 ou la revendication 2 dans lequel X est le chlore. The fluorination process of claim 1 or claim 2 wherein X is chlorine.
4. Procédé de fluoration selon l'une des revendications 1 à 3 dans lequel l'halogénure métallique MX est le chlorure de potassium. 4. fluorination process according to one of claims 1 to 3 wherein the metal halide MX is potassium chloride.
5. Procédé de fluoration selon l'une des revendications 1 à 4 dans lequel le mélange réactionnel aqueux comprend un mélange d'halogénures métalliques. 5. fluorination process according to one of claims 1 to 4 wherein the aqueous reaction mixture comprises a mixture of metal halides.
6. Procédé de fluoration selon la revendication 5 dans lequel ledit mélange réactionnel comprend ledit halogénure métallique MX et un fluorure métallique M'F dans lequel le métal M', choisi parmi les métaux alcalins et alcalino-terreux, est identique ou différent au métal M présent dans ledit halogénure métallique MX. The fluorination process of claim 5 wherein said reaction mixture comprises said metal halide MX and a metal fluoride M'F wherein the metal M ', selected from alkali and alkaline earth metals, is the same as or different from the metal M present in said metal halide MX.
7. Procédé de fluoration selon l'une des revendications 1 à 6 dans lequel le mélange réactionnel aqueux comprend des espèces minérales autres que le(s)dit(s) halogénure(s) métallique(s). 7. fluorination process according to one of claims 1 to 6 wherein the aqueous reaction mixture comprises mineral species other than the (s) said (s) metal halide (s).
8. Procédé de fluoration selon l'une des revendications 1 à 7 dans lequel le mélange réactionnel aqueux comprend au moins un acide autre que l'acide fluorhydrique. 8. fluorination process according to one of claims 1 to 7 wherein the aqueous reaction mixture comprises at least one acid other than hydrofluoric acid.
9. Procédé de fluoration selon l'une des revendications 1 à 8 dans lequel le(s)dit(s) halogénure(s) métallique(s) MX et l'acide fluorhydrique sont utilisés dans une proportion telle que 0,5 à 5 équivalent(s) molaire(s) d'anions fluorures par atome d'halogène X est(sont) mis en œuvre. 9. fluorination process according to one of claims 1 to 8 wherein the (s) says (s) metal halide (s) MX and hydrofluoric acid are used in such a proportion 0.5 to 5 molar equivalent (s) of fluoride anions per halogen atom X is (are) used.
10. Procédé de fluoration selon l'une des revendications 1 à 9 dans lequel ladite quantité d'eau présente dans le mélange réactionnel aqueux est telle que le rapport molaire halogénure(s) métallique(s) MX/eau est compris entre 0,01 et 1 . 10. fluorination process according to one of claims 1 to 9 wherein said amount of water present in the aqueous reaction mixture is such that the molar ratio metal halide (s) MX / water is between 0.01 and 1.
1 1. Procédé de fluoration selon l'une des revendications 1 à 10 dans lequel la réaction de fluoration en elle-même, réalisée entre au moins ledit halogénure métallique MX et l'acide fluorhydrique, est mise en œuvre à une température comprise entre 50 et 160°C. 1 1. fluorination process according to one of claims 1 to 10 wherein the fluorination reaction itself, carried out between at least said metal halide MX and hydrofluoric acid is carried out at a temperature between 50 and 160 ° C.
12. Procédé de fluoration selon l'une des revendications 1 à 1 1 tel qu'en fin de réaction, le bouilleur est vidangé de manière à récupérer une solution aqueuse de fluorure métallique MF présentant un rapport molaire X/F inférieur à 0,3. 12. fluorination process according to one of claims 1 to 1 1 such that at the end of the reaction, the boiler is drained so as to recover an aqueous solution of MF metal fluoride having a molar ratio X / F less than 0.3. .
13. Procédé de fluoration selon l'une des revendications 1 à 12 tel que lesdites vapeurs d'hydracide sont mises en contact avec de l'eau dans ledit système d'absorption. 13. fluorination process according to one of claims 1 to 12 such that said vapors of hydracid are brought into contact with water in said absorption system.
14. Procédé de fluoration selon l'une des revendications 1 à 13 tel que ledit système d'absorption est refroidi par un système de refroidissement tel que la température au sein dudit système d'absorption est comprise entre 10 et 70°C. 14. fluorination process according to one of claims 1 to 13 such that said absorption system is cooled by a cooling system such that the temperature within said absorption system is between 10 and 70 ° C.
15. Procédé de fluoration selon l'une des revendications 1 à 14 tel que l'hydracide se trouve présent en solution aqueuse après absorption dans l'eau au sein dudit système d'absorption. 15. fluorination process according to one of claims 1 to 14 such that the hydracid is present in aqueous solution after absorption in water within said absorption system.
16. Procédé de fluoration selon la revendication 15 tel que la température de ladite solution aqueuse comprenant l'hydracide sortant dudit système d'absorption est comprise entre 20 et 90°C. The fluorination process according to claim 15, wherein the temperature of said aqueous solution comprising the hydracid exiting said absorption system is between 20 and 90 ° C.
17. Procédé de fluoration selon l'une des revendications 1 à 16 tel que le matériau constituant le bouilleur et la colonne de distillation est choisi parmi les matériaux graphites, le carbure de silicium et les polymères fluorés. 17. fluorination process according to one of claims 1 to 16 such that the material constituting the boiler and the distillation column is selected from graphite materials, silicon carbide and fluoropolymers.
18. Procédé selon l'une des revendications 1 à 17 dans lequel ledit halogénure métallique MX est présent dans des effluents produits par la mise en œuvre d'une réaction d'échange halogène/fluor entre un substrat halogéné et un sel apportant un anion fluorure. 18. Method according to one of claims 1 to 17 wherein said metal halide MX is present in effluents produced by the implementation of a halogen / fluorine exchange reaction between a halogenated substrate and a salt providing a fluoride anion .
PCT/EP2012/065465 2011-08-12 2012-08-07 Method of fluorination of a metal halide in an aqueous medium WO2013023964A1 (en)

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