WO2013023964A1 - Procede de fluoration d'un halogenure metallique en milieu aqueux - Google Patents

Procede de fluoration d'un halogenure metallique en milieu aqueux 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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WIPO (PCT)
Prior art keywords
metal
process according
metal halide
fluorination process
fluorination
Prior art date
Application number
PCT/EP2012/065465
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English (en)
French (fr)
Inventor
Olivier Buisine
Julien TOURNAYRE
Original Assignee
Rhodia Operations
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations filed Critical Rhodia Operations
Priority to CN201280044082.9A priority Critical patent/CN103781725A/zh
Priority to IN1632DEN2014 priority patent/IN2014DN01632A/en
Publication of WO2013023964A1 publication Critical patent/WO2013023964A1/fr

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Classifications

    • 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.

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  • Inorganic Chemistry (AREA)
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PCT/EP2012/065465 2011-08-12 2012-08-07 Procede de fluoration d'un halogenure metallique en milieu aqueux WO2013023964A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280044082.9A CN103781725A (zh) 2011-08-12 2012-08-07 在水性介质中氟化金属卤化物的方法
IN1632DEN2014 IN2014DN01632A (enrdf_load_html_response) 2011-08-12 2012-08-07

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FR1157318 2011-08-12
FR1157318 2011-08-12

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J. S. THRASHER; S. STRAUSS: "Inorgic Fluorine Chemistry", 1994, ACS SYMPOSIUM SERIES 555, pages: 237

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