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    • 专利摘要:
    The invention relates to a method for treating a gas stream containing hydrochloric acid, hydrofluoric acid and fluoro-oxygen compounds, wherein the gas stream is successively subjected to: a catalytic hydrolysis step; a washing step with an acidic solution; a step of adsorbing impurities with activated carbon; an adiabatic or isothermal absorption step of hydrochloric acid in an aqueous solution, making it possible to collect a solution of hydrochloric acid.
    公开号:FR3013606A1
    申请号:FR1361736
    申请日:2013-11-28
    公开日:2015-05-29
    发明作者:Bertrand Collier；Dominique Deur-Bert；Anne Pigamo；Joaquin Lacambra
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method for purifying hydrochloric acid, as well as to an installation adapted to the implementation of this process. BACKGROUND OF THE INVENTION The invention can be used in particular in the context of the treatment of effluents resulting from a catalytic fluorination reaction.
    [0002] BACKGROUND It is known to produce fluorinated compounds such as hydrofluorocarbons by fluorination of chlorinated compounds such as hydrochlorocarbons in particular. This fluorination is generally a catalytic fluorination using hydrofluoric acid (HF) as fluorinating agent. During this type of reaction, hydrochloric acid (HCl) is co-produced. It is known to separate the HCl from the other gases produced via a distillation column and then to absorb the HCl in an adiabatic absorption column to generate a commercial type HCl solution. The document FR 1507252 describes stages of treatment with active carbon, at high temperature and in the presence of water, and washing with concentrated aqueous hydrochloric acid.
    [0003] US 3,353,911 describes the purification of an HF / HCl gas mixture by contact with an absorbent solution, which is a saturated solution of boric acid. However, the known techniques for purifying hydrochloric acid do not allow, in certain cases, to reach the purity of HCl required. There is therefore a need to provide an improved method for purifying hydrochloric acid in a gas stream. SUMMARY OF THE INVENTION The invention relates first of all to a method of treating a gas stream containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds, in which the gas stream is successively subjected to: a catalytic hydrolysis step; a washing step with an acidic solution; a step of adsorbing impurities with activated carbon; an adiabatic or isothermal absorption step of hydrochloric acid in an aqueous solution, making it possible to collect a solution of hydrochloric acid. According to one embodiment, the catalytic hydrolysis step is performed on a bed of activated carbon. According to one embodiment, the acid solution used during the washing step is a hydrochloric acid solution and preferably comes from the hydrochloric acid solution collected at the end of the adiabatic or isothermal absorption step. . According to one embodiment, the method further comprises: a step of bringing the hydrochloric acid solution into contact with a silica gel. According to one embodiment, the fluoro-oxygenated compounds comprise carbonyl difluoride, chlorofluorocarbonyl, trifluoroacetyl fluoride and / or trifluoroacetic acid; and preferably, the gaseous stream comprises at least 50 mg / l, in particular at least 100 mg / l, or even at least 200 mg / l of trifluoroacetyl fluoride and / or trifluoroacetic acid. In one embodiment, boric acid is added to the acid solution used for the washing step. According to one embodiment, the gas stream is a stream resulting from a catalytic fluorination reaction of at least one chlorinated compound in at least one fluorinated compound, said stream preferably being collected at the outlet of a distillation of a stream. of products of the catalytic fluorination reaction. According to one embodiment, the catalytic fluorination reaction is carried out in the presence of oxygen.
    [0004] According to one embodiment: the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; the chlorinated compound is preferably chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane. , 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and their mixtures; and preferably the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 2-chloroacethane, 3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof. The invention also relates to a process for preparing a fluorinated compound comprising: - providing a chlorinated compound and hydrofluoric acid; the catalytic reaction of the chlorinated compound with hydrofluoric acid and the collection of a flow of raw products; separation of the stream of raw products, preferably by distillation, making it possible to recover, on the one hand, a stream of fluorinated compound and, on the other hand, a gas stream containing mainly hydrochloric acid, as well as minority amounts of hydrofluoric acid and fluoro-oxygen compounds; the treatment of the gaseous flow containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds as described above. According to one embodiment, the catalytic reaction is carried out in the presence of oxygen. According to one embodiment: the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; the chlorinated compound is preferably chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane. , 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and their mixtures; and preferably the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 2-chloroacethane, 3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof. The invention also relates to a plant for treating a gaseous flow containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds, comprising: a feed gas flow line containing hydrochloric acid; , hydrofluoric acid and fluorooxygen compounds, feeding a catalytic hydrolysis unit; a washing unit, fed on the one hand by a hydrolysed gas flow collection line from the catalytic hydrolysis unit, and on the other hand by an acid solution supply line; an impurity adsorption unit, comprising an active charcoal bed, fed by a washed gas flow collection line coming from the washing unit; an adiabatic or isothermal absorption unit fed on the one hand by a purified or isothermal flow collection line resulting from the adsorption unit and on the other hand by an aqueous solution supply line; a collection line of hydrochloric acid solution at the outlet of the adiabatic or isothermal absorption unit. According to one embodiment, the catalytic hydrolysis unit comprises a bed of activated carbon.
    [0005] According to one embodiment, the acid solution supply pipe is directly or indirectly derived from the hydrochloric acid solution collection pipe. According to one embodiment, the installation further comprises: a complementary adsorption unit comprising a silica gel fed by the hydrochloric acid solution collection pipe; and a collection line of purified hydrochloric acid solution from the additional adsorption unit. According to one embodiment, the installation comprises an addition of boric acid solution to the washing unit. According to one embodiment, the gas flow supply line containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds is derived from a distillation unit; the distillation unit is preferably fed by a raw product collection pipe at the outlet of a catalytic reactor. According to one embodiment, the catalytic reactor is fed by a chlorine compound supply line and a hydrofluoric acid supply line, and the raw product collection line carries a stream comprising a fluorinated compound, and preferably - the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; more particularly, the chlorinated compound is chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane. , 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and their mixtures; and more particularly the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof.
    [0006] According to one embodiment, the installation comprises a supply of oxygen to the catalytic reactor. The present invention overcomes the disadvantages of the state of the art. More particularly, it provides an improved method for purifying hydrochloric acid in a gas stream. This is accomplished through the implementation of three successive treatment steps of the gas stream, namely a catalytic hydrolysis step, a washing step and an adsorption step on activated carbon, and this before the step of adiabatic or isothermal absorption generating a concentrated hydrochloric acid solution. The invention is based on the identification by the present inventors that the HCl gas recovered at the top of the distillation column can be contaminated by a small amount of free HF (entrained due to azeotropes with light fluorinated compounds) but also by fluorinated oxygen compounds, such as carbonyl difluoride (COF2), carbonyl chlorofluoride (COFCI) and trifluoroacetyl fluoride (CF3COF). These compounds are in particular generated when the gas stream to be treated is derived from a fluorination reaction carried out in the presence of oxygen.
    [0007] These compounds are highly toxic and are hydrolyzable. They are therefore likely to release HF in particular during the adiabatic or isothermal absorption step in water, thus contaminating the HCl solution obtained with HF. In addition, trifluoroacetyl fluoride generates trifluoroacetic acid (or TFA) during its hydrolysis, which compound is harmful. The invention makes it possible to separate the HCl from the HF with which it is mixed, but also to separate it from the fluoro-oxygenated compounds mentioned above. The invention is also based on the identification by the present inventors that the HCl gas recovered at the top of the distillation column can be contaminated with light organic compounds. The invention also makes it possible to eliminate these light organic compounds satisfactorily during processing. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 schematically represents an embodiment of an installation according to the invention.
    [0008] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. The invention applies in particular to the treatment of a gas stream resulting from a catalytic fluorination reaction of at least one chlorinated compound in at least one fluorinated compound. The gaseous flow treated according to the invention may be directly the gaseous flow of products from the reactor, or more preferably a flow resulting from a distillation (carried out in a distillation column or in a series of several successive distillation columns) after the catalytic fluorination. In this case, the gaseous flow to be treated according to the invention has previously been essentially separated from the fluorinated compound and / or the unreacted chlorine compound and / or by-products of the reaction. The gas stream to be treated according to the invention preferably contains predominantly HCl, with minor amounts of contaminants such as HF and fluoro-oxygenated compounds mentioned above (and in particular trifluoroacetyl fluoride). By chlorinated compound (which represents the main reagent of the catalytic fluorination reaction) is meant an organic compound comprising one or more chlorine atoms, and by fluorinated compound (which represents the desired product of the catalytic fluorination reaction), is meant an organic compound comprising one or more fluorine atoms. It is understood that the chlorinated compound may comprise one or more fluorine atoms, and that the fluorinated compound may comprise one or more chlorine atoms. In general, the number of chlorine atoms of the fluorinated compound is less than the number of chlorine atoms of the chlorinated compound; and the number of fluorine atoms of the fluorinated compound is greater than the number of fluorine atoms of the chlorinated compound. The chlorinated compound may be an alkane or an alkene optionally having substituents selected from F, Cl, I and Br (preferably from F and Cl), and having at least one Cl substituent. The fluorinated compound may be an alkane or an alkene optionally having substituents selected from F, Cl, I and Br (preferably from F and Cl), and having at least one substituent F.
    [0009] The chlorinated compound may especially be an alkane with one or more substituents chlorine (hydrochlorocarbon or chlorocarbon) or an alkane with one or more substituents chlorine and fluorine (hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one or more substituents chlorine (chloroolefin or hydrochlorohefin) or an alkene with one or more substituents chlorine and fluorine (hydrochlorofluoroolefin or chlorofluoroolefin). The fluorinated compound may in particular be an alkane with one or more fluorine substitutions (fluorocarbon or hydrofluorocarbon) or an alkane with one or more substituents chlorine and fluorine (hydrochlorofluorocarbon or chlorofluorocarbon) or an alkene with one or more fluorine substituents (fluoroolefin or hydrofluoroolefin) or an alkene with one or more substituents chlorine and fluorine (hydrochlorofluoroolefin or chlorofluoroolefin).
    [0010] The chlorinated compound and the fluorinated compound may be linear or branched, preferably linear. According to one embodiment, the chlorinated compound and the fluorinated compound comprise a single carbon atom. According to one embodiment, the chlorinated compound and the fluorinated compound comprise two carbon atoms. According to one embodiment, the chlorinated compound and the fluorinated compound comprise three carbon atoms. According to one embodiment, the chlorinated compound and the fluorinated compound comprise four carbon atoms.
    [0011] According to one embodiment, the chlorinated compound and the fluorinated compound comprise five carbon atoms. The invention is particularly applicable to the following fluorination reactions: fluorination of perchlorethylene (PER) to pentafluoroethane (HFC-125); - fluorination of 1,1,1,2,3-pentachloropropane (HCC-240db) to 2-chloro-3,3,3-trifluoropropene (HCF0-1233xf), - fluorination of 1,1,1,2,3- pentachloropropane (HCC-240db) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 1,1,1,3,3-pentachloropropane (HCC-240fa) to 1,3,3,3-tetrafluoropropene (HFO-1234ze); fluorination of 1,1,1,3,3-pentachloropropane (HCC-240fa) to 1-chloro-3,3,3-trifluoropropene (HCF0-1233zd); fluorination of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 1,1,2,2,3-pentachloropropane (HCC-240aa) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 1,1,2,2,3-pentachloropropane (HCC-240aa) to 2-chloro-3,3,3-trifluoropropene (HCF0-1233xf); fluorination of 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 1-chloro-3,3,3-trifluoropropene (HCF0-1233zd); fluorination of 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 1,3,3,3-tetrafluoropropene (HFO-1234e); fluorination of 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2-chloro-3,3,3-trifluoropropene (HCF0-1233xf); fluorination of 1,1,2,3-tetrachloropropene (HCO-1230xa) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 1,1,2,3-tetrachloropropene (HCO-1230xa) to 2-chloro-3,3,3-trifluoropropene (HCF0-1233xf); fluorination of 2,3,3,3-tetrachloropropene (HCO-1230xf) to 2,3,3,3-tetrafluoropropene (HFO-1234yf); fluorination of 2,3,3,3-tetrachloropropene (HCO-1230xf) to 2-chloro-3,3,3-trifluoropropene (HCF0-1233xf); fluorination of 1,1,3,3-tetrachloropropene (HCO-1230za) to 1-chloro-3,3,3-trifluoropropene (HCF0-1233zd); fluorination of 1,1,3,3-tetrachloropropene (HCO-1230za) to 1,3,3,3-tetrafluoropropene (HFO-1234ze); fluorination of 1,3,3,3-tetrachloropropene (HCO-1230zd) to 1-chloro-3,3,3-trifluoropropene (HCF0-1233zd); fluorination of 1,3,3,3-tetrachloropropene (HCO-1230zd) to 1,3,3,3-tetrafluoropropene (HFO-1234ze); - fluorination of 1-chloro-3,3,3-trifluoropropene (HCF0-1233zd) to 1,3,3,3-tetrafluoropropene (HF0-1234ze); fluorination of 1,1,2-trichloroethane to 1-chloro, 2,2-difluoroethane (HCFC-142); - fluorination of 1,2-dichloroethylene to 1-chloro-2,2-difluoroethane (HCFC-142) The conversion of the chlorinated compound to the fluorinated compound may be a direct conversion (with a single reaction step or with a single set of conditions reaction) or indirect conversion (with two or more reaction steps or using two or more sets of reaction conditions). The fluorination reaction may be carried out: with an HF / chloro compound molar ratio of from 3: 1 to 150: 1, preferably from 4: 1 to 100: 1 and more preferably from 5: 1 to 50: 1 ; with a contact time of 1 to 100 seconds, preferably 1 to 50 seconds and more particularly 2 to 40 seconds (volume of catalyst divided by the total incoming flow, adjusted to the temperature and to the operating pressure); at an absolute pressure ranging from 0.1 to 50 bar, preferably from 0.3 to 15 bar; at a temperature (temperature of the catalyst bed) of 100 to 500 ° C, preferably of 200 to 450 ° C, and more particularly of 300 to 400 ° C. In order to avoid rapid deactivation of the catalyst during the reaction, an oxidation agent (for example oxygen or chlorine) may be added, for example in an oxidation agent / organic compounds molar ratio of 0.005 to 2, preferably from 0.01 to 1.5. For example, it is possible to use a flow of pure oxygen or pure chlorine, or an oxygen / nitrogen or chlorine / nitrogen mixture. Preferably, an oxygen-containing stream is used for the implementation of the fluorination (this use correspondingly entails the appearance in the product stream of contaminants such as trifluoroacetyl fluoride and fluorinated phosgene derivatives). The catalyst used may for example be based on a metal comprising a transition metal oxide or a derivative or a halide or an oxyhalide of such a metal. Mention may be made, for example, of FeCl 3, chromium oxyfluoride, chromium oxides (optionally subjected to fluorination treatments), chromium fluorides and mixtures thereof. Other possible catalysts are carbon supported catalysts, antimony catalysts, aluminum catalysts (for example AlF 3 and Al 2 O 3, alumina oxyfluoride and alumina fluoride). It is generally possible to use a chromium oxyfluoride, a fluoride or an aluminum oxyfluoride, or a supported or non-supported catalyst containing a metal such as Cr, Ni, Fe, Zn, Ti, V, Zr, Mo, Ge or Sn. Pb, Mg, Sb.
    [0012] Reference can be made in this regard to document WO 2007/079431 (at p.7, 1.1-5 and 28-32), EP 939071 (paragraph [0022]), WO 2008/054781 (at p.9). I.22-p.10 1.34), and WO 2008/040969 (claim 1), to which reference is expressly made. Prior to use, the catalyst is preferably activated with air, oxygen or chlorine and / or with HF. Before use, the catalyst is preferably subjected to activation with air or oxygen and HF at a temperature of 100 to 500 ° C, preferably 250 to 500 ° C and more preferably 300 to 500 ° C. 400 ° C. The activation time is preferably from 1 to 200 hours and more particularly from 1 to 50 hours. This activation may be followed by a final fluorination activation step in the presence of an oxidizing agent, HF and organic compounds.
    [0013] The molar ratio of HF / organic compounds is preferably from 2 to 40 and the molar ratio of oxidation agent / organic compounds is preferably from 0.04 to 25. The temperature of the final activation is preferably from 300 to 400 ° C. C and its duration preferably from 6 to 100 h. The catalyst is preferably based on chromium and is more particularly a mixed catalyst comprising chromium. According to one embodiment, a mixed catalyst comprising chromium and nickel is used. The molar ratio Cr / Ni (based on the metal element) is generally 0.5 to 5, for example 0.7 to 2, for example about 1. The catalyst may contain from 0.5 to 20% by weight of chromium, and from 0.5 to 20% by weight of nickel, preferably from 2 to 10% of each. The metal may be present in metallic form or in the form of a derivative, for example an oxide, halide or oxyhalide. These derivatives are preferably obtained by activation of the catalytic metal.
    [0014] The support is preferably made of aluminum, for example alumina, activated alumina or aluminum derivatives, such as aluminum halides and aluminum oxyhalides, for example described in US Pat. US 4,902,838, or obtained by the activation method described above.
    [0015] The catalyst may comprise chromium and nickel in an activated or non-activated form, on a support which has been subjected to activation or not. Reference can be made to WO 2009/118628 (in particular in p.4, I.30-p.71.16), to which reference is expressly made herein.
    [0016] Another preferred embodiment is based on a chromium-containing mixed catalyst and at least one element selected from Mg and Zn. The atomic ratio of Mg or Zn / Cr is preferably from 0.01 to 5. Referring now to FIG. 1, the plant according to the invention may comprise three successive treatment units, namely a unit of catalytic hydrolysis 2, a washing unit 4 and an adsorption unit for impurities 7, upstream of an adiabatic or isothermal absorption unit 9. Downstream of the absorption unit 9, an adsorption unit Complementary 13 is provided as an option.
    [0017] The gas stream to be treated, which preferably constitutes a part of a stream of catalytic fluorination reaction products (separated by distillation), is fed through a feed gas flow line 1 to the catalytic hydrolysis unit 2 In this catalytic hydrolysis unit 2, the fluoroxygenated compounds of the gas stream are hydrolysed. The main hydrolysis reactions are as follows: COF 2 + H 2 O CO 2 + HF COFCI + H 2 O CO 2 + HCl + HF CF 3 COF + H 2 O CF 3 COOH + HF The catalytic hydrolysis unit 2 is provided with a catalytic bed, which preferably is an active carbon bed. The temperature of the catalytic hydrolysis step is preferably from 100 to 200 ° C, in particular from 120 to 170 ° C, and more particularly from 130 to 150 ° C. The pressure is preferably 0.5 to 3 barg, especially 1 to 2 barg.
    [0018] The residence time of the species of interest in the unit is preferably from 1 s to 1 min, in particular from 2 s to 30 s, more particularly from 4 s to 15 s, and most particularly from 5 s to 10 s. The amount of water in the mixture subjected to catalytic hydrolysis is adjusted so that the molar ratio of water to the sum of the fluoro-oxygen compounds is greater than 1, preferably greater than or equal to 2, or at 3, or 4, or 5, or 6 or 6.5. A water supply can be provided if necessary. The degree of hydrolysis (molar proportion of hydrolysed fluoro-oxygenated compounds) is preferably greater than 90%, more particularly greater than 95%, 98%, 99%, 99.5%, 99.9%, 99.95% or 99.99%. At the outlet of the catalytic hydrolysis unit 2, the gas stream is taken from a hydrolysed gas stream collection pipe 3. This feeds a washing unit 4. The washing unit 4 may be a plate column , such as a column with perforated trays, or with bells, or valves or Dualflow® type. It can also be a packed column. The gas stream is preferably washed countercurrently: the gas stream is fed at the bottom, and an acidic solution is fed at the top, via a feed line for the acid solution 6. As an acidic solution, it is possible to in particular using a solution of HCl, at a mass concentration ranging for example from 5 to 60%, especially from 10 to 50%, more preferably from 20 to 45% and in particular from 30 to 35%. The washing with the acid solution is preferably carried out at a temperature of 5 to 50 ° C, and more particularly of 7 to 40 ° C; and / or at a pressure of 0.1 to 4 barg, preferably from 0.3 to 2 barg, more preferably from 0.5 to 1.5 barg.
    [0019] The absorption efficiency of HF and TFA in the acidic solution depends on the number of theoretical plates installed, the reflux ratio and the temperature of the concentrated HCl solution. In general, HF is easier to absorb than TFA. An addition of boric acid at the stage of the washing with the acid solution makes it possible to complex the fluoride ions. For example, the addition of 2000 to 8000 ppm of H3B03 improves absorption efficiency and achieves TFA levels in the commercial HCl solution of less than 25 ppm. In other words, this boric acid addition solution makes it possible to install a column having a lower theoretical number of stages and operating with a lower reflux ratio, to obtain the same efficiency of HF absorption and of TFA in the concentrated HCI solution. At the acid solution wash stage, the vast majority of the HF and TFA of the gas stream is passed into solution and is thus removed via a spent acid solution collection line at the bottom of the column. Further hydrolysis of any remaining fluoro-oxygen compounds in the gas stream may take place at the washing stage. The washed gas stream from the washing unit 4 is recovered via a washed gas flow collection line 5. This feeds an impurity adsorption unit 7, which comprises a bed of activated carbon. The impurities adsorbed by the activated carbon bed are primarily volatile organic compounds (VOCs). In fact, the gaseous HCl can be polluted by light organic compounds entrained with it at the head of the distillation at very low levels (or at higher levels during a disruption of distillation, for example). These light organic compounds may include trifluoromethane (F23), pentafluoroethane (F125), chloropentafluoroethane (F115), 1,1,1-trifluoroethane (F143a), fluoromethane (F41), trifluoropropyl, and the like.
    [0020] For example, F125 and F115 form an azeotrope with HCI. The activated carbon bed adsorption step may be carried out in pressure and temperature ranges which have already been indicated above in connection with the acid solution washing step. At the outlet of the impurity adsorption unit 7, the purified gas stream is recovered in a purified flow collection line 8, which is connected at the input of an adiabatic or isothermal absorption unit 9. The unit absorption absorber 9 makes it possible to absorb the HCl from the gas stream in an aqueous solution, provided by an aqueous solution supply line 10. This aqueous solution may simply be demineralized water, or alternatively may be an acidic solution. Generally, the absorption unit 9 comprises a countercurrent contacting column, the aqueous solution being supplied at the top and the gas stream at the bottom. Since the absorption reaction of HCl in the water is exothermic, it is preferable to limit the pressure at which this operation is conducted. In general, the pressure is less than 2 barg and preferably less than 1.5 barg. In this way the absorption temperature does not exceed 130 ° C, and preferably 120 ° C. To resist corrosion, the column may be made of graphite or steel coated with polytetrafluoroethylene (PTFE). The column internals may be for example either graphite or polyvinylidene fluoride (PVDF). A deacidified gaseous stream is collected at the top, via a deacidified gaseous flow collection line 11. This stream may be either vented to the atmosphere via a neutralization safety column, or sent to an incinerator. A solution of HCl is collected at the bottom, via a collection line of hydrochloric acid solution 12. The mass concentration of HCl in the solution can be from 5 to 50%, preferably from 15 to 40%, and more. especially from 30 to 35%. Part of this solution can be used as a washing solution in the washing unit 4. In this case, the acid solution supply line 6 can be connected to the hydrochloric acid solution collection line 12. The proportion of HCI solution thus used for the purposes of the washing may represent from 2 to 15% by weight, preferably from 5 to 10%. If the purity of the HCl solution collected is not sufficient, and especially if the HF content remains above the desired threshold, it is possible to proceed to another treatment step, namely an adsorption step in a complementary adsorption unit 13, supplied by the hydrochloric acid solution collection line 12. This complementary adsorption unit 13 may comprise, for example, a silica gel.
    [0021] The temperature of the HCl solution should be as low as possible, for example less than or equal to 35 ° C, since the adsorption on the silica gel is exothermic. Above this temperature, the adsorption efficiency decreases sharply. The contact time is between a few minutes and a few hours (preferably between 10 and 60 minutes). The speeds of passage are slow and between 1 and 20 m / h and preferably between 3 and 10 m / h. The operating pressure is a few bars (1 to 7 barg and preferably 1 to 5 barg). Silica gel typically has a pore size of 50A, whereas conventional gels generally have pore sizes of up to 20A. The fluoride content of the input HCl solution is preferably less than or equal to 100 ppm to avoid any risk of degradation of the silica gel. It is therefore a finishing operation. After this step of complementary adsorption on silica gel, it is possible to reach HF contents of less than 1 ppm in the HCl solution.
    [0022] At the outlet of the complementary adsorption unit 13, a purified solution of HCl is recovered in a collection line of purified hydrochloric acid solution 14. The solution of HCl (or purified HCl solution) recovered at the outcome of the process of the invention can be upgraded commercially.
    [0023] Preferably, the maximum content of fluorides in this solution of HCl (or solution of purified HCl) recovered at the end of the process is 5 ppm, or even 1 ppm. The maximum content of fluorooxygenated organic compounds (and in particular TFA) may be, for example, 25 ppm.
    权利要求:
    Claims (20)
    [0001]
    REVENDICATIONS1. Process for the treatment of a gaseous flow containing hydrochloric acid, hydrofluoric acid and fluoroxygenated compounds, in which the gaseous flow is successively subjected to: a catalytic hydrolysis step; a washing step with an acidic solution; a step of adsorbing impurities with activated carbon; an adiabatic or isothermal absorption step of hydrochloric acid in an aqueous solution, making it possible to collect a solution of hydrochloric acid.
    [0002]
    2. The method of claim 1, wherein the catalytic hydrolysis step is performed on a bed of activated carbon.
    [0003]
    3. Method according to claim 1 or 2, wherein the acid solution used during the washing step is a hydrochloric acid solution and preferably comes from the hydrochloric acid solution collected at the end of the step adiabatic or isothermal absorption.
    [0004]
    4. Method according to one of claims 1 to 3, further comprising: - a step of contacting the hydrochloric acid solution with a silica gel.
    [0005]
    5. Process according to one of claims 1 to 4, in which the fluoro-oxygenated compounds comprise carbonyl difluoride, chlorofluorocarbonyl, trifluoroacetyl fluoride and / or trifluoroacetic acid; and wherein, preferably, the gas stream comprises at least 50 mg / L, especially at least 100 mg / L, or even at least 200 mg / L of trifluoroacetyl fluoride and / or trifluoroacetic acid.
    [0006]
    6. Method according to one of claims 1 to 5, wherein boric acid is added to the acid solution used for the washing step.
    [0007]
    7. Method according to one of claims 1 to 6, wherein the gas stream is a stream from a catalytic fluorination reaction of at least one chlorinated compound in at least one fluorinated compound, said stream preferably being collected in output of a distillation of a product stream of the catalytic fluorination reaction.
    [0008]
    The process of claim 7, wherein the catalytic fluorination reaction is carried out in the presence of oxygen.
    [0009]
    The process according to claim 7 or 8, wherein: the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and wherein the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; the chlorinated compound is preferably chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane; 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3- trifluoropropene and mixtures thereof; and preferably the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and 2-chloro. -3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof.
    [0010]
    A process for preparing a fluorinated compound comprising: - providing a chlorinated compound and hydrofluoric acid; the catalytic reaction of the chlorinated compound with hydrofluoric acid and the collection of a flow of raw products; separation of the stream of raw products, preferably by distillation, making it possible to recover, on the one hand, a stream of fluorinated compound and, on the other hand, a gas stream containing mainly hydrochloric acid, as well as minority amounts of hydrofluoric acid and fluoro-oxygen compounds; the treatment of the gaseous flow containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds according to one of claims 1 to 9.
    [0011]
    11. The method of claim 10, wherein the catalytic reaction is carried out in the presence of oxygen.
    [0012]
    The process according to claim 10 or 11, wherein: the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and wherein the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; the chlorinated compound is preferably chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane; 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3- trifluoropropene and mixtures thereof; and preferably the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and 2-chloro. -3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof.
    [0013]
    13. Installation for treating a gaseous flow containing hydrochloric acid, hydrofluoric acid and fluorooxygen compounds, comprising: - a gas flow supply line containing hydrochloric acid, hydrofluoric acid and fluoro-oxygenated compounds (1), feeding a catalytic hydrolysis unit (2); - a washing unit (4), fed on the one hand by a hydrolysed gas stream collection pipe (3) from the catalytic hydrolysis unit (2), and on the other hand by a supply line acid solution (6); an impurity adsorption unit (7), comprising an active charcoal bed, fed by a washed gas flow collection line (5) issuing from the washing unit; an adiabatic or isothermal absorption unit (9) fed on the one hand by a purified flow collection line (8) issuing from the adsorption unit and on the other hand by a solution supply line aqueous (10); a hydrochloric acid solution collection line (12) at the outlet of the adiabatic absorption unit (9).
    [0014]
    14. Installation according to claim 13, wherein the catalytic hydrolysis unit (2) comprises a bed of activated carbon.
    [0015]
    15. Installation according to claim 13 or 14, wherein the supply line of acid solution (6) is directly or indirectly from the hydrochloric acid solution collection pipe (12).
    [0016]
    16. Installation according to one of claims 13 to 15, further comprising: - a complementary adsorption unit (13) comprising a silica gel fed by the hydrochloric acid solution collection pipe (12); and - a collection line of purified hydrochloric acid solution (14) from the additional adsorption unit (13).
    [0017]
    17. Installation according to one of claims 13 to 16, comprising a supply of boric acid solution to the washing unit (4).
    [0018]
    18. Installation according to one of claims 13 to 17, wherein the gas flow supply line containing hydrochloric acid, hydrofluoric acid and fluoro-oxygen compounds (1) is derived from a unit. distillation; the distillation unit is preferably fed by a raw product collection pipe at the outlet of a catalytic reactor.
    [0019]
    19. Installation according to claim 18, wherein the catalytic reactor is fed by a chlorine compound supply line and a hydrofluoric acid supply line, and the raw product collection line carries a stream comprising a fluorinated compound. and in which preferably: the chlorinated compound is a chlorocarbon, a hydrochlorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a chloroolefin, a hydrochloroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; and wherein the fluorinated compound is a fluorocarbon, a hydrofluorocarbon, a chlorofluorocarbon, a hydrochlorofluorocarbon, a fluoroolefin, a hydrofluoroolefin, a chlorofluoroolefin or a hydrochlorofluoroolefin; more particularly, the chlorinated compound is chosen from 1,1,2-trichloroethane, 1,1,1,2,3-pentachloropropane, 1,1,1,3,3-pentachloropropane, 1,1,2-trichloroethane and 1,1,1,2,3-pentachloropropane. 2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, perchlorethylene, 1,2-dichloroethylene, 1,1,2,3-tetrachloropropene, 2,3,3, 3-tetrachloropropene, 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and their mixtures; and more particularly the fluorinated compound is chosen from pentafluoroethane, 1-chloro, 2,2-difluoroethane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and 2-chloro. -3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and mixtures thereof.
    [0020]
    20. Installation according to claim 18 or 19, comprising a supply of oxygen to the catalytic reactor.
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    同族专利:
    公开号 | 公开日
    PL3074342T3|2018-04-30|
    US20170158586A1|2017-06-08|
    EP3074342B1|2018-01-17|
    FR3013606B1|2015-11-13|
    CN104812700B|2018-07-17|
    HUE036551T2|2018-07-30|
    CN104812700A|2015-07-29|
    EP3074342A1|2016-10-05|
    MX2016006288A|2016-09-06|
    JP6463756B2|2019-02-06|
    CA2942595A1|2015-06-04|
    US9828314B2|2017-11-28|
    JP6463756B6|2019-02-27|
    JP2016539904A|2016-12-22|
    WO2015079137A1|2015-06-04|
    ES2659843T3|2018-03-19|
    KR20160091937A|2016-08-03|
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    法律状态:
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    2016-10-14| PLFP| Fee payment|Year of fee payment: 4 |
    2017-10-12| PLFP| Fee payment|Year of fee payment: 5 |
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    2019-10-14| PLFP| Fee payment|Year of fee payment: 7 |
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    2021-11-09| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1361736A|FR3013606B1|2013-11-28|2013-11-28|PROCESS FOR PURIFYING HYDROCHLORIC ACID|FR1361736A| FR3013606B1|2013-11-28|2013-11-28|PROCESS FOR PURIFYING HYDROCHLORIC ACID|
    PL14809480T| PL3074342T3|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    KR1020167016442A| KR20160091937A|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    JP2016534736A| JP6463756B6|2013-11-28|2014-11-10|Method for purification of hydrochloric acid|
    CA2942595A| CA2942595A1|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    HUE14809480A| HUE036551T2|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    MX2016006288A| MX2016006288A|2013-11-28|2014-11-10|Hydrochloric acid purification process.|
    PCT/FR2014/052868| WO2015079137A1|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    EP14809480.8A| EP3074342B1|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    ES14809480.8T| ES2659843T3|2013-11-28|2014-11-10|Hydrochloric acid purification procedure|
    US15/039,294| US9828314B2|2013-11-28|2014-11-10|Hydrochloric acid purification process|
    CN201480002715.9A| CN104812700B|2013-11-28|2014-11-10|The purification process of hydrochloric acid|
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