EP2027064A1 - Procédé de production de chlore à partir de gaz chlorhydrique et d'oxygène - Google Patents

Procédé de production de chlore à partir de gaz chlorhydrique et d'oxygène

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Publication number
EP2027064A1
EP2027064A1 EP07725513A EP07725513A EP2027064A1 EP 2027064 A1 EP2027064 A1 EP 2027064A1 EP 07725513 A EP07725513 A EP 07725513A EP 07725513 A EP07725513 A EP 07725513A EP 2027064 A1 EP2027064 A1 EP 2027064A1
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EP
European Patent Office
Prior art keywords
oxygen
hydrogen chloride
chlorine
gas
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07725513A
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German (de)
English (en)
Inventor
Rainer Weber
Andreas Bulan
Michel Haas
Rafael Warsitz
Knud Werner
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Publication of EP2027064A1 publication Critical patent/EP2027064A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • 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
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • 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
    • C01B7/07—Purification ; Separation
    • C01B7/0743—Purification ; Separation of gaseous or dissolved chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a process for the preparation of chlorine by thermal reaction of hydrogen chloride with oxygen using catalysts in which the gas mixture formed in the reaction, consisting at least of the target products of chlorine and water, unreacted hydrogen chloride and oxygen and other secondary components such as Carbon dioxide and nitrogen, and optionally phosgene is cooled to the condensation of hydrochloric acid, the resulting liquid hydrochloric acid is separated from the gas mixture, the remaining in the gas mixture residues of water, especially by washing with concentrated sulfuric acid are removed.
  • the invention particularly relates to the operation of the process using PHg of air or oxygen of lower purity.
  • the reaction can be carried out in the presence of catalysts at temperatures of about 200 0 C to 45O 0 C.
  • Suitable catalysts for the Deacon-V experienced contain transition metal compounds such as copper and ruthenium compounds or compounds of other metals such as gold, palladium and bismuth.
  • Such catalysts are described, for example, in the documents: DE 1 567 788 A1, EP 251 731 A2, EP 936 184 A2, EP 761 593 A1, EP 711 599 A1 and DE 102 50 131 A1.
  • the catalysts are usually applied to a support. These carriers consist for example of silica, alumina, titania or zirconia.
  • the Deacon processes are generally carried out in fluidized-bed reactors or fixed-bed reactors, preferably tube-bundle reactors. Hydrogen chloride is freed in the known methods before the reaction of impurities to avoid poisoning of the catalysts used.
  • Oxygen is usually used as pure gas with an O 2 content of> 99% by volume.
  • a major disadvantage of the aforementioned chlorine production process is the comparatively high energy consumption for the liquefaction of the chlorine gas stream.
  • Another disadvantage is that in the liquefaction of the chlorine gas stream remains an oxygen-containing gas phase, which still contains significant amounts of chlorine gas and other minor components such as carbon dioxide.
  • This chlorine- and oxygen-containing gas phase is usually recycled to the reaction of hydrogen chloride with oxygen. Due to also containing minor constituents, in particular carbon dioxide and nitrogen, a part of this gas stream must be discharged and disposed of in order to avoid excessive accumulation of these by-products in the material cycle. However, some of the valuable products chlorine and oxygen are lost.
  • the gas stream discharged from the overall process must be fed to an additional exhaust gas treatment, which further impairs the economy of the process.
  • gas permeation generally means the selective separation of a gas mixture by means of membranes. Processes for gas permeation are known in principle and described, for example, in "T. Melin, R. Rautenbach; Membrane process - basics of module and system design; 2nd Edition; Springer Verlag 2004, Chapter 1, pp. 1-17, and Chapter 14, pp. 437-493, or Ullmann, Encyclopedia of Industrial Chemistry; Seventh Release 2006; Wiley-VCH Verlag ".
  • the invention is a process for the production of chlorine by
  • stage d) from the resulting chlorine-containing gas mixture from stage c) chlorine by means of gas permeation of oxygen, carbon dioxide and nitrogen and optionally additionally separated from other secondary constituents.
  • the process is preferably carried out continuously, since an equally possible batch or semibatch operation is somewhat more technically complicated than the continuous process.
  • the residues of water remaining in the gas mixture from stage c) are removed, in particular by washing with concentrated sulfuric acid.
  • the drying has the advantage that the formation of liquid hydrochloric acid in subsequent apparatus can be avoided (no corrosion), s.d. can be dispensed with the use of higher quality materials in these parts of the apparatus.
  • remaining residues of hydrogen chloride are optionally removed before or after the chlorine separation in step d).
  • the separation of hydrogen chloride also has the advantage that the formation of liquid hydrochloric acid from hydrogen chloride and traces of water can be avoided.
  • the removal of the optionally remaining residues of hydrogen chloride takes place directly after the removal of hydrochloric acid according to step c).
  • the removal of any residual hydrogen chloride is most preferably carried out by absorption, in particular by washing with water.
  • an oxygen-containing gas having an oxygen content of not more than 99% by volume is used.
  • a technically pure oxygen having an oxygen content of typically 93.5% by volume which is obtainable by the so-called "PSA process.”
  • Oxygen production by the PSA process is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry - the Ultimate Reference, Release 2006, 7th Edition
  • the oxygen produced by the PSA process is generally much less expensive than the oxygen produced after the cryogenic separation of air.
  • the separation d) by means of gas permeation provided in the new process is preferably carried out with membranes which operate on the molecular sieve principle.
  • membranes which operate on the molecular sieve principle.
  • used membranes are molecular sieve membranes based on carbon and / or SiO 2 and / or zeolites.
  • the minor components are separated, which have a smaller Lennard Jones (ie a smaller kinetic) diameter than the main component chlorine.
  • the effective pore size of the molecular sieve for the step d) is 0.2 to 1 nm, preferably 0.3 to 0.5 nm.
  • the gas permeation When using the gas permeation to separate off oxygen and possibly secondary constituents in the chlorine-containing gas mixture, a very pure chlorine gas is obtained, the energy requirement for the chlorine gas purification carried out according to the invention being significantly reduced in comparison with the previously known processes.
  • the gas mixture obtained as a further gas stream contains essentially oxygen, as well as minor constituents carbon dioxide and optionally nitrogen and is essentially free of chlorine.
  • Substantially free of chlorine here means a gas mixture with a content of at most 1% by weight of chlorine, based on the resulting gas mixture.
  • a content of at most 1000 ppm of chlorine, more preferably of at most 100 ppm of chlorine in the resulting gas mixture is achieved.
  • the gas permeation is preferably carried out using so-called carbon membranes.
  • Known carbon membranes consist of pyrolyzed polymers, eg pyrolyzed Polymers from the series: phenolic resins, furfuryl alcohols, cellulose, polyacrylonitriles and polyimides. Such are for example in chapter 2.4 of T. Melin, R. Rautenbach; Membrane process - basics of module and system design; 2nd Edition; Springer Verlag 2004, pp. 47-59.
  • Current typical operating pressures for the treatment of chlorine-containing gas streams are in the range of 7,000 to 12,000 hPa (7 to 12 bar).
  • a further preferred variant of the process according to the invention is characterized in that air or oxygen-enriched air (up to 99% by volume O 2 ) is used for the reaction of hydrogen chloride with oxygen as the oxygen source and that the oxygen obtained in step d) and optionally Secondary constituents such as carbon dioxide and nitrogen-containing gas mixture may be disposed of after pollutant control or discarded or is partially recycled.
  • the preferred process with a disposal or rejection of the chlorine-separated gas mixture from stage d) has the particular advantage that it does not lead to a strong accumulation of
  • a further preferred variant of the process according to the invention is characterized in that the air enriched with oxygen for the reaction of hydrogen chloride with oxygen or air enriched with oxygen is used.
  • An air or oxygen enriched air operated process has other advantages. On the one hand eliminates the use of air instead of pure oxygen, a significant cost factor, since the processing of the air is much less technically complex than the recovery of pure oxygen. Since increasing the oxygen content drives the reaction equilibrium in the direction of chlorine production, the amount of inexpensive air or oxygen-enriched air can be increased without further objections as needed.
  • Air or with oxygen-enriched air is due to an efficient process gas processing is given with this invention, only possible.
  • Chlorine may then be removed by methods known in the art, e.g. With
  • Carbon monoxide can be converted to phosgene, which can be used for the production of MDI or TDI from MDA or TDA.
  • the catalytic process known as the Deacon process is used.
  • hydrogen chloride is oxidized with oxygen in an exothermic equilibrium reaction to chlorine, whereby water vapor is obtained.
  • the reaction temperature is usually 150 to 500 ° C, the usual reaction pressure is 1 to 25 bar. Since it is an equilibrium reaction, it is expedient to work at the lowest possible temperatures at which the catalyst still has sufficient activity.
  • oxygen in excess of stoichiometric amounts of hydrogen chloride. For example, a two- to four-fold excess of oxygen is customary. Since no loss of selectivity is to be feared, it can be economically advantageous to work at relatively high pressure and, correspondingly, at a longer residence time than normal pressure.
  • Suitable preferred catalysts for the Deacon process include ruthenium oxide, ruthenium chloride or other ruthenium compounds supported on silica, alumina, titania or zirconia. Suitable catalysts can be obtained, for example, by applying ruthenium chloride to the support and then drying or drying and calcining. Suitable catalysts may, in addition to or instead of a ruthenium compound, also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium. Suitable catalysts may further contain chromium (i ⁇ ) oxide or bismuth compounds.
  • the catalytic hydrogen chloride oxidation can be adiabatic or preferably isothermal or approximately isothermal, batchwise, but preferably continuously or as a fixed bed process, preferably as a fixed bed process, particularly preferably in tube bundle reactors to heterogeneous catalysts at a reactor temperature of 180 to 500 0 C, preferably 200 to 400 0th C, particularly preferably 220 to 350 ° C. and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, particularly preferably 1.5 to 17 bar and in particular 2.0 to 15 bar are performed.
  • Typical reactors in which the catalytic hydrogen chloride oxidation is carried out are fixed bed or fluidized bed reactors.
  • the catalytic hydrogen chloride oxidation can preferably also be carried out in several stages.
  • a further preferred embodiment of a device suitable for the method consists in using a structured catalyst bed in which the catalyst activity increases in the flow direction.
  • Such structuring of the catalyst bed can be done by different impregnation of the catalyst support with active material or by different dilution of the catalyst with an inert material.
  • an inert material for example, rings, cylinders or balls of titanium dioxide, zirconium dioxide or mixtures thereof, alumina, steatite, ceramic, glass, graphite or stainless steel can be used.
  • the inert material should preferably have similar external dimensions.
  • Suitable shaped catalyst bodies are shaped bodies with any desired shapes, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, particular preference being given to rings, cylinders or star strands as molds.
  • Ruthenium compounds or copper compounds on support materials are particularly suitable as heterogeneous catalysts, preference being given to optionally doped ruthenium catalysts.
  • suitable carrier materials are silicon dioxide, graphite, rutile or anatase titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, preferably titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably ⁇ - or ⁇ -aluminum oxide or mixtures thereof.
  • the copper or ruthenium catalysts for example, by impregnating the support material with aqueous solutions of Q1CI 2 and RuCl 3 and optionally a Promoter for doping, preferably in the form of their chlorides, can be obtained.
  • the shaping of the catalyst can take place after or preferably before the impregnation of the support material.
  • the catalysts are suitable as promoters alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, more preferably lanthanum and cerium, or mixtures thereof.
  • alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, Rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yt
  • the moldings can then be dried at a temperature of 100 to 400 0 C, preferably 100 to 300 0 C, for example, under a nitrogen, argon or air atmosphere and optionally calcined.
  • the shaped bodies are preferably calcined first at 100 to 15O 0 C and then dried at 200 to 400 0 C.
  • the conversion of hydrogen chloride in a single pass may preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 70%. Unreacted chlorine hydrogen can be partially or completely recycled to the catalytic hydrogen chloride oxidation after separation.
  • the volume ratio of hydrogen chloride to oxygen at the reactor inlet is preferably from 1: 1 to 20: 1, more preferably 2: 1 to 8: 1, most preferably 2: 1 to 5: 1.
  • the heat of reaction of the catalytic hydrogen chloride oxidation can be used advantageously for the production of high-pressure steam.
  • This can e.g. be used for the operation of a phosgenation reactor and / or distillation columns, in particular of isocyanate distillation columns.
  • the chlorine formed in the deaconium oxidation is separated off.
  • the separation step usually comprises several stages, namely the separation and optionally recycling of unreacted hydrogen chloride from the product gas stream of the catalytic hydrogen chloride oxidation, the drying of the obtained, substantially chlorine and oxygen-containing stream and the separation of chlorine from the dried stream.
  • the separation of unreacted hydrogen chloride and water vapor formed can be carried out by condensation of aqueous hydrochloric acid from the product gas stream of hydrogen chloride oxidation by cooling. Hydrogen chloride can also be absorbed in dilute hydrochloric acid or water.
  • a further preferred process is characterized in that the hydrogen chloride used as the starting material for the new process is the product of a preparation process of isocyanates and that the purified chlorine gas freed of oxygen and optionally of secondary constituents is used in the preparation of isocyanates, in particular as part of a material cycle is used
  • a particular advantage of such a combined preferred process is that the usual chlorine liquefaction can be dispensed with and that the chlorine is available for recycling to the isocyanate production process at approximately the same pressure level as the starting stage of the isocyanate preparation process.
  • phosgene is carried out by reaction of chlorine with carbon monoxide.
  • the synthesis of phosgene is well known and is described, for example, in Ullmanns Enzyklopädie industrial chemistry, 3 Edition, Volume 13, page 494-500 shown on an industrial scale phosgene is prepared mainly by reaction of carbon monoxide with chlorine, preferably activated carbon as a catalyst.
  • the highly exothermic gas phase reaction is typically carried out at a temperature of at least 25O 0 C to a maximum of 600 0 C usually in tube bundle reactors
  • the removal of the heat of reaction can take place in different ways, for example by a liquid heat exchange agent, such as in WO 03/072237 Al or by boiling through a secondary cycle while utilizing the heat of reaction to generate steam, as disclosed, for example, in US Pat. No. 4,764,308.
  • At least one isocyanate is formed by reaction with at least one organic amine or a mixture of two or more amines in a next process step.
  • This second process step is also referred to below as phosgenation.
  • the reaction takes place to form hydrogen chloride ais By-product which accumulates as a mixture with the isocyanate
  • phosgenation solvents are chlorinated aromatic hydrocarbons, such as chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, T ⁇ chlorbenzole, the corresponding chlorotoluenes or chloroxylenes , Chlorethylbenzol, monochlorodiphenyl, ⁇ - or ß-Naphthylchlo ⁇ d, ethyl benzoate, dialkyl phthalate, D ⁇ sodiethylphthalat, toluene and xylenes Suitable solvents are known in principle from the prior art.
  • the solvent formed for phosgene may also be the isocyanate itself.
  • the phosgenation especially of suitable aromatic and aliphatic diamines, takes place in the gas phase, ie above the boiling point of the amine.
  • the gas phase phosgenation is described, for example, in EP 570 799 A1. Advantages of this method over the otherwise customary byssigphasenphosgentechnik lie in the energy savings, due to the minimization of a complex solvent and phosgene cycle.
  • Suitable organic amines are in principle all primary amines having one or more primary amino groups which can react with phosgene to form one or more isocyanates having one or more isocyanate groups.
  • the amines have at least one, preferably two, or optionally three or more primary amino groups.
  • suitable organic primary amines are aliphatic, cycloaliphatic, aliphatic-aromatic, aromatic amines, di- and / or polyamines, such as aniline, halogen-substituted phenylamines, e.g.
  • 4-chlorophenylamine 1,6-diaminohexane, 1-amino-3,3,5-trimethyl-5-amino-cyclohexane, 2,4-, 2,6-diaminotoluene or mixtures thereof, 4,4'-, 2,4'- or 2,2'-diphenylmethanediamine or mixtures thereof, as well as higher molecular weight isomeric, oligomeric or polymeric derivatives of said amines and polyamines.
  • Other possible amines are known in principle from the prior art.
  • Preferred amines for the present invention are the amines of the diphenylmethanediamine series (monomeric, oligomeric and polymeric amines), 2,4-, 2,6-diaminotoluene, isophoronediamine and hexamethylenediamine.
  • MDI diisocyanododiphenylmethane
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the amines can be reacted with phosgene in a one-step or two-step or possibly multi-step reaction. In this case, a continuous as well as discontinuous operation is possible.
  • the reaction is carried out above the boiling point of the amine preferably within a mean contact time of 0.5 to 5 s and at a temperature of 200 to 600 0 C.
  • the phosgenation in the liquid phase is usually carried out at a temperature of 20 to 24O 0 C and a pressure of 1 to about 50 bar.
  • the phosgenation in the liquid phase can be carried out in one or more stages, wherein phosgene can be used in stoichiometric excess.
  • the amine solution and the phosgene solution are combined via a static mixing element and then, for example, from bottom to top by one or passed several reaction towers, where the mixture reacted to the desired isocyanate.
  • reaction vessels with stirring device can also be used.
  • special dynamic mixing elements can also be used. Suitable static and dynamic mixing elements are basically known from the prior art.
  • continuous liquid phase isocyanate production is carried out in two stages on an industrial scale.
  • the first stage generally at a temperature of at most 220 0 C, preferably at most 160 0 C from amine and phosgene, the carbamoyl chloride and amine and split off hydrogen chloride amine hydrochloride formed.
  • This first stage is highly exothermic.
  • both the carbamoyl chloride is cleaved to isocyanate and hydrogen chloride, and the amine hydrochloride is converted to the carbamoyl chloride.
  • the second stage is usually carried out at a temperature of at least 9O 0 C, preferably from 100 to 24O 0 C performed.
  • the separation of the isocyanates formed during the phosgenation takes place in a third step. This is achieved by first separating the reaction mixture of the phosgenation into a liquid and a gaseous product stream in a manner which is generally known to the person skilled in the art.
  • the liquid product stream contains essentially the isocyanate or isocyanate mixture, the solvent and a small amount of unreacted phosgene.
  • the gaseous product stream consists essentially of hydrogen chloride gas, stoichiometrically excess phosgene, and minor amounts of solvents and inert gases, such as nitrogen and carbon monoxide.
  • liquid stream is then subjected to a work-up, preferably a work-up by distillation, successively phosgene and the solvent for the phosgenation are separated.
  • a work-up preferably a work-up by distillation
  • successively phosgene and the solvent for the phosgenation are separated.
  • the hydrogen chloride obtained in the reaction of phosgene with an organic amine generally contains organic minor components which are used in the thermal catalyzed HCl oxidation.
  • organic constituents include, for example, the solvents used in the production of isocyanate, such as chlorobenzene, o-dichlorobenzene or p-dichlorobenzene.
  • the separation of the hydrogen chloride produced during the phosgenation from the gaseous product stream is preferably carried out in a further process step.
  • the gaseous product stream obtained in the separation of the isocyanate is treated in such a way that the phosgene can again be supplied to the phosgenation and the hydrogen chloride to an electrochemical oxidation.
  • the separation of the hydrogen chloride is preferably carried out initially by phosgene is separated from the gaseous product stream.
  • the separation of the phosgene is achieved by liquefaction of phosgene, for example on one or more capacitors connected in series.
  • the liquefaction is preferably carried out at a temperature in the range of -15 to -4O 0 C, depending on the solvent used. By this freezing also parts of the solvent residues can be removed from the gaseous product stream.
  • the phosgene may be washed out of the gas stream in one or more stages with a cold solvent or solvent-phosgene mixture.
  • Suitable solvents for this purpose are, for example, the solvents used in the phosgenation, chlorobenzene and o-dichlorobenzene.
  • the temperature of the solvent or the solvent-phosgene mixture for this purpose is in the range of -15 to -46 0 C.
  • the separated from the gaseous product stream phosgene can be fed back to the phosgenation.
  • the hydrogen chloride obtained after separation of the phosgene and a portion of the solvent residue may contain, in addition to the inert gases such as nitrogen and carbon monoxide, 0.1 to 1% by weight of solvent and 0.1 to 2% by weight of phosgene.
  • a purification of the hydrogen chloride to reduce the proportion of traces of solvent can be done, for example by freezing, by depending on the physical properties of the solvent, the hydrogen chloride is passed, for example, by one or more cold traps.
  • the heat exchangers are preferably operated alternately, with the gas stream thawing out the previously frozen-out solvent in the first throughflowed heat exchanger.
  • the solvent can be used again for the preparation of a phosgene solution.
  • the gas is preferably cooled below the fixed point of the solvent, so that this crystallized.
  • the hydrogen chloride-containing gas stream can be depleted in this way to preferably not more than 500 ppm, particularly preferably not more than 50 ppm, very particularly preferably not more than 20 ppm of solvent content.
  • the purification of the hydrogen chloride can preferably be carried out in two series-connected heat exchangers, for example according to US Pat. No. 6,719,957.
  • the hydrogen chloride is preferably compressed to a pressure of 5 to 20 bar, preferably 10 to 15 bar, compressed and the compressed gaseous hydrogen chloride at a temperature of 20 to 60 0 C, preferably 30 to 50 0 C 1 fed to a first heat exchanger.
  • This condense organic components that can be supplied to a disposal or recycling.
  • the current conducted into the first heat exchanger hydrochloric leaves it at a temperature of -20 to 0 0 C, and is cooled in the second heat exchanger to a temperature of -10 to -30 ° C.
  • the resulting in the second heat exchanger condensate consists of other organic components and small amounts of hydrogen chloride.
  • the condensate draining from the second heat exchanger is fed to a separation and evaporator unit.
  • This may be, for example, a distillation column in which the hydrogen chloride is expelled from the condensate and returned to the second heat exchanger. It is also possible to return the expelled hydrogen chloride in the first heat exchanger.
  • the cooled in the second heat exchanger and freed of organic hydrogen chloride is passed at a temperature of -10 to -3O 0 C in the first heat exchanger. After heating to 10 to 3O 0 C leaves the liberated from organic components hydrogen chloride, the first heat exchanger.
  • the optionally intended purification of the hydrogen chloride from organic impurities, such as solvent residues takes place on activated carbon by means of adsorption.
  • the hydrogen chloride is passed after removal of excess phosgene at a pressure difference of 0 to 5 bar, preferably from 0.2 to 2 bar, over or through an activated carbon bed.
  • the flow rate and residence time is adjusted in a manner known to those skilled in the content of impurities.
  • Adsorption of organic contaminants is also possible on other suitable adsorbents, e.g. on zeolites.
  • a distillation of the hydrogen chloride may be provided for the optionally provided purification of the hydrogen chloride from the phosgenation. This takes place after condensation of the gaseous hydrogen chloride from the phosgenation.
  • the purified hydrogen chloride is taken off as the top product of the distillation, the distillation being carried out under conditions known to those skilled in the art and customary for such a distillation of pressure, temperature and the like.
  • the hydrogen chloride separated off and optionally purified according to the above-described process can then be supplied to the HCl oxidation with oxygen.
  • Fig. 1 is a diagram of a chlorine oxidation with single-stage gas permeation
  • Fig. 2 is a diagram of the gas permeation after step d) for the separation of chlorine
  • Fig. 1 an example of the use of the method as a supplement and part of an isocyanate production is shown.
  • a first stage 11 of isocyanate production chlorine is converted with carbon monoxide to phosgene.
  • stage 12 phosgene from stage 11 with an amine (eg toluene diamine) to an isocyanate (eg toluene diisocyanate, TDI) and hydrogen chloride is used, the isocyanate is separated (stage 13) and recycled and the HCl gas of a purification 14 subjected.
  • the purified HCl gas is reacted with air (ie, 20.95% by volume O 2 ) in the HCl oxidation process 15, for example, in a Deacon process by means of a catalyst.
  • reaction mixture from 15 is cooled (step 16).
  • Aqueous hydrochloric acid which may be mixed with water or dilute hydrochloric acid, is discharged.
  • the resulting gas mixture consisting at least of chlorine, oxygen and minor components such as nitrogen, carbon dioxide, etc. and is treated with conc. Sulfuric acid (96%) dried (step 17).
  • the chlorine gas obtained from the gas permeation 18 is used again directly in the phosgene synthesis 11.
  • a supported catalyst was prepared by the following procedure. 10 g of titanium dioxide having the rutile structure (Sachtleben) were suspended in 250 ml of water by stirring. 1.2 g of ruthenium (IH) chloride hydrate (4.65 mmol Ru) were dissolved in 25 ml of water. The resulting aqueous ruthenium chloride solution was added to the carrier suspension. This suspension was added dropwise within 30 minutes in 8.5 g of 10% sodium hydroxide solution and then stirred for 60 minutes at room temperature. Subsequently, the reaction mixture was heated to 70 0 C and stirred for 2 hours. The solid was then separated by centrifugation and washed neutral with 4 x 50 ml of water. The solid was then dried and then calcined h at 80 0 C in a vacuum drying cabinet for 24 4 hours at 300 ° C in air.
  • FIG. 2 shows the flow chart of the test apparatus.
  • the feed gas supply takes place from compressed gas cylinders and is adjusted via flow meter type Bronkhorst.
  • the trans-membrane pressure difference is set either by means of overpressure on the upstream side and / or by means of connection of a vacuum pump 4 on the permeate side.
  • the permeate flow HiVm 2 Ii
  • the gas concentrations are determined by sampling 2, 3 by gas chromatography (GC).
  • a carbon membrane shows, according to MB. Hägg, Journal of Membrane Science 177 (2000) 109-128 the following permeabilities:
  • Chlorine 9842 kg / h The oxygen-rich retentate stream can be recycled to the process.
  • the chlorine-rich stream is fed to a chlorine treatment.

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Abstract

Procédé de production de chlore par (a) conversion thermique de gaz chlorhydrique avec de l'oxygène à l'aide de catalyseurs et / ou par conversion active non thermique de gaz chlorhydrique avec de l'oxygène. Selon ledit procédé, (b) le mélange gazeux résultant de la conversion (a) et étant constitué au moins des produits cibles chlore et eau, du gaz chlorhydrique n'ayant pas réagi ainsi que d'autres constituants secondaires tels que du dioxyde de carbone et de l'azote, et éventuellement de phosgène, est refroidi en vue de la condensation de l'acide chlorhydrique, et (c) l'acide chlorhydrique liquide ainsi obtenu est séparé du mélange gazeux, un gaz ayant une teneur en oxygène de 99 % en volume au maximum étant utilisé lors de la conversion de l'étape (a). Lors d'une étape (d), à partir du mélange gazeux obtenu à l'étape (c), le chlore est séparé par perméation gazeuse de l'oxygène, du dioxyde de carbone, de l'azote et en outre éventuellement d'autres constituants secondaires.
EP07725513A 2006-05-23 2007-05-21 Procédé de production de chlore à partir de gaz chlorhydrique et d'oxygène Withdrawn EP2027064A1 (fr)

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DE102006024506A DE102006024506A1 (de) 2006-05-23 2006-05-23 Verfahren zur Herstellung von Chlor aus Chlorwasserstoff und Sauerstoff
PCT/EP2007/004614 WO2007134861A1 (fr) 2006-05-23 2007-05-21 Procédé de production de chlore à partir de gaz chlorhydrique et d'oxygène

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EP2027064A1 true EP2027064A1 (fr) 2009-02-25

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JP (1) JP2009537453A (fr)
KR (1) KR20090009894A (fr)
CN (1) CN101448737A (fr)
DE (1) DE102006024506A1 (fr)
RU (1) RU2008150592A (fr)
TW (1) TW200811040A (fr)
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US9352270B2 (en) 2011-04-11 2016-05-31 ADA-ES, Inc. Fluidized bed and method and system for gas component capture
AU2013317997B2 (en) 2012-09-20 2016-04-07 ADA-ES, Inc. Method and system to reclaim functional sites on a sorbent contaminated by heat stable salts
JP6203654B2 (ja) * 2014-01-28 2017-09-27 住友精化株式会社 塩化水素精製方法および塩化水素精製装置
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RU2008150592A (ru) 2010-06-27
WO2007134861A1 (fr) 2007-11-29
US20070274898A1 (en) 2007-11-29
DE102006024506A1 (de) 2007-11-29
TW200811040A (en) 2008-03-01
JP2009537453A (ja) 2009-10-29
CN101448737A (zh) 2009-06-03

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