Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
  • C01B13/02—Preparation of oxygen
  • C01B13/0229—Purification or separation processes
  • C01B13/0248—Physical processing only
  • C01B13/0251—Physical processing only by making use of membranes
• • 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

Definitions

• the invention is based on a process for the preparation of chlorine by thermal reaction of hydrogen chloride with oxygen using catalysts, and / or by non-thermally activated reaction of hydrogen chloride with oxygen, in which the gas mixture formed during the reaction, consisting at least of the target products chlorine and water, unreacted hydrogen chloride and oxygen and other secondary components such as carbon dioxide and nitrogen, and optionally phosgene for the condensation of hydrochloric acid is cooled, the resulting liquid hydrochloric acid is separated from the gas mixture, which removes residual water in the gas mixture, in particular by washing with concentrated sulfuric acid become.
• the invention particularly relates to the separation of the chlorine gas formed.
• the reaction can be carried out in the presence of catalysts at temperatures of about 250 to 450 0 C.
• Suitable catalysts for this thermal reaction are described, for example, in 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.
• - high-energy radiation e.g. Laser radiation or other photochemical radiation sources, UV radiation, infrared radiation u. a.
• a low temperature plasma eg generated by electrical discharges magnetic stimulation
• Tribomechanical activation e.g. Excitation by shock waves
• Ionizing radiation e.g. Gamma and X-ray radiation, ⁇ and ⁇ rays from nuclear decay, high-energy electrons, protons, neutrons and heavy ions
• Oxygen is usually used as pure gas with a CV content of> 98% 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.
• a further particular disadvantage of the known methods consists in the losses of chlorine resulting from the liquefaction of the chlorine, which occur during the rejection or destruction of partial streams of the oxygen stream usually returned to the HCl oxidation and containing residual chlorine. Since the commonly used pure oxygen is expensive to produce and therefore expensive, there is a need for a process improvement.
• gas permeation generally means the selective separation of a gas mixture by means of membranes.
• Processes for gas permeation are known in principle and for example in "T. Melin, R. Rautenbach; Membrane process - basics of module and system design; 2nd Edition; Springer Verlag 2004 “, Chapter 1 pages 1-17 and Chapter 14, pages 437-493 or” Ullmann, Encyclopedia of Industrial Chemistry; Seventh Release 2006; Wiley-VCH Verlag ".
• the invention relates to a process for the preparation of chlorine by thermal reaction of hydrogen chloride with oxygen using catalysts and / or by non-thermally activated reaction of hydrogen chloride with oxygen, in which
• the gas mixture resulting from the reaction consisting of the target products chlorine and water, unreacted hydrogen chloride and oxygen and other secondary constituents, such as carbon dioxide and nitrogen and optionally phosgene, is cooled for the purpose of condensing hydrochloric acid,
• the resulting chlorine-containing gas mixture is freed by means of gas permeation of oxygen and optionally additionally of secondary constituents, in particular of carbon dioxide and / or nitrogen and / or of phosgene.
• 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 separation d) by means of gas permeation provided in the novel process is preferably carried out with membranes which operate on the molecular sieve principle which are described, for example, in Chapter 3.4 of T. Melin, R. Rautenbach; Membrane process - basics of module and system design; 2nd Edition; Springer Verlag 2004, pp. 96-105.
• Preferably used membranes are molecular sieve membranes based on carbon and / or SiC> 2 and / or zeolites.
• the secondary 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 stage d) is 0.2 to 1 nm, preferably 0.3 to 0.5 nm.
• 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 are made of pyrolyzed polymers, e.g. 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 method - Basics of module and system design; 2nd Edition; Springer Verlag 2004, pp. 47-59.
• 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).
• Another preferred subject of the invention is a process for the preparation of chlorine by thermal reaction of hydrogen chloride with oxygen using catalysts and / or by non-thermally activated reaction of hydrogen chloride with oxygen, which is characterized in that in the separation of oxygen and the Secondary constituents from the chlorine-containing gas mixture by gas permeation (step d) resulting gas mixture of oxygen and minor constituents in a further gas permeation e) is separated into a substream containing essentially oxygen and a substream containing essentially carbon dioxide.
• the substream which contains essentially oxygen from step e) is at least partially recycled to the reaction of hydrogen chloride with oxygen.
• polymer membranes are used, which operate on the solution diffusion principle.
• polymer membranes are described, for example, in "T. Melin, R. Rautenbach; Membrane process - basics of module and system design; 2nd Edition; Springer Verlag 2004, Chapter 14.2 pp. 438-451.
• Polymer membranes for step e) which are particularly preferred are membranes of polysulfone, polyimide, polyaramide, polycarbonate, cellulose acetate and polysiloxane, in particular those based on polydimethylsiloxane (PDMS) or polyoctylmethylsiloxane (POMS).
• PDMS polydimethylsiloxane
• POMS polyoctylmethylsiloxane
• the PDMS membranes particularly preferably used for gas permeation e) preferably have a crosslinked structure.
• the preferred process with a recirculation of the oxygen has the particular advantage that there is no strong accumulation of secondary components such as carbon dioxide in the system cycle, which would require a significant discharge of the recirculated oxygen-containing gas stream. This discharge leads to significant losses of oxygen, which impairs the economics of the overall process of producing chlorine by reacting hydrogen chloride with oxygen.
• the preferred new process makes it possible to utilize very high utilization of the oxygen used by recycling the essentially oxygen-containing substream.
• a further preferred variant of the inventive method is characterized in that air or oxygen-enriched air is used for the reaction of hydrogen chloride with oxygen as the oxygen source and that in step d) resulting gas mixture containing oxygen and optionally secondary constituents such as carbon dioxide and nitrogen optionally discarded becomes.
• the gas mixture containing oxygen may, if appropriate after a pre-cleaning, be discharged directly into the ambient air in a controlled manner.
• 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. 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.
• step d) By using membranes, the chlorine in step d) can be successfully separated from oxygen, optionally nitrogen and further secondary components.
• the chlorine obtained by the process according to the invention may then be purified by the methods known in the art, e.g. be converted with carbon monoxide 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 0 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 superstoichiometric amounts. For example, a two- to four-fold excess of oxygen is customary. Since no loss of selectivity is to be feared, it may be economically advantageous to work at relatively high pressure and, accordingly, 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 (IH) oxide.
• IH chromium
• 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 outer 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-supported catalysts can be obtained, for example, by impregnating the support material with aqueous solutions of CuCl 2 or RUCl 3 and optionally motors for doping, preferably in the form of their chlorides, are 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 ° C, for example, under a nitrogen, argon or air atmosphere and optionally calcined.
• the moldings are first dried at 100 to 150 0 C and then calcined 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 1: 1 and 20: 1, preferably 2: 1 and 8: 1, more preferably 2: 1 and 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 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 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 input stage of the isocyanate preparation process.
• the combined process according to the invention is thus an integrated process for the preparation of isocyanates and the oxidation of hydrogen chloride for the recovery of chlorine for the synthesis of phosgene as the starting material for isocyanate production.
• the preparation of phosgene is carried out by reaction of chlorine with carbon monoxide.
• the synthesis of phosgene is well known and is, for example, in Ulimann's Encyclopedia of Industrial Chemistry, 3rd Edition, Volume 13, page 494-500 shown. Further processes for the preparation of isocyanates are described, for example, in US Pat. No. 4,764,308 and WO 03/072237.
• phosgene is produced predominantly by reaction of carbon monoxide with chlorine, preferably on activated carbon as catalyst. The highly exothermic gas phase reaction takes place at temperatures of at least 25O 0 C to a maximum of 600 0 C usually in tube bundle reactors.
• the dissipation of the heat of reaction can take place in different ways, for example by a liquid heat exchange medium, as described for example in WO 03/072237, or by evaporative cooling via a secondary cooling circuit with simultaneous use of the heat of reaction for steam generation, as disclosed for example in US 4764308.
• 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.
• the process step is also referred to below as phosgenation.
• the reaction takes place with formation of hydrogen chloride as by-product.
• isocyanates typically phosgene in a stoichiometric excess, based on the amine, is used. Usually, the phosgenation takes place in the liquid phase, wherein the phosgene and the amine can be dissolved in a solvent.
• Preferred solvents are chlorinated aromatic hydrocarbons, such as, for example, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, trichlorobenzenes, the corresponding chlorotoluenes or chloroxylenes, chloroethylbenzene, monochlorobenzene diphenyl, ⁇ - or ⁇ -naphthyl chloride, ethyl benzoate, dialkyl phthalate, diisodiethyl phthalate, toluene and xylenes.
• suitable solvents are known in the art.
• the solvent formed for phosgene may also be the isocyanate itself.
• the phosgenation in particular 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 A. 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 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 diisocyanatodiphenylmethane
• 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 seconds and at temperatures of 200 to 600 0 C.
• phosgenation in the liquid phase usually temperatures of 20 to 240 0 C and pressures of 1 to about 50 bar are used.
• 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 passed through a static mixing element and subsequently passed, for example, from bottom to top through one or more reaction towers, where the mixture reacts to the desired isocyanate.
• reaction towers which are provided with suitable mixing elements
• reaction vessels with stirring device can also be used.
• special dynamic mixing elements can also be used. Suitable static and dynamic mixing elements are known in the art.
• continuous liquid phase isocyanate production is carried out in two stages on an industrial scale.
• the first stage generally at temperatures of at most 220 0 C, preferably not more than 160 ° C from amine and phosgene, the carbamoyl chloride and formed from amine and split off hydrogen chloride amine hydrochloride.
• 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 temperatures of at least 90 ° C., preferably from 100 to 240 ° C.
• the separation of the isocyanates formed in the phosgenation is carried out in step. This is achieved by first separating the reaction mixture of the phosgenation into a liquid and a gaseous product stream in a manner 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 according to the isocyanate separation is then fed to a workup, preferably a distillative workup, wherein successively phosgene and the solvent are separated.
• a workup preferably a distillative workup
• the hydrogen chloride obtained in the reaction of phosgene with an organic amine generally contains organic components which can interfere with further processing.
• organic constituents include, for example, the solvents used in the preparation of isocyanates, such as chlorobenzene, o-dichlorobenzene or p-dichlorobenzene.
• Fig. 1 is a diagram of a chlorine oxidation with double-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 oxygen in the HCl oxidation process 15 (e.g., in a Deacon process via 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).
• a first gas permeation stage 18 chlorine is separated from the gas mixture from stage 17.
• the residual stream comprising oxygen and secondary constituents is purified in a second gas permeation stage 19 of secondary constituents such as carbon dioxide.
• the oxygen stream resulting from step 19 is returned to the HCl oxidation 15.
• the chlorine gas obtained from the first gas permeation 18 can be 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 (IIi) chloride hydrate (4.65 mmol of 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 60 minutes stirred 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 at 80 0 C in a vacuum oven for 24 h and then calcined for 4 hours at 300 0 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 (mVm 2 h) through the membrane is determined by standardization on the membrane surface.
• the gas concentrations are determined by sampling 2, 3 by gas chromatography (GC). example
• the two resulting material flows are composed as follows:
• Chlorine 11087 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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• 2006
  • 2006-05-23 DE DE102006024516A patent/DE102006024516A1/de not_active Withdrawn
• 2007
  • 2007-05-21 EP EP07764547A patent/EP2027065A2/de not_active Withdrawn
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  • 2007-05-21 RU RU2008150596/15A patent/RU2008150596A/ru not_active Application Discontinuation
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