EP2146927A2 - Intégration thermique dans un procédé deacon - Google Patents

Intégration thermique dans un procédé deacon

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Publication number
EP2146927A2
EP2146927A2 EP08735020A EP08735020A EP2146927A2 EP 2146927 A2 EP2146927 A2 EP 2146927A2 EP 08735020 A EP08735020 A EP 08735020A EP 08735020 A EP08735020 A EP 08735020A EP 2146927 A2 EP2146927 A2 EP 2146927A2
Authority
EP
European Patent Office
Prior art keywords
chlorine
column
oxygen
heat
gas
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.)
Withdrawn
Application number
EP08735020A
Other languages
German (de)
English (en)
Inventor
Knud Werner
Lutz Gottschalk
Meik Bernhard Franke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP2146927A2 publication Critical patent/EP2146927A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • 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
    • 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
    • C01B7/075—Purification ; Separation of liquid 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
    • Y02P20/20—Improvements relating to chlorine production

Definitions

  • the invention relates to the heat recovery in a hydrogen chloride oxidation process (Deacon process).
  • the method comprises the one- or multi-stage cooling of the process gases and separation of unreacted hydrogen chloride and reaction water from the process gas, drying of the product gases, separation of chlorine from the mixture, and recycling of unreacted oxygen in the hydrogen chloride oxidation process.
  • the object of the invention is to reduce the energy consumption in the Deacon process by heat recovery.
  • the invention relates to a process for the catalytic oxidation of hydrogen chloride with oxygen to chlorine and water in the gas phase, characterized in that at least a portion of the heat content of the product gases for heating the educt gases is used
  • Another object of the invention is a process for the catalytic oxidation of hydrogen chloride with oxygen to chlorine and water, which can be combined in particular with the aforementioned method, wherein after the oxidation reaction chlorine is separated from oxygen and optionally inert gases, by liquefying the chlorine and Removing the optionally present inert gases and the oxygen and subsequent evaporation of the chlorine formed, characterized in that at least a portion of the heat content of the reaction products of the oxidation for the evaporation of pure liquefied chlorine is used.
  • Another object of the invention is a process for the catalytic oxidation of hydrogen chloride with oxygen to chlorine and water, which can be combined in particular with at least one of the aforementioned method, wherein the product gases from the chlorine is obtained by liquefaction, wherein the liquid chlorine production-related shares of Containing carbon dioxide and then carbon dioxide is evaporated from the liquefied chlorine, characterized in that at least a portion of the heat content of the product gases of the oxidation reaction is used to evaporate the carbon dioxide from the liquefied chlorine.
  • the invention also provides a process for the catalytic oxidation of hydrogen chloride with oxygen to chlorine and water, which can be combined in particular with at least one of the aforementioned methods, in which from the product gases chlorine by
  • Containing carbon dioxide and then carbon dioxide is evaporated from the liquefied chlorine, characterized in that the vaporized with the carbon dioxide chlorine is partially condensed and the non-condensed cold gases for precooling the product gases before
  • Liquefaction can be used.
  • the aforementioned methods can preferably be combined with one another.
  • the catalytic oxidation of HCl gas with O 2 to Cl 2 and H 2 O (see eg Fig. 5) is carried out at elevated pressure and elevated temperature.
  • the HCl gas is compressed 1, fresh O 2 supplied under pressure, the mixture heated 2 and then reacted in a reactor 5.
  • the reactor can be operated isothermally or adiabatically. In the case of adiabatic operation, several reactors can be connected in series instead of a single reactor. The series connection of up to 7 reactors is advantageous. Between the reactors, the heat of reaction can then be removed in intercoolers. Since this heat is produced at high temperatures, it can be conveniently used for steam generation. For this, the intercooler can be fed directly with water, which evaporates. Alternatively, a heat transfer medium such as e.g. a molten salt are used. This heats up when absorbing the heat of reaction and can be used in a separate apparatus for the evaporation of water.
  • a heat transfer medium such as e.g. a molten salt are used. This heats up when absorbing the heat of reaction and can be used in a separate apparatus for the evaporation of water.
  • HCl and H 2 O are first removed by cooling 6 and washing 8 with water 9 (see, for example, EP 233 773) and discharged as hydrochloric acid from the process.
  • the complete removal of H 2 O is typically done by drying 10 with concentrated sulfuric acid.
  • the condensed Cl 2 usually contains CO 2 , which is removed with a distillation / stripping column 14 from the liquid Cl 2 . Subsequently, the pure Cl 2 thus obtained is evaporated again 16 and used for further processes, such as the isocyanate production.
  • the implementation of the process requires both very high and very low temperatures.
  • the catalytic oxidation typically takes place at temperatures of 300-500 ° C. while the condensation of Cl 2 is carried out at temperatures well below 0 0 C.
  • a first heat recovery measure utilizes the high temperature of the gas leaving the reactor to heat the reactants entering the reactor. For this purpose, these streams (see, for example, Fig. 1) are passed to the two sides of a heat exchanger 3 and cooled or heated. This measure can provide a large part of the heat for heating the reactants to reaction temperature.
  • the separation of unreacted HCl and resulting H 2 O is done by cooling and washing with water.
  • the temperature of the cooled, for example, in the context of the first measure for heat recovery gas flow is further reduced.
  • a heat transfer fluid water, steam, a thermal oil or other suitable fluids for this purpose can be used.
  • Such a process stream is the pure, liquid Cl 2 , which can be vaporized with warm heat transfer fluid in the evaporator 16 '.
  • Another suitable process stream flows through the evaporator 15 'of the distillation / stripping column 14 for CO 2 removal from liquid Cl 2 . Again, warm heat transfer fluid for operating the evaporator can be used advantageously.
  • a third way of recovering heat is by coupling the gas stream to the chlorine condensation and the gas stream leaving the top of the distillation / stripping column in a heat exchanger 18 '(see, for example, Figure 4).
  • the latter stream has the lowest temperature in the entire process and can therefore be used advantageously for precooling the gas stream for chlorine condensation.
  • JP 2003-292304 and DE 195 35 716 describe a heat recovery in the region of the distillation / stripping column for CO 2 removal from liquid Cl 2 .
  • the bottom stream of liquid, pure Cl 2 is released and then passed into a heat exchanger in which he is evaporated and cooled on the other side of the apparatus, the entering into the column stream and the Cl 2 contained in it condenses.
  • This shading has the disadvantage that the heat recovery of the pressure and the composition of the condensing and the pressure of the evaporating stream must be closely coordinated.
  • JP 2003-292304 describes that the pressure of the stream entering the column must be> 6 bar at a content of> 45 mol% Cl 2 . This corresponds to a Cl 2 partial pressure of> 2.7 bar.
  • the coupling according to the invention of the cooler 7 'with the bottom evaporator 15' of the column 14 and the chlorine evaporator 16 'via a heat transfer fluid does not have this tight coupling.
  • the heat transfer fluid may well have temperatures of 80 0 C and more.
  • the thus evaporated Cl 2 can then reach at least temperatures of 60 - 70 0 C, which corresponds to a Cl 2 vapor pressure between 17.8 and 21.8 bar.
  • the catalytic process known as the Deacon process can be described in particular as follows: Hydrogen chloride is oxidized to chlorine in an exothermic equilibrium reaction with oxygen to produce water vapor.
  • 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 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 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, tin dioxide 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 compounds of other noble metals, For example, gold, palladium, platinum, osmium, iridium, silver, copper or rhenium. Suitable catalysts may further contain chromium (III) oxide.
  • the catalytic hydrogen chloride oxidation may be adiabatic or preferably isothermal or approximately isothermal, batchwise, but preferably continuously or as a fixed bed process, preferably as a fixed bed process, more preferably in tube bundle reactors to heterogeneous catalysts at a reactor temperature of 180 to 500 0 C, preferably 200 to 400 0th C, more preferably 220 to 380 0 C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, more 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.
  • the adiabatic, isothermal or approximately isothermal mode of operation it is also possible to use a plurality of reactors with intermediate cooling, that is to say 2 to 10, preferably 2 to 8, particularly preferably 4 to 8, in particular 5 to 8, connected in series.
  • the hydrogen chloride can be added either completely together with the oxygen before the first reactor or distributed over the various reactors.
  • the oxygen is passed completely in front of the first reactor and the hydrogen chloride is added distributed to the various reactors.
  • This series connection of individual reactors can also be combined in one apparatus.
  • 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, stainless steel or nickel alloys 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 which may also be doped, 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 impregnation of the support material with aqueous solutions of CuCl 2 or RuCl 3 and optionally a promoter for doping, preferably in the form of their chlorides.
  • 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 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 can be limited to 15 to 90%, preferably 30 to 90%, particularly preferably 40 to 90%. After conversion, unreacted hydrogen chloride can be partly or completely recycled to the catalytic hydrogen chloride oxidation.
  • the volume ratio of hydrogen chloride to oxygen at the reactor inlet is in particular 1: 1 to 20: 1, preferably 1: 1 to 8: 1, particularly preferably 1: 1 to 5: 1.
  • the volume ratio of hydrogen chloride to oxygen at the inlet to the first reactor is 1: 8 to 2: 1, preferably 1: 5 to 2: 1, more preferably 1: 5 to 1: 2.
  • the chlorine formed 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.
  • Fig. 1 shows the process described below for the oxidation of hydrogen chloride, which is characterized in that part of the heat of reaction of the process is used to heat the incoming gas streams.
  • 55.5 kg / h of HCl gas having a composition of 1.1% by weight of N 2 , 0.2% by weight of CO, 1.8% by weight of CO 2 , 0.2% by weight of monochlorobenzene and 0.2% by weight of orthodichlorobenzene is removed in a compressor 1 from ambient pressure to 6.5 bar abs compressed. Subsequently, the compressed HCl gas 10.9 kg / h of oxygen is added under pressure.
  • the gas mixture is heated to 150 0 C after supplying a recirculated from the process, oxygen-containing gas stream in a preheater 2. Thereafter, it enters a next preheater 3, in which the further preheating takes place by utilizing the heat content of the product gases behind the reactor 5.
  • the gas mixture heats up to 260 ° C. and the product gases simultaneously cool to about 250 ° C.
  • the reactor inlet temperature is set to about 280 0 C.
  • the reactor 5 is filled with calcined supported ruthenium chloride as a catalyst and is operated adiabatically.
  • the product gases are cooled after passing through the apparatus 3 in a first aftercooler 6 to a temperature less than 250 0 C, but still above the dew point.
  • the temperature is lowered below the dew point and set to a value of about 100 0 C.
  • the resulting water and unreacted HCl from the gas stream is removed as hydrochloric acid in an absorption column 8.
  • the column is provided in its lower part with a pumped circulation in which a cooler is installed.
  • a cooler is installed to wash out all HCl from the gas stream.
  • 20 liters / h of fresh water 9 is abandoned at the top of the column.
  • the gas stream passes into a drying column 10, in which the residual water is separated down to traces with sulfuric acid.
  • a cooled Umpumpniklauf is set up to dissipate the heat of absorption in the lower part of the column.
  • 2 liters / h of a 96% strength by weight sulfuric acid is charged at the top of the column. As it trickles through the column, the sulfuric acid dilutes and is discharged in the bottom of the column as dilute sulfuric acid.
  • the gas stream is then compressed in the compressor 11 to 12 bar abs and cooled in the cooler 12 to about 40 0 C.
  • the temperature is lowered to -10 0 C to condense a portion of the chlorine contained in the gas stream.
  • carbon dioxide partially condenses in the gas stream, so that the quality of the liquid chlorine is not sufficient for its further use.
  • the remaining chlorine is completely evaporated in the evaporator 16 and fed into a pipeline network.
  • the gas stream is passed through a condenser 17 and cooled to -40 0 C or lower. In this case, further chlorine and carbon dioxide condenses and is returned to the column 14.
  • the remaining residual gas essentially contains the unreacted oxygen and is therefore recycled back to the reactor 5. Since it comprises coming from the condenser 17 to a temperature of -40 0 C, it must first be heated. For this purpose it flows through the heat exchanger 18 and is heated to ambient temperature. Subsequently, a part of the residual gas is led out of the process to discharge Inerte. This is followed by a wash in the column 19. The washing is carried out with 5 liters / h of water, which is trickled in countercurrent to the gas in the column 19. In this case, catalyst poisons that result from the drying with sulfuric acid, washed out. The purified residual gas is now returned to the process.
  • a process for the oxidation of hydrogen chloride is shown in which a portion of the heat of reaction of the process is used to evaporate a product stream.
  • 40 kg / h of HCl gas are mixed with the composition as in Example 1 and after compression of ambient pressure to 6.5 bar abs in 1 with 8 kg / h of oxygen under pressure.
  • the gas mixture is heated to 280 0 C after supplying a recirculated from the process, oxygen-containing gas stream in a preheater 2.
  • the reactor 5 is filled with calcined supported ruthenium chloride as a catalyst and is operated adiabatically.
  • the product gases are cooled in the aftercooler 6 to a temperature less than 250 0 C, but still above the dew point.
  • the product gases are passed into the recuperator 16 'and further cooled.
  • the liquid chlorine evaporates on the other side of the recuperator 16 'and thus uses part of the heat content of the product gases. Since the required heat flow is not sufficient to cool the product gases below the dew point, These are passed at a temperature above the dew point at about 150 0 C in the absorption column 8.
  • the resulting water and unreacted HCl from the gas stream is removed as hydrochloric acid.
  • the column is provided in its lower part with a recirculation circuit in which a cooler is installed. To wash out all HCl from the gas stream, 15 liters / h of fresh water 9 is abandoned at the top of the column.
  • the gas stream passes into a drying column 10, in which the residual water is separated down to traces with sulfuric acid.
  • a cooled Umpumpniklauf is set up to dissipate the heat of absorption in the lower part of the column.
  • 2 liters / h of a 96% strength by weight sulfuric acid is charged at the top of the column. As it trickles through the column, the sulfuric acid dilutes and is discharged in the bottom of the column as dilute sulfuric acid.
  • the gas stream is then compressed in the compressor 11 to 12 bar abs and cooled in the cooler 12 to about 40 0 C.
  • the temperature is lowered to -10 0 C to condense a portion of the chlorine contained in the gas stream.
  • carbon dioxide partially condenses in the gas stream, so that the quality of the liquid chlorine is not sufficient for its further use.
  • the carbon dioxide is stripped in the tray 14 equipped with trays and the largely carbon dioxide-free liquid chlorine leaves the column. A portion of this chlorine is vaporized in the evaporator 15 at the lower end of the column 14 and fed to this as stripping steam.
  • the remaining chlorine is completely evaporated in the recuperator 16 ', as described above, and fed into a pipeline network and reused.
  • the gas stream is passed through a condenser 17 and cooled to -40 0 C or lower. In this case, further chlorine and carbon dioxide condenses and is returned to the column 14.
  • the remaining residual gas essentially contains the unreacted oxygen and is therefore recycled back to the reactor 5. Since it comprises coming from the condenser 17 to a temperature of -40 0 C, it must first be heated. For this purpose it flows through the heat exchanger 18 and is heated to ambient temperature. Subsequently, a part of the residual gas is led out of the process to discharge Inerte. This is followed by a wash in the column 19. The washing is carried out with 4 liters / h of water, which is trickled in countercurrent to the gas in the column 19. In this case, catalyst poisons that result from the drying with sulfuric acid, washed out. The purified residual gas is now returned to the process.
  • Fig. 3 shows a process for the oxidation of hydrogen chloride, in which two in-process streams are heat-integrated.
  • HCl gas according to Example 2 is compressed in the compressor 1 to 6.5 bar abs and then mixed with 8 kg / h of oxygen under pressure.
  • the gas mixture is heated to 280 0 C after supplying a recirculated from the process, oxygen-containing gas stream in a preheater 2.
  • the gas mixture flows through the reactor 5, in which the reaction of hydrogen chloride to chlorine takes place.
  • the reactor 5 is filled with calcined supported ruthenium chloride as a catalyst and is operated adiabatically.
  • the product gases are cooled in the aftercooler 6 below the dew point, to a temperature of about 100 0 C and passed into the absorption column 8.
  • the resulting water and unreacted HCl from the gas stream is removed as hydrochloric acid.
  • the column is provided in its lower part with a pumped circulation in which a cooler is installed. To wash out all HCl from the gas stream, 15 liters / h of fresh water 9 is abandoned at the top of the column.
  • the gas stream passes into a drying column 10, in which the residual water is separated down to traces with sulfuric acid.
  • a cooled Umpumpniklauf is set up to dissipate the heat of absorption in the lower part of the column.
  • 2 liters / h of a 96% strength by weight sulfuric acid is charged at the top of the column. As it trickles through the column, the sulfuric acid dilutes and is discharged in the bottom of the column as dilute sulfuric acid.
  • the gas stream is then compressed in the compressor 11 to 12 bar abs and cooled in the cooler 12 to about 40 0 C.
  • the gas stream is pre-cooled in a recuperator 18 'to a temperature of about 0 0 C.
  • a recuperator 18 ' On the other side of the apparatus 18 ', the cold residual gas is passed out of apparatus 17 and simultaneously heated to ambient temperature. Only then will its temperature be in
  • Capacitor 13 lowered to -10 0 C to a portion of the chlorine contained in the gas stream condense. In this case, carbon dioxide partially condenses in the gas stream, so that the quality of the liquid chlorine is not sufficient for its further use.
  • the remaining chlorine is completely evaporated in the evaporator 16 and fed into a pipeline network.
  • the gas stream is passed through a condenser 17 and cooled to -40 0 C or lower. In this case, further chlorine and carbon dioxide condenses and is returned to the column 14.
  • the remaining residual gas essentially contains the unreacted oxygen and is therefore recycled back to the reactor 5. Since it comprises coming from the condenser 17 to a temperature of -40 0 C, it must first be heated. For this purpose, it flows through the recuperator 18 ', as described above, and is heated to ambient temperature. This has the additional benefit of the residual gas flow, that when heated, no heat carrier such as water must be used, which could freeze and thus damage the apparatus required for heating.
  • the recuperator 18 ' can also be installed behind the condenser 13 (not shown in FIG. 3) and thus cause a further condensation of chlorine.
  • Fig. 4 shows a highly heat integrated process for the oxidation of hydrogen chloride, in which, as in Example 1, part of the heat of reaction of the process is used to heat the incoming gas streams. Another portion of the heat of reaction is used via an interposed heat transfer medium for the evaporation of a product stream and for operating a column evaporator. Furthermore, as in Example 3, two in-process streams are heat-integrated. An HCl gas stream of 55.5 kg / h, as described in Example 1 is compressed in the compressor 1 to 6.5 bar abs and then mixed with 10.9 kg / h of oxygen under pressure.
  • the gas mixture is heated to 150 0 C after supplying a recirculated from the process, oxygen-containing gas stream in a preheater 2. Thereafter, it enters a next preheater 3, in which the further preheating takes place by utilizing the heat content of the product gases behind the reactor 5.
  • the gas mixture heats up to 260 ° C. and the product gases simultaneously cool to about 250 ° C.
  • the reactor inlet temperature is set to about 280 0 C.
  • the reactor 5 is filled with calcined supported ruthenium chloride as a catalyst and is operated adiabatically.
  • the product gases are cooled after passing through the apparatus 3 in a first aftercooler 6 to a temperature less than 250 0 C, but still above the dew point.
  • the temperature is lowered below the dew point and set to a value of about 100 0 C.
  • the aftercooler 7 ' is equipped with a heat transfer circuit.
  • the heat transfer fluid is water, steam, thermal oils or other suitable fluids
  • the heat transfer fluid absorbs the heat released in heat exchanger 7 'upon cooling of the product gas and gives it to both the evaporator 16' and to the evaporator
  • the resulting water and unreacted HCl from the gas stream is removed as hydrochloric acid in an absorption column 8.
  • the column is provided in its lower part with a pumped circulation in which a cooler is installed.
  • 20 liters / h of fresh water 9 is abandoned at the top of the column.
  • the gas stream passes into a drying column 10, in which the residual water is separated down to traces with sulfuric acid.
  • a cooled Umpumpniklauf is set up to dissipate the heat of absorption in the lower part of the column.
  • 2 liters / h of a 96% strength by weight sulfuric acid is charged at the top of the column.
  • the sulfuric acid dilutes and is discharged in the bottom of the column as dilute sulfuric acid.
  • the gas stream is then compressed in the compressor 11 to 12 bar abs and cooled in the cooler 12 to about 40 0 C.
  • the gas stream is pre-cooled in a recuperator 18 'to a temperature of about 0 0 C.
  • the cold residual gas is passed out of apparatus 17 and simultaneously heated to ambient temperature. Only then the temperature of the gas stream in the condenser 13 is lowered to -10 0 C to condense a portion of the chlorine contained in the gas stream. In this case, carbon dioxide partially condenses in the gas stream, so that the quality of the liquid chlorine is not sufficient for its further use.
  • the carbon dioxide is stripped in the tray 14 equipped with trays and the largely carbon dioxide-free liquid chlorine leaves the column.
  • a portion of this chlorine is vaporized in the evaporator 15 'at the lower end of the column 14 and fed to this as stripping steam.
  • the evaporator 15 ' is, as described above, operated with a heat transfer medium, which transfers heat from the product gas to the evaporator.
  • the remaining chlorine is completely evaporated in the evaporator 16 'and fed into a pipeline network. Also, this evaporator is, as described above, supplied with a heat transfer medium to use heat from the product gas for chlorine evaporation.
  • the gas stream is passed through a condenser 17 and cooled to -40 0 C or lower. In this case, further chlorine and carbon dioxide condenses and is returned to the column 14.
  • the remaining residual gas essentially contains the unreacted oxygen and is therefore recycled back to the reactor 5. Since it comprises coming from the condenser 17 to a temperature of -40 0 C, it must first be heated. For this purpose, it flows through the recuperator 18 ', as described above, and is heated to ambient temperature. This has, as in Example 3, for the residual gas flow the additional benefit that when heated no heat carrier such as water must be used, which could freeze and thus damage the apparatus required for heating. Alternatively, the recuperator 18 'can also be installed behind the condenser 13 (not shown in FIG. 4) and thus cause a further condensation of chlorine.
  • Fig. 5 is shown for comparison with the previous examples, a process for the oxidation of hydrogen chloride without heat integration.
  • 76.9 kg / h of HCl gas having the composition as in Example 1 are compressed in 1 to 6.5 bar abs and mixed with 15.1 kg / h of oxygen under pressure.
  • the gas mixture is heated to 280 0 C after supplying a recirculated from the process, oxygen-containing gas stream in a preheater 2.
  • the gas mixture flows through the reactor 5, in which the reaction of hydrogen chloride to chlorine takes place.
  • the reactor 5 is filled with calcined supported ruthenium chloride as a catalyst and is operated adiabatically.
  • the product gases are cooled in the aftercooler 6 below the dew point, to a temperature of about 100 0 C and passed into the absorption column 8.
  • the resulting water and unreacted HCl from the gas stream is removed as hydrochloric acid.
  • the column is provided in its lower part with a pumped circulation in which a cooler is installed. To wash out all HCl from the gas stream, 30 liters / h of fresh water 9 is abandoned at the top of the column.
  • the gas stream passes into a drying column 10, in which the residual water is separated down to traces with sulfuric acid.
  • a cooled Umpumpniklauf is set up to dissipate the heat of absorption in the lower part of the column.
  • 3 liters / h of a 96% strength by weight sulfuric acid is charged at the top of the column. As it trickles through the column, the sulfuric acid dilutes and is discharged in the bottom of the column as dilute sulfuric acid.
  • the gas stream is then compressed in the compressor 11 to 12 bar abs and cooled in the cooler 12 to about 40 0 C.
  • the temperature of the gas stream in the condenser 13 is lowered to -10 0 C to condense a portion of the chlorine contained in the gas stream.
  • carbon dioxide partially condenses in the gas stream, so that the quality of the liquid chlorine is not sufficient for its further use.
  • the carbon dioxide is stripped in the tray 14 equipped with trays and the largely carbon dioxide-free liquid chlorine leaves the column. A portion of this chlorine is vaporized in the evaporator 15 at the lower end of the column 14 and fed to this as stripping steam.
  • the remaining chlorine is completely evaporated in the evaporator 16 and fed into a pipeline network.
  • the gas stream is passed through a condenser 17 and cooled to -40 0 C or lower. In this case, further chlorine and carbon dioxide condenses and is returned to the column 14.
  • the remaining residual gas essentially contains the unreacted oxygen and is therefore recycled back to the reactor. Since it comprises coming from the condenser 17 to a temperature of -40 0 C, it must first be heated. For this purpose it flows through the heat exchanger 18 and is heated to ambient temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de réalisation d'un procédé d'oxydation de chlorure d'hydrogène éventuellement assisté par catalyseur, au moyen d'oxygène. Le procédé comporte le refroidissement en une ou plusieurs étapes des gaz de processus; la séparation de chlorure d'hydrogène n'ayant pas réagi et d'eau de réaction hors du gaz de processus; le séchage des gaz de produit; la séparation de chlore hors du mélange; et la recirculation de l'oxygène n'ayant pas réagi dans le procédé d'oxydation de chlorure d'hydrogène, au moins une partie de la capacité thermique des gaz de produit étant employée pour la récupération thermique et au moins une partie des flux gazeux les plus froids étant employée dans le procédé pour le refroidissement.
EP08735020A 2007-04-17 2008-04-04 Intégration thermique dans un procédé deacon Withdrawn EP2146927A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007018014A DE102007018014A1 (de) 2007-04-17 2007-04-17 Wärmeintegration in einem Deacon-Prozess
PCT/EP2008/002688 WO2008125236A2 (fr) 2007-04-17 2008-04-04 Intégration thermique dans un procédé deacon

Publications (1)

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EP2146927A2 true EP2146927A2 (fr) 2010-01-27

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Application Number Title Priority Date Filing Date
EP08735020A Withdrawn EP2146927A2 (fr) 2007-04-17 2008-04-04 Intégration thermique dans un procédé deacon

Country Status (7)

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US (1) US20080260619A1 (fr)
EP (1) EP2146927A2 (fr)
JP (1) JP2010524815A (fr)
KR (1) KR20100015632A (fr)
CN (1) CN101663233A (fr)
DE (1) DE102007018014A1 (fr)
WO (1) WO2008125236A2 (fr)

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WO2012110587A1 (fr) * 2011-02-18 2012-08-23 Basf Se Procédé de distillation pour séparer le chlore présent dans des flux gazeux contenant de l'oxygène et du chlore

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WO2011018443A2 (fr) 2009-08-11 2011-02-17 Basf Se Procédé de production de diisocyanates par phosgénation en phase gazeuse
WO2012142084A1 (fr) 2011-04-11 2012-10-18 ADA-ES, Inc. Méthode par lit fluidisé et système de capture de composant gazeux
KR101399338B1 (ko) 2011-08-08 2014-05-30 (주)실리콘화일 이중 감지 기능을 가지는 기판 적층형 이미지 센서
KR101334099B1 (ko) 2011-11-17 2013-11-29 (주)실리콘화일 이중 감지 기능을 가지는 기판 적층형 이미지 센서
IN2015DN02082A (fr) 2012-09-20 2015-08-14 Ada Es Inc
CN105228951B (zh) * 2013-05-22 2018-09-25 科思创德国股份公司 用于通过分馏纯化原料气体的方法
CN105480946A (zh) * 2014-09-19 2016-04-13 上海氯碱化工股份有限公司 氯化氢制氯工艺中氧气回收循环利用的方法

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DE3436139A1 (de) 1984-10-02 1986-04-10 Wacker-Chemie GmbH, 8000 München Verfahren zur waermerueckgewinnung bei der verbrennung von organischen chlorverbindungen
US4774070A (en) 1986-02-19 1988-09-27 Mitsui Toatsu Chemicals, Incorporated Production process of chlorine
US4994256A (en) * 1989-05-31 1991-02-19 Medalert, Inc. Recovery of chlorine from hydrogen chloride by carrier catalyst process
DE19535716A1 (de) 1995-09-26 1997-03-27 Bayer Ag Verfahren zur Aufarbeitung der Reaktionsgase bei der Oxidation von HCI zu Chlor
JP2003292304A (ja) 2002-03-29 2003-10-15 Sumitomo Chem Co Ltd 純塩素ガスの製造方法

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WO2012110587A1 (fr) * 2011-02-18 2012-08-23 Basf Se Procédé de distillation pour séparer le chlore présent dans des flux gazeux contenant de l'oxygène et du chlore

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Publication number Publication date
KR20100015632A (ko) 2010-02-12
WO2008125236A2 (fr) 2008-10-23
DE102007018014A1 (de) 2008-10-23
WO2008125236A3 (fr) 2009-04-16
CN101663233A (zh) 2010-03-03
JP2010524815A (ja) 2010-07-22
US20080260619A1 (en) 2008-10-23

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