Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/63—Platinum group metals with rare earths or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
  • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
  • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
  • B01J27/13—Platinum group metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/46—Ruthenium, rhodium, osmium or iridium
  • B01J23/462—Ruthenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0207—Pretreatment of the support

Definitions

• the invention is based on known processes for the catalyzed gas phase oxidation of hydrogen chloride with oxygen.
• the object of the invention is to modify a ruthenium-based catalyst for the Deacon process so that the activity is maintained over the longest possible period of time, in particular for at least hours, while the activity of the catalyst remains unchanged.
• a catalyst which is characterized in that it is supported and comprises as support material a material from the series silicon oxide, titanium oxide, aluminum oxide, tin oxide and zirconium oxide and optionally mixtures of these substances.
• Another particularly preferred catalyst is characterized in that the activity of the catalyst for the reaction of hydrogen chloride with oxygen at different conversion and at a pressure of 5 bar and a temperature of 300 0 C is at least 5 mmol of chlorine per g of ruthenium and minute.
• the invention also relates to the use of the catalyst for use in gas-phase oxidation processes, in particular in the reaction of hydrogen chloride with oxygen in the gas phase.
• Another object of the invention is a process for the reaction of hydrogen chloride with oxygen in the gas phase in the presence of a catalyst, characterized in that a catalyst according to the invention is used.
• the catalyst is preferably used in the abovementioned catalytic process known as the Deacon process.
• This hydrogen chloride is oxygen in an exothermic
• 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. Furthermore, it is expedient to use 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 catalysts can be obtained, for example, by applying ruthenium chloride to the support and then drying or drying and calcining.
• suitable catalysts may also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium.
• Suitable catalysts may additionally contain chromium oxide.
• the catalytic hydrogen chloride oxidation may preferably be adiabatic or 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, more preferably 220 to 350 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.
• a plurality of reactors with intermediate cooling that is to say 2 to 10, preferably 2 to 6, particularly preferably 2 to 5, in particular 2 to 3, 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.
• 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.
• 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.
• the dimensions (diameter in the case of spheres) of the shaped bodies are preferably in the range from 0.2 to 10 mm, particularly preferably 0.5 to 7 mm.
• the support may also be a monolith of support material, e.g. not only a "classical" carrier body with parallel, radially non-interconnected channels, it also includes foams, sponges or the like with three-dimensional connections within the carrier body to the monoliths and carrier body with cross-flow channels.
• a monolith according to the present invention is e.g. in "Monoliths in multiphase catalytic processes - aspects and prospects" by F. Kapteijn, J.J. Heiszwolf T.A. Nijhuis and J.A. Moulijn, Cattech 3, 1999, p24.
• suitable carrier materials are tin dioxide, silicon dioxide, graphite, rutile or anatase titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, preferably tin dioxide, titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof, particularly preferably ⁇ - or ⁇ -aluminum oxide or mixtures thereof ,
• the conversion of hydrogen chloride in a single pass can preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 80%. 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 preferably 1: 1 to 20: 1, preferably 2: 1 to 8: 1, particularly 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 be used to operate a phosgenation reactor and / or distillation columns, in particular of isocyanate distillation columns.
• 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. Examples
• 0.2 g of the dried catalyst was diluted with 0.5 g of SiO 2 (Saint Gobain, 1.5 mm) and passed through at 540 ° C. with 80 ml / min (STP) of oxygen and 160 ml / min (STP) of hydrogen chloride.
• the amount of chlorine formed was determined via introduction into a 16% potassium iodide solution and titration of the resulting iodine with thiosulphate. The result was the time profile of the space-time yield shown in FIG.
• 0.2 g of the dried catalyst was diluted with 0.5 g of SiO 2 (Saint Gobain, 1.5 mm) and perfused at 540 ° C. with 80 ml / min (STP) of oxygen and 160 ml / min (STP) of hydrogen chloride.
• the amount of chlorine formed was determined via introduction into a 16% potassium iodide solution and titration of the resulting iodine with thiosulphate. The result was the time profile of the space-time yield shown in FIG.
• 0.2 g of the dried catalyst was diluted with 0.5 g of SiO 2 (Saint Gobain, 1.5 mm) and perfused at 540 ° C. with 80 ml / min (STP) of oxygen and 160 ml / min (STP) of hydrogen chloride.
• the amount of chlorine formed was determined via introduction into a 16% potassium iodide solution and titration of the resulting iodine with thiosulphate. The result was the time profile of the space-time yield shown in FIG.
• FIG. 1 clearly shows the prolongation of the long-term stability of the promoted catalysts (> 24 h) compared to the unpromoted catalyst (18 h).
• Table 1 shows no significant influence of different promoters in a RuCl 3 / SnO 2 catalyst and 300 0 C reaction temperature. Only the promotion with CsNO 3 shows a significant deterioration, which does not occur when using CsCl.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Catalysts (AREA)

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• 2007
  • 2007-04-26 DE DE102007020143A patent/DE102007020143A1/de not_active Withdrawn
• 2008
  • 2008-04-16 WO PCT/EP2008/003006 patent/WO2008131857A1/de active Application Filing
  • 2008-04-16 JP JP2010504500A patent/JP2010524673A/ja not_active Withdrawn
  • 2008-04-16 EP EP08735261A patent/EP2142296A1/de not_active Ceased
  • 2008-04-16 CN CN200880013132A patent/CN101663092A/zh active Pending
  • 2008-04-16 KR KR1020097022236A patent/KR20100015864A/ko not_active Application Discontinuation
  • 2008-04-23 US US12/108,116 patent/US20080267857A1/en not_active Abandoned
  • 2008-04-25 TW TW097115159A patent/TW200909050A/zh unknown

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