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
• • 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
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/612—Surface area less than 10 m2/g
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • 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
• • 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
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying

Definitions

• the present invention relates to a process for the production of chlorine by catalytic gas-phase oxidation of hydrogen chloride with oxygen, wherein the catalyst comprises tin dioxide and at least one halogen-containing ruthenium compound, a catalyst composition and the use thereof.
• the oxidation of hydrogen chloride to chlorine is an equilibrium reaction.
• the position of the equilibrium shifts with increasing temperature to the detriment of the desired end product. It is therefore advantageous to use catalysts with the highest possible activity, which allow the reaction to proceed at low temperature.
• the first catalysts for the hydrogen chloride oxidation contained as active component copper chloride or oxide and were already described in 1868 by Deacon. However, these showed low activity at low temperature ( ⁇ 400 0 C). Although the activity could be increased by increasing the reaction temperature, it was disadvantageous that the volatility of the active components at high temperatures led to a rapid decrease in the catalyst activity.
• EP 0 184 413 describes the oxidation of hydrogen chloride with catalysts based on chromium oxides.
• the first catalysts for the hydrogen chloride oxidation with the catalytically active component ruthenium were already described in 1965 in DE 1 567 788. In this case, starting from RuCl 3, for example, supported on silica and alumina. However, the activity of these RuCl 3 / SiO 2 catalysts is very low.
• Ru-based catalysts with the active material ruthenium oxide or ruthenium mixed oxide and as carrier material various oxides, such as, for example, titanium dioxide, zirconium dioxide, etc., have been claimed in DE-A 197 48 299.
• the content of ruthenium oxide is from 0.1% by weight to 20% by weight and the average particle diameter of ruthenium oxide is from 1.0 nm to 10.0 nm.
• Further Ru catalysts supported on titanium dioxide or zirconium dioxide are known from DE-A 197 34 412 known.
• Ru starting compounds such as, for example, ruthenium-carbonyl complexes, ruthenium salts of inorganic acids, ruthenium-nitrosyl complexes, Ruthenium-amine complexes, ruthenium complexes of organic amines or ruthenium-acetylacetonate complexes.
• TiO 2 was used as a carrier in the form of rutile.
• the ruthenium oxide catalysts have quite high activity, but their preparation is complicated and requires a series of operations such as precipitation, impregnation followed by precipitation, etc., whose scale-up is technically difficult. In addition, ruthenium oxide catalysts also tend to sinter at high temperatures and thus to deactivate.
• EP 0 936 184 A2 describes a process for catalytic hydrogen chloride oxidation wherein the catalyst is selected from an extensive list of possible catalysts.
• the catalysts is the variant designated by number (6), which consists of the active component (A) and a component (B).
• the component (B) is a compound component having a certain thermal conductivity.
• the component (A) can be mounted on a support.
• possible carriers do not include tin dioxide. There is not a single example in which tin dioxide was used.
• this patent exclusively describes the use of ruthenium oxide as a catalyst component.
• the object of the present invention was to provide a catalytic system which accomplishes the oxidation of hydrogen chloride at low temperatures and with high activities.
• the task is solved by the development of a very specific combination of catalytically active components and a specific carrier material.
• the present invention thus provides a process for producing chlorine by catalytic gas-phase oxidation of hydrogen chloride with oxygen, wherein the catalyst comprises at least tin dioxide and at least one halogen-containing ruthenium compound.
• tin (IV) oxide is used as a carrier of the catalytically active component, particularly preferably tin dioxide in rutile structure.
• a halogen-containing ruthenium compound is used as the catalytically active component. It is a compound in which halogen ionic to polarized is covalently bonded to a ruthenium atom.
• the halogen in the halogen-containing ruthenium compound is preferably selected from the group consisting of chlorine, bromine and iodine. Particularly preferred is chlorine.
• the halogen-containing ruthenium compound includes those consisting solely of halogen and ruthenium. However, preference is given to those which contain both oxygen and halogen, in particular chlorine or chloride. At least one ruthenium oxychloride compound is particularly preferably used as the catalytically active species.
• a ruthenium oxychloride compound in the context of the invention is a compound in which both oxygen and chlorine are present ionically to polarized covalently bonded to ruthenium. Such a compound thus has the general composition RuO x CI y .
• various such ruthenium oxychloride compounds can be present side by side in the catalyst. Examples of defined Ruthenium oxychloride compounds include in particular the following compositions: Ru 2 OCl 4 , RuOCl 2 , Ru 2 OCl 5 and Ru 2 OCl 6 .
• the halogen-containing ruthenium compound is a mixed compound corresponding to the general formula RuCl x Oy, wherein x is a number from 0.8 to 1.5 and y is a number from 0.7 to 1.6.
• the catalytically active ruthenium oxychloride compound according to the invention is preferably obtainable by a process which comprises first applying a particular aqueous solution or suspension of at least one halogen-containing ruthenium compound to tin dioxide and removing the solvent.
• a preferred method involves applying an aqueous solution of RuCl 3 to the tin dioxide.
• the application includes in particular the impregnation of the optionally freshly precipitated tin dioxide with the solution of the halogen-containing ruthenium compound.
• a drying step which is conveniently carried out in the presence of oxygen or air to at least partially to allow conversion to the preferred ruthenium oxychloride compounds.
• the drying should preferably be less than 280 ° C carried out, in particular at least 80 0 C, more preferably at least 100 0 C.
• a preferred method is characterized in that the catalyst is obtainable in that a containing a halogen-containing ruthenium compound tin dioxide at a temperature of at least 200 0 C, preferably at least 22O 0 C, more preferably at least 25O 0 C to 500 0 C, in particular is calcined in an oxygen-containing atmosphere, more preferably under air.
• the proportion of ruthenium from the halogen-containing ruthenium compound in relation to the total catalyst composition, in particular after calcining is 0.5 to 5% by weight, preferably 1.0 to 3% by weight, more preferably 1.5 to 3% by weight. If, as a catalytically active species, halogen-ruthenium compounds which contain no oxygen are to be absorbed, drying is also possible at elevated temperatures, with exclusion of oxygen.
• the substantial conversion of the halogen-ruthenium compound into the preferred ruthenium oxyhalogen compounds is preferably carried out in the reactor under the conditions of the oxidation process.
• HR-TEM High Resolution - Transmission Electron Microscopy
• the catalyst is obtainable by a process which comprises applying an aqueous solution or suspension of at least one halogen-containing ruthenium compound to tin dioxide and then drying at less than 280 ° C., and then activating under the conditions of gas-phase oxidation of hydrogen chloride, in which a substantial conversion takes place in the Rutheniumoxychloride. The longer the drying takes place in the presence of oxygen, the more oxychloride forms.
• the loading of the catalytically active component i. of the halogen-containing ruthenium compound, in the range of 0.1-80% by weight, preferably in the range of 1-50% by weight, particularly preferably in the range of 1-20% by weight, based on the total weight of the catalyst ( Catalyst component and carrier).
• the catalytic component i. the halogen-containing ruthenium compound
• a carrier with suitable present in solution starting compounds or starting compounds in liquid or colloidal form, up and co-Aufsocilclar, and ion exchange and gas phase coating (CVD, PVD) are applied to the support.
• CVD ion exchange and gas phase coating
• Suitable promoters are in particular basic metals - e.g. Alkali, alkaline earth and rare earth metals -, alkali metals are particularly preferred Na and Cs and alkaline earth metals, particularly preferred are alkaline earth metals, in particular Sr and Ba.
• the promoters may, but are not limited to, be applied to the catalyst by impregnation and CVD processes; preference is given to impregnation, particularly preferably after application of the main catalytic component.
• various dispersion stabilizers such as For example, scandium oxides, manganese oxides and lanthanum oxides, etc. are used.
• the stabilizers are preferably applied together with the main catalytic component by impregnation and / or precipitation.
• the tin dioxide used according to the invention is commercially available (eg from Chempur, Alfa Aesar) or obtainable, for example, by alkaline precipitation of tin (TV) chloride and subsequent drying. It has in particular BET surface areas of about 1 to 300 m 2 / g.
• the tin dioxide used as the carrier according to the invention may under thermal stress (such as at temperatures greater than 250 0 C) undergo a reduction in the specific surface area, which may be accompanied by a reduction in the catalyst activity.
• the pretreatment of the Vicinal carrier can be done by calcination, for example at 250-1500 ° C, but more preferably at 300-1200 0 C.
• the above-mentioned dispersion stabilizers may also serve to stabilize the surface of the tin dioxide at high temperatures.
• a further preferred method is namely characterized in that the reaction temperature in the catalytic gas phase oxidation up to 450 0 C, preferably at most 420 0 C.
• the catalysts can be dried under normal pressure or preferably at reduced pressure, preferably at 40 to 200 ° C.
• the drying time is preferably 10 minutes to 6 hours.
• the catalysts according to the invention for the hydrogen chloride oxidation are characterized by a high activity at low temperatures.
• the new catalyst composition is used in the catalytic process known as the Deacon process.
• hydrogen chloride is oxidized with oxygen in an exothermic equilibrium reaction to chlorine, whereby water vapor is obtained.
• the reaction temperature is usually from 180 to 500 0 C, particularly preferably 200 to 400 0 C, particularly preferably 220 to 350 0 C
• the reaction pressure can be 1 to 25 bar, preferably 1, 2 to 20 bar, particularly preferably 1.5 to 17 bar, most preferably 2 to 15 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.
• Suitable preferred catalysts for the Deacon process which may be combined with the novel catalyst support include ruthenium oxide, ruthenium chloride or other ruthenium compounds supported on silica, alumina, titania or zirconia.
• suitable catalysts may also contain compounds of other noble metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium. Suitable catalysts may further 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 35O 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 particularly preferably carried out 2.0 to 15 bar become.
• 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.
• Another preferred embodiment of a suitable device for the method is that one uses a structured catalyst bed, in which the catalyst activity in
• Such structuring of the catalyst bed can be achieved by different impregnation of the catalyst support with active material or by different
• an inert material for example, rings, cylinders or balls of tin dioxide, titanium dioxide, zirconium dioxide or mixtures thereof, alumina, steatite, ceramic, glass, graphite or stainless steel can be used.
• the inert material should preferably similar outer
• Ais shaped catalyst bodies are molded body with arbitrary shapes, preferably are tablets, rings, cylinders, stars, wagon wheels or balls, particularly preferred are rings, cylinders, balls or star strands as a form.
• the spherical shape is preferred.
• the size of the shaped catalyst body, bsp. On average, the diameter of spheres or the maximum cross-sectional width is 0.3 to 7 mm, more preferably 0.8 to 5 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.
• the monolithic carrier may have a honeycomb structure, but also an open or closed cross-channel structure.
• the monolithic carrier has a preferred cell density of 100 to 900 cpsi (cells per square inch), more preferably 200 to 600 cpsi.
• 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.
• Preferred binder is alumina or zirconia.
• the proportion of binder, based on the finished catalyst, can be 1 to 70% by weight, preferably 2 to 50% by weight and very preferably 5 to 30% by weight.
• the binder increases the mechanical stability (strength) of the shaped catalyst bodies.
• the catalytically active component is substantially on the surface of the actual support material, e.g. of the tin oxide, but not present on the surface of the binder.
• 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, more 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.
• 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%.
• 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.
• the invention further provides the use of tin dioxide as a catalyst support for a catalyst in the catalytic gas phase oxidation of hydrogen chloride with oxygen.
• the invention further provides a catalyst composition comprising tin dioxide and at least one halogen-containing ruthenium compound.
• halogen is selected from the group: chlorine, bromine and iodine.
• the halogen-containing ruthenium compound particularly preferably comprises a ruthenium oxychloride compound.
• the halogen-containing ruthenium compound is a mixed compound corresponding to the general formula RuCl x Oy, wherein x is a number from 0.8 to 1.5 and y is a number from 0.7 to 1.6.
• the catalyst composition is preferably obtainable by a process which comprises applying a particular aqueous solution or suspension of at least one halogen-containing ruthenium compound to tin dioxide and removing the solvent.
• the halogen-containing ruthenium compound RuCl 3 is particularly preferred.
• the catalyst composition is obtainable, in particular, by a process which comprises applying an aqueous solution or suspension of at least one halogen-containing ruthenium compound to tin dioxide and subsequently drying it at at least 80 ° C., preferably at least 100 ° C.
• the catalyst composition is particularly preferably obtainable by a method that a loaded with a halogen-containing ruthenium compound Zinndioxidtik at a temperature of at least 200 0 C, preferably at least 240 0 C, particularly preferably at least 27O 0 C to 500 0 C, in particular in an oxygen-containing Atmosphere, particularly preferably calcined under air.
• the proportion of the halogen-containing ruthenium compound in relation to the total catalyst composition is, in particular after calcining, 0.5 to 5% by weight, preferably 1.0 to 3% by weight.
• Another object of the invention is the use of the catalyst composition as a catalyst, in particular for oxidation reactions, particularly preferably as a catalyst in the catalytic gas phase oxidation of hydrogen chloride with oxygen.
• Ru was 4.1% by weight of Cl 1.1% by weight.
• Example 1 a catalyst ruthenium chloride was prepared on silica (silica gel 100, Merck) and calcined for 3 h at 250 0 C in an air stream.
• the amount of Ru determined by elemental analysis (ICP-OES) was 4.1% by weight, of Cl 0.8% by weight.
• the reaction mixture was then heated to 65 ° C and kept for 1 h at this temperature and cooled with stirring to 40 0 C. Thereafter, the suspension was filtered off and the solid was washed five times with 50 ml of water. The moist solid was dried at 120 ° C. in a vacuum drying oven for 4 hours and then calcined in a muffle furnace for 2 hours at 300 ° C.
• the amount of Ru determined by elemental analysis (ICP-OES) was 4.0% by weight of that of Cl ⁇ 0.2% by weight.
• the catalysts from Examples 1 to 5 were in a fixed bed in a quartz reaction tube (internal diameter 10 mm) at 300 0 C with a gas mixture of 80 ml / min
• Example 1 The catalyst of Example 1 was tested as described above, but the experimental time was extended and several samples were taken by bubbling into 16% potassium iodide solution for 10 minutes. This results in the chlorine quantities listed in FIG.
• Ni reactor was heated by means of a heat transfer medium. After 30 min was the
• ruthenium chloride n-hydrate (Heraeus) were dissolved in 0.39 ml of water and added to 2.5 g of the carrier prepared in Example 7 and mixed until the solution was taken up by the carrier. The impregnation time was 1.5 h. The moist solid was then dried at 60 ° C. in the oven (air) for about 5 hours. The yield was 2.615 g. The thus prepared ruthenium-containing catalyst was finally calcined for 16 h at 250 0 C in a muffle furnace. The ruthenium content was 1, lWew .-% based on the catalyst material.
• FIG. 2 shows a scanning electron micrograph of the extrudate cross section.
• Figures 3 and 4 show the tin and the ruthenium distribution of this section. Taking into account the carrier-free image sections, the uniform distribution of ruthenium in the carrier extrudate can be seen.
• the catalyst from Example 8 was in a solid bed in a quartz reaction tube (diameter 10 mm) at 300 0 C with a gas mixture of 80 ml / min (STP) of hydrogen chloride and 80 ml / min (STP) oxygen flowed through.
• the quartz reaction tube was heated by an electrically heated sand fluid bed. After 30 minutes, the product gas stream was passed into 16% potassium iodide solution for 10 minutes. The resulting iodine was then back titrated with 0.1 N thiosulfate standard solution to determine the amount of chlorine introduced. The result was a space-time yield of 1.46 kg ca / kg K a f h.

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• 2007
  • 2007-04-26 DE DE102007020154A patent/DE102007020154A1/de not_active Withdrawn
  • 2007-05-16 JP JP2009511377A patent/JP2009537449A/ja not_active Withdrawn
  • 2007-05-16 EP EP07725285A patent/EP2026905A1/de not_active Withdrawn
  • 2007-05-16 BR BRPI0712011-7A patent/BRPI0712011A2/pt not_active IP Right Cessation
  • 2007-05-16 WO PCT/EP2007/004369 patent/WO2007134772A1/de not_active Ceased
  • 2007-05-16 RU RU2008150585/15A patent/RU2008150585A/ru not_active Application Discontinuation
  • 2007-05-16 KR KR1020087028582A patent/KR20090009896A/ko not_active Ceased
  • 2007-05-22 TW TW096118060A patent/TW200812909A/zh unknown
  • 2007-05-23 US US11/752,403 patent/US20070274897A1/en not_active Abandoned

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