WO2010058810A1 - Procédé de fabrication de chlore - Google Patents

Procédé de fabrication de chlore Download PDF

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Publication number
WO2010058810A1
WO2010058810A1 PCT/JP2009/069606 JP2009069606W WO2010058810A1 WO 2010058810 A1 WO2010058810 A1 WO 2010058810A1 JP 2009069606 W JP2009069606 W JP 2009069606W WO 2010058810 A1 WO2010058810 A1 WO 2010058810A1
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Prior art keywords
hydrogen chloride
compound
catalyst
titanium oxide
gas
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PCT/JP2009/069606
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English (en)
Japanese (ja)
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ビエレン カルロス グスタボ クナップ
航平 関
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住友化学株式会社
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Priority to CN2009801463915A priority Critical patent/CN102224101A/zh
Publication of WO2010058810A1 publication Critical patent/WO2010058810A1/fr

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    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid

Definitions

  • the present invention provides a mixed gas containing at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and organic compounds and hydrogen chloride in the presence of a catalyst in which a ruthenium compound is supported on titanium oxide, It is related with the manufacturing method of the chlorine which oxidizes the said compound by contacting with the gas containing this, and oxidizes hydrogen chloride.
  • Patent Document 1 discloses a method in which the oxidation reaction is performed in the presence of a catalyst in which ruthenium and / or a ruthenium compound is supported on titanium oxide. Are known.
  • the above-described conventional methods are not necessarily sufficient in terms of the conversion rate of the oxidation reaction in at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and organic compounds.
  • the present invention provides a mixed gas containing at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and an organic compound and hydrogen chloride in the presence of a catalyst in which silica and a ruthenium compound are supported on titanium oxide. Is contacted with a gas containing oxygen to oxidize the compound and provide a method for producing chlorine that oxidizes hydrogen chloride.
  • chlorine can be produced by satisfactorily oxidizing at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and an organic compound, and also satisfactorily oxidizing hydrogen chloride.
  • Examples of the mixed gas containing at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and organic compounds and hydrogen chloride include, for example, a reaction between hydrogen and chlorine, a thermal decomposition reaction or combustion reaction of a chlorine compound, an organic Any compound containing phosgenation reaction or chlorination reaction of a compound, production of chlorofluoroalkane, hydrolysis reaction of chlorinated hydrocarbon, heating of hydrochloric acid, combustion in an incinerator, etc. can be used. It should be noted that oxygen and inert gas that can be recovered from each of these reactions and hydrogen chloride oxidation reaction can also be used.
  • thermal decomposition reaction of chlorine compounds examples include the production of vinyl chloride from 1,2-dichloroethane and the production of tetrafluoroethylene from chlorodifluoromethane.
  • Examples of the phosgenation reaction of an organic compound include production of isocyanate by reaction of amine and phosgene, and production of carbonate ester by reaction of alcohol and / or aromatic alcohol with phosgene.
  • the chlorination reaction of organic compounds includes the production of allyl chloride by the reaction of propylene and chlorine, the production of ethyl chloride by the reaction of ethane and chlorine, the production of trichloroethylene and tetrachloroethylene by the reaction of 1,2-dichloroethane and chlorine, Examples include production of chlorobenzene by reaction of benzene and chlorine.
  • the production of chlorofluoroalkane includes the production of dichlorodifluoromethane and trichloromonofluoromethane by the reaction of carbon tetrachloride and hydrogen fluoride, and the production of dichlorodifluoromethane and trichloromonofluoromethane by the reaction of methane, chlorine and hydrogen fluoride. Manufacturing etc. are mentioned.
  • Examples of the hydrolysis reaction of chlorinated hydrocarbons include the production of phenol by the reaction of chlorobenzene and water.
  • a mixed gas containing hydrogen chloride and at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and an organic compound is brought into contact with a gas containing oxygen.
  • the compounds such as carbon monoxide, phosgene, hydrogen and organic compounds mentioned here are usually contained as impurities in hydrogen chloride as described above. However, in the present invention, not only impurities contained in hydrogen chloride but also chlorine production. Carbon monoxide, phosgene, hydrogen and organic compounds contained in all gases used in the process can also be oxidized.
  • the organic compound is appropriately selected, but preferably at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, alcohols and phenols. It is a seed.
  • aliphatic hydrocarbon herein include aliphatic saturated hydrocarbons such as methane, ethane, propane, butane, and hexane, and aliphatic unsaturated hydrocarbons such as ethylene, propylene, butene, hexene, and acetylene. Of these, methane, ethane, ethylene, propylene, and acetylene are preferable.
  • chlorinated aliphatic hydrocarbons examples include dichloroethane such as methyl chloride, dichloromethane, trichloromethane, carbon tetrachloride, ethyl chloride, and 1,2-dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, and 2-chloropropane.
  • chloropropene such as chloropropane, vinyl chloride, dichloroethylene, trichloroethylene, and tetrachloroethylene, allyl chloride, and dichloropropene such as 1,3-dichloro-1-propene.
  • methyl chloride methyl chloride, dichloromethane, trichloromethane, carbon tetrachloride, ethyl chloride, vinyl chloride, dichloroethane, chloropropane, dichloropropane, allyl chloride, and dichloropropene are preferable.
  • aromatic hydrocarbon examples include benzene, toluene, xylene and the like.
  • chlorinated aromatic hydrocarbons include dichlorobenzene such as monochlorobenzene and orthodichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, and phenyl chloroformate. Of these, monochlorobenzene and dichlorobenzene are preferable.
  • alcohol examples include methanol, ethanol, propanol and the like.
  • aromatic alcohols examples include phenol and cresol.
  • the content thereof is usually 5% by volume or less, preferably 1% by volume or less, more preferably 0.1% by volume or less with respect to hydrogen chloride.
  • the activity of a catalyst may fall.
  • the content of the organic compound is 0.1 volume ppm or more with respect to hydrogen chloride, the present invention is advantageously employed.
  • the content thereof is usually 5% by volume or less, preferably 1% by volume or less, more preferably 0.1% by volume or less with respect to hydrogen chloride.
  • the content of carbon monoxide is too large, the activity of the catalyst may decrease.
  • the content of carbon monoxide is 0.1 volume ppm or more with respect to hydrogen chloride, the present invention is advantageously employed.
  • the content thereof is usually 5% by volume or less, preferably 2% by volume or less, more preferably 1% by volume or less with respect to hydrogen chloride. If the hydrogen content is too high, the activity of the catalyst may be reduced. On the other hand, the present invention is advantageously employed when the hydrogen content is 0.1 volume ppm or more with respect to hydrogen chloride.
  • the content thereof is usually 5% by volume or less, preferably 1% by volume or less, more preferably 0.5% by volume or less with respect to hydrogen chloride. If the phosgene content is too high, the activity of the catalyst may be reduced. On the other hand, the present invention is advantageously employed when the phosgene content is 0.1 ppm by volume or more with respect to hydrogen chloride.
  • Hydrogen chloride may be diluted with a gas inert to the oxidation reaction such as nitrogen gas or argon gas.
  • a gas inert to the oxidation reaction such as nitrogen gas or argon gas.
  • the concentration of hydrogen chloride in the mixed gas is usually 30% by volume or more, preferably 50% by volume. As mentioned above, More preferably, it is 60 volume% or more.
  • oxygen source air or pure oxygen is used as the oxygen source.
  • Pure oxygen can be prepared by an air pressure swing method, a cryogenic separation method, or the like.
  • the molar ratio of oxygen to hydrogen chloride is preferably 0.1 or more, and more preferably 0.2 or more. If the amount of oxygen is too small, the conversion rate of the oxidation reaction in carbon monoxide, phosgene, hydrogen or an organic compound may be low.
  • the present invention satisfactorily oxidizes compounds such as carbon monoxide, phosgene, hydrogen, and organic compounds by performing the oxidation reaction in the presence of a catalyst in which silica and a ruthenium compound are supported on titanium oxide, and hydrogen chloride. It can oxidize well and produce chlorine.
  • the ruthenium compound include metal ruthenium which is ruthenium as a simple metal, ruthenium oxide, ruthenium chloride, ruthenium chloride hydrate, nitrosyl ruthenium nitrate, a ruthenium carbonyl complex, and a mixture of any combination thereof.
  • ruthenium oxide is preferable.
  • titanium oxide in the present invention includes a composite oxide of titanium oxide and other metal oxides, and a mixture of titanium oxide and other metal oxides such as alumina, zirconium oxide, and silica. It is. Among these, titanium oxide itself is preferable. Titanium oxide includes amorphous ones, anatase crystal form (anatase type titanium oxide), and rutile crystal form (rutile type titanium oxide). Especially, what consists of a rutile type titanium oxide and / or an anatase type titanium oxide is preferable. Furthermore, the ratio of rutile type titanium oxide to rutile type titanium oxide and anatase type titanium oxide is preferably 20% or more, more preferably 30% or more, and even more preferably 90% or more. The higher the rutile titanium oxide ratio, the better the activity of the resulting catalyst.
  • Examples of the catalyst in which silica and a ruthenium compound are supported on titanium oxide in the present invention include the following. (1) A product obtained by supporting a silicon compound on titanium oxide, then supporting a ruthenium compound, and then firing in an oxidizing gas atmosphere. (2) Titanium halide and silicon halide are heat-treated in an oxidizing gas atmosphere to obtain a titanium oxide carrier on which silica is supported, and obtained by firing after supporting a ruthenium compound on the carrier. thing. (3) A product obtained by supporting a ruthenium compound on titanium oxide, then supporting a silicon compound, and then firing in an oxidizing gas atmosphere. (4) A product obtained by firing a titanium oxide with a silicon compound and a ruthenium compound supported thereon.
  • firing may be performed in an oxidizing gas atmosphere.
  • ruthenium compound after the silicon compound is supported, firing may be performed in an oxidizing gas atmosphere.
  • the catalyst is obtained by supporting a silicon compound or ruthenium compound on titanium oxide and then firing in an atmosphere of an oxidizing gas to obtain a titanium oxide support on which silica or ruthenium is supported. It may be a supported ruthenium oxide catalyst obtained by supporting a silicon compound and calcining in an oxidizing gas atmosphere.
  • examples of the titanium halide include titanium chloride (TiCl 4 ) and titanium bromide (TiBr 4 ).
  • silicon halide examples include silicon chloride (SiCl 4 ) and silicon bromide ( SiBr 4 ) and the like.
  • SiCl 4 silicon chloride
  • SiBr 4 silicon bromide
  • the catalyst obtained in the above (1) is particularly preferable.
  • silicon compound examples include silicon alkoxide compounds such as Si (OR) 4 (hereinafter, R represents an alkyl group having 1 to 4 carbon atoms), silicon chloride (SiCl 4 ), silicon bromide (SiBr 4 ), and the like.
  • silicon halide alkoxide compounds such as silicon halide, SiCl (OR) 3 , SiCl 2 (OR) 2 , and SiCl 3 (OR).
  • the hydrate may be used as needed and 2 or more types thereof may be used.
  • silicon alkoxide compounds are preferable, and silicon tetraethoxide, that is, tetraethyl orthosilicate [Si (OC 2 H 5 ) 4 ] is more preferable.
  • the amount of the silicon compound used is appropriately adjusted so that the silica in the catalyst is usually 0.001 to 0.3 mol, preferably 0.004 to 0.03 mol, per 1 mol of titanium oxide.
  • a method for supporting a silicon compound or ruthenium compound on titanium oxide a method in which each compound is dissolved in an appropriate solvent is impregnated in titanium oxide, or titanium oxide is immersed in the solution, Examples include a method of adsorbing a compound.
  • titanium oxide powdered or sol-like titanium oxide can be kneaded, molded, and then fired.
  • the calcined titanium oxide can be prepared based on a known method. For example, after powdery or sol-like titanium oxide is kneaded with a molding aid such as an organic binder and water and extruded into a noodle shape. It can be prepared by drying, crushing to obtain a molded body, and then firing the obtained molded body in an oxidizing gas atmosphere such as air.
  • the ruthenium compound for example, RuCl 3, such as halides RuBr 3, K 3 RuCl 6, K 2 RuCl such halogeno salt of 6, such as oxo acid salt of K 2 RuO 4, Ru 2 OCl 4, Ru 2 OCl 5 , oxyhalides such as Ru 2 OCl 6 , K 2 [RuCl 5 (H 2 O) 4 ], [RuCl 2 (H 2 O) 4 ] Cl, K 2 [Ru 2 OCl 10 ], Cs 2 [Ru 2 OCl 4] such halogeno complex, [Ru (NH 3) 5 H 2 O] Cl 2, [Ru (NH 3) 5 Cl] Cl 2, [Ru (NH 3) 6] Cl 2, [Ru (NH 3 ) 6 ] Cl 3 , an ammine complex such as [Ru (NH 3 ) 6 ] Br 3, a carbonyl complex such as Ru (CO) 5 , Ru 3 (CO) 12 , [Ru 3 O (OCOCH 3 ) 6 (H 2 O) 3] OCOCH 3,
  • the use ratio of the ruthenium compound and titanium oxide is such that the weight ratio of ruthenium compound / titanium oxide is usually 0.1 / 99.9 to 20/80, preferably 0.3 / 99.7 to 10/90, more preferably What is necessary is just to adjust suitably so that it may be set to 0.5 / 99.5-5 / 95.
  • the amount of the ruthenium compound used is preferably adjusted so that the ruthenium compound in the catalyst is 0.1 to 4 mol per 1 mol of the supported silica, and is preferably 0.3 to 2 mol. It is more preferable to adjust.
  • the oxidizing gas is a gas containing an oxidizing substance, and examples thereof include an oxygen-containing gas.
  • the oxygen concentration is usually about 1 to 30% by volume.
  • air or pure oxygen is usually used, and diluted with an inert gas as necessary. Of these, air is preferable as the oxidizing gas.
  • the firing temperature is usually 100 to 500 ° C., preferably 200 to 350 ° C.
  • the catalyst may be used in the form of a spherical granule, a cylindrical pellet, an extruded shape, a ring shape, a honeycomb shape, or an appropriately sized granule that has been pulverized and classified after molding.
  • the diameter of the catalyst is preferably 5 mm or less. If the diameter of the catalyst is too large, the conversion rate of the oxidation reaction of carbon monoxide, phosgene, hydrogen and organic compounds may be low, or the conversion rate of hydrogen chloride to chlorine may be low.
  • the lower limit of the diameter of the catalyst is not particularly limited, but if it becomes excessively small, pressure loss in the catalyst layer increases, and therefore, a catalyst having a diameter of 0.5 mm or more is usually used.
  • the diameter of the catalyst here means the diameter of a sphere in the case of spherical particles, the diameter of a circular cross section in the case of a cylindrical pellet, and the maximum diameter of the cross section in other shapes.
  • a catalyst in which silica and a ruthenium compound are supported on titanium oxide can be obtained.
  • a method for preparing the catalyst for example, JP 2008-155199 A and JP 2002-292279 A can be referred to.
  • the amount of the catalyst used is usually 10 to 50000 h ⁇ 1 in terms of the ratio (GHSV) of at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and an organic compound and hydrogen chloride in the standard state (GHSV). It is.
  • the reaction temperature in the oxidation reaction according to the present invention is usually 200 to 500 ° C., preferably 250 to 450 ° C., more preferably 300 to 400 ° C. If the reaction temperature is too low, the conversion rate of the oxidation reaction of carbon monoxide, phosgene, hydrogen or an organic compound or the conversion rate of hydrogen chloride may be low. On the other hand, if the reaction temperature is too high, the catalyst component may volatilize.
  • the pressure of the oxidation reaction is usually 0.1 to 5 MPa, but preferably 0.1 to 1 MPa.
  • the gas linear velocity based on the empty tower is usually 0.1 to 20 m / s.
  • the superficial gas linear velocity means the ratio of the total supply rate of all the gases supplied to the reactor in the standard state to the cross-sectional area of the reactor.
  • reaction method examples include a fixed bed gas phase flow reaction method and a fluidized bed gas phase flow reaction method.
  • the heat exchange system means a system having a jacket portion outside the reaction tube filled with the catalyst and removing the reaction heat generated by the reaction by the heat medium in the jacket.
  • the temperature of the catalyst packed bed in the reaction tube is controlled by the heat medium in the jacket.
  • chlorine can usually be obtained by the following steps.
  • Reaction step oxidizing the compound by contacting a mixed gas containing hydrogen chloride with at least one compound selected from the group consisting of carbon monoxide, phosgene, hydrogen and an organic compound with a gas containing oxygen.
  • absorption step by cooling, bringing the gas obtained in the reaction step into contact with water and / or hydrochloric acid, or with water and / or hydrochloric acid
  • Drying step obtained in an absorption step Step of obtaining dried gas by removing moisture in gas
  • Purification step The dried gas obtained in the drying step is a liquid or gas mainly composed of chlorine and unreacted acid.
  • the mixed gas can be used in the reaction step after being brought into contact with activated carbon.
  • the solution mainly composed of hydrogen chloride and water obtained in the absorption step is used as it is or after removing chlorine contained in the solution by heating and / or bubbling with an inert gas such as nitrogen, and then the electrolytic cell.
  • an inert gas such as nitrogen
  • PH adjustment neutralization of boiler feed water, production of 4,4′-diphenylmethanediamine by condensation rearrangement reaction between aniline and formalin, and hydrochloric acid electrolysis.
  • hydrogen chloride is recovered from the top of the distillation column by being subjected to distillation for hydrogen chloride recovery and used in the reaction as a part of the mixed gas. A part or all of the liquid at the bottom of the distillation column is distilled for dehydration. Then, water can be recovered from the top of the distillation column, and part or all of the liquid at the bottom of the distillation column can be supplied to the distillation column for recovering hydrogen chloride.
  • the sulfuric acid mist can be removed by bubbling a part or all of the gas mainly composed of unreacted oxygen obtained in the purification step with an aeration member.
  • Chlorine obtained in the purification step is produced from 1,2-dichloroethane by reaction with ethylene, chlorobenzene by reaction with benzene, phosgene by reaction with carbon monoxide, allyl chloride by reaction with propylene.
  • Can be used in the manufacture of Phosgene can be used in the production of isocyanates by reaction with amines, and in the production of carbonate esters by reaction with alcohols and / or aromatic alcohols.
  • Examples of the isocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene-1,6-diisocyanate.
  • the carbonate ester include diphenyl carbonate and dimethyl carbonate.
  • Example 1 (Preparation of catalyst A) 100 parts of titanium oxide powder [F-1R manufactured by Showa Titanium Co., Ltd., rutile-type titanium oxide ratio 93%], 0.5 part of Serander [YB-152A manufactured by Yuken Industry Co., Ltd.] and sugar ester [Mitsubishi Chemical Foods S-1570] 2 parts were mixed, and then 25.5 parts of pure water and 12.5 parts of titanium oxide sol [CSB manufactured by Sakai Chemical Co., Ltd., titanium oxide content 40%] were added and kneaded. This mixture was extruded into a noodle shape having a diameter of 3.0 mm ⁇ , dried at 110 ° C. for 2 hours, and then crushed to a length of about 3 to 5 mm.
  • the obtained molded body was heated in air from room temperature to 600 ° C. over 1.7 hours and then calcined by holding at the same temperature for 3 hours. Further, a solution prepared by dissolving 31.93 g of tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 manufactured by Wako Pure Chemical Industries, Ltd.) in 137.70 g of ethanol in 900.0 g of the obtained fired product. And allowed to stand at 22 ° C. for 3.3 hours in an air atmosphere. 900.0 g of the obtained solid was heated from room temperature to 300 ° C.
  • reaction After the catalytic activity was stabilized by oxidizing the hydrogen chloride with oxygen using the catalyst A, carbon tetrachloride and hydrogen chloride were brought into contact with oxygen as described below to carry out an oxidation reaction. That is, 3.4 g (2.7 cm 3 ) of catalyst A was charged in an upright quartz reaction tube (inner diameter 14 mm), and 7.8 g (6.1 cm 3 ) of catalyst A and 2 mm in diameter were further above catalyst A. Of .alpha.-alumina spheres with a mixture of 6.4 g.
  • the gas is collected by circulating the gas at the outlet of the reaction tube through a 30% by mass potassium iodide aqueous solution, the amount of chlorine produced by iodine titration method, and the amount of unreacted hydrogen chloride by neutralization titration method.
  • the amount of outlet carbon dioxide was measured by chromatographic analysis. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to carbon tetrachloride after 51 hours from the start of the supply of carbon tetrachloride gas.
  • Example 2 The same operation as in Example 1 was performed except that chloromethane gas diluted to 2.6% by volume with nitrogen gas was supplied at a flow rate of 10.0 ml / min instead of carbon tetrachloride. The amount of chloromethane relative to hydrogen chloride in the feed is calculated to be 0.3% by volume.
  • Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to chloromethane after 44 hours from the start of the supply of chloromethane gas.
  • Example 3 The same operation as in Example 1 was performed except that ethylene gas diluted to 3.9% by volume with nitrogen gas instead of carbon tetrachloride was supplied at a flow rate of 4.1 ml / min. The amount of ethylene relative to hydrogen chloride in the raw material is calculated to be 0.2% by volume. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to ethylene after 42 hours had passed since the start of the ethylene gas supply.
  • Example 4 instead of carbon tetrachloride, the same operation as in Example 1 was performed, except that phenol gas diluted to 0.5 volume% with nitrogen gas was supplied at a flow rate of 15.6 ml / min. The amount of phenol relative to hydrogen chloride in the raw material is calculated to be 0.1% by volume. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to phenol after 45 hours from the start of the supply of phenol gas.
  • Comparative Example 1 (Preparation of catalyst B) Titanium oxide and ⁇ -alumina were mixed at a weight ratio of 34:66 (titanium oxide: alumina), and then pure water was added and kneaded. This mixture was extruded into a cylindrical shape having a diameter of 1.5 mm ⁇ , dried, and then crushed to a length of about 2 to 4 mm. The obtained molded body was fired in air at 700 to 730 ° C. for 3 hours to obtain a carrier made of a mixture of titanium oxide and ⁇ -alumina. This support was impregnated with an aqueous solution of ruthenium chloride, dried, and then calcined in air at 250 ° C. for 2 hours to obtain a catalyst B having a ruthenium oxide content of 2% by weight.
  • Titanium oxide and ⁇ -alumina were mixed at a weight ratio of 50:50 (titanium oxide: alumina), and then a titanium oxide sol having a weight ratio of 12.8 with respect to the mixture 100 of titanium oxide and ⁇ -alumina (Sakai Chemical Co., Ltd.) ) CSB made of 39% titanium oxide) was diluted with pure water and kneaded. This mixture was extruded into a cylindrical shape having a diameter of 1.5 mm ⁇ , dried, and then crushed to a length of about 2 to 4 mm. The obtained molded body was fired in the air at 650 to 680 ° C. for 3 hours to obtain a carrier made of a mixture of titanium oxide and ⁇ -alumina. This support was impregnated with an aqueous solution of ruthenium chloride, dried, and then calcined in air at 250 ° C. for 2 hours to obtain a catalyst C having a ruthenium oxide content of 4% by weight.
  • reaction After stabilizing the catalytic activity by carrying out the reaction of oxidizing hydrogen chloride with oxygen using catalysts B and C, the oxidation reaction was carried out by contacting carbon tetrachloride and hydrogen chloride with oxygen as follows. It was. That is, 3.7 g (2.7 cm 3 ) of catalyst C was filled in an upright quartz reaction tube (inner diameter 14 mm), and 8.1 g (6.1 cm 3 ) of catalyst B and 2 mm in diameter were further above catalyst C. Of ⁇ -alumina spheres (Nikkato Corp., SSA995) 6.0 g.
  • Gas is collected by circulating the gas at the outlet of the reaction tube through a 30% by mass aqueous potassium iodide solution, and the amount of chlorine produced by iodine titration method, the amount of unreacted hydrogen chloride by neutralization titration method, and gas chromatography. And the amount of carbon dioxide at the outlet was measured.
  • Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide relative to carbon tetrachloride after 48 hours from the start of the supply of carbon tetrachloride gas.
  • Comparative Example 2 The same operation as in Comparative Example 1 was performed except that chloromethane gas diluted to 2.6% by volume with nitrogen gas was supplied at a flow rate of 10.0 ml / min instead of carbon tetrachloride. The amount of chloromethane relative to hydrogen chloride in the feed is calculated to be 0.3% by volume. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to chloromethane after 29 hours from the start of the supply of chloromethane gas.
  • Comparative Example 3 The same operation as in Comparative Example 1 was performed except that ethylene gas diluted to 3.9% by volume with nitrogen gas instead of carbon tetrachloride was supplied at a flow rate of 4.1 ml / min. The amount of ethylene relative to hydrogen chloride in the raw material is calculated to be 0.2% by volume. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to ethylene after 46 hours from the start of the supply of ethylene gas.
  • Comparative Example 4 instead of carbon tetrachloride, the same operation as in Comparative Example 1 was performed except that phenol gas diluted to 0.4 volume% with nitrogen gas was supplied at a flow rate of 20.0 ml / min. The amount of phenol relative to hydrogen chloride in the raw material is calculated to be 0.1% by volume. Table 1 shows the conversion rate of hydrogen chloride and the yield of carbon dioxide with respect to phenol after 43 hours from the start of the supply of phenol gas.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication de chlore qui, tout en oxydant de façon satisfaisante au moins un composé choisi parmi un ensemble comprenant du monoxyde de carbone, du phosgène, de l'hydrogène et un composé organique, oxyde aussi de façon satisfaisante du chlorure d'hydrogène. L'invention concerne également un procédé de fabrication de chlore qui oxyde du chlorure d'hydrogène en présence d'un catalyseur soutenu par de l'oxyde de titane, du silice et un composé de ruthénium, tout en oxydant le composé susmentionné, grâce à la mise en contact, avec un gaz contenant de l'oxygène, d'un mélange gazeux contenant du chlorure d'hydrogène et au moins un composé choisi parmi un ensemble comprenant du monoxyde de carbone, du phosgène, de l'hydrogène et un composé organique.
PCT/JP2009/069606 2008-11-21 2009-11-19 Procédé de fabrication de chlore WO2010058810A1 (fr)

Priority Applications (1)

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CN2009801463915A CN102224101A (zh) 2008-11-21 2009-11-19 氯的制备方法

Applications Claiming Priority (4)

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JP2008-297758 2008-11-21
JP2008297758 2008-11-21
JP2009104041A JP5267305B2 (ja) 2008-11-21 2009-04-22 塩素の製造方法
JP2009-104041 2009-04-22

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WO2010058810A1 true WO2010058810A1 (fr) 2010-05-27

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PCT/JP2009/069606 WO2010058810A1 (fr) 2008-11-21 2009-11-19 Procédé de fabrication de chlore

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JP (1) JP5267305B2 (fr)
CN (1) CN102224101A (fr)
WO (1) WO2010058810A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005289800A (ja) * 2004-03-22 2005-10-20 Sumitomo Chemical Co Ltd 塩素の製造方法
JP2008155199A (ja) * 2006-11-27 2008-07-10 Sumitomo Chemical Co Ltd 担持酸化ルテニウムの製造方法および塩素の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005289800A (ja) * 2004-03-22 2005-10-20 Sumitomo Chemical Co Ltd 塩素の製造方法
JP2008155199A (ja) * 2006-11-27 2008-07-10 Sumitomo Chemical Co Ltd 担持酸化ルテニウムの製造方法および塩素の製造方法

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CN102224101A (zh) 2011-10-19
JP5267305B2 (ja) 2013-08-21

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