JP2012206960A - Production method of methyl acetylene and propadiene - Google Patents

Abstract

Disclosed is a method for producing methylacetylene and propadiene, which can produce methylacetylene and propadiene in high yield.
Propane and / or propylene with hydrogen halide and oxygen in the presence of a catalyst comprising at least one selected from the group consisting of Group 7 metal, Group 8 metal, and Group 11 metal compounds. A step of producing a halogenated propane and / or a halogenated propene by reacting or reacting with a halogen molecule, and selected from the group consisting of a group 4 metal, a group 7 metal, and a group 13 metal compound A process for producing methylacetylene and propadiene, comprising a step of dehydrohalogenating the halogenated propane and / or halogenated propene obtained in the above step in the presence of at least one catalyst.
[Selection figure] None

Description

  The present invention relates to a process for producing methylacetylene and propadiene from a gas containing propane and / or propylene.

  Methylacetylene has a terminal carbon-carbon triple bond rich in reactivity, and is expected to be used as a starting material for various compounds. Recently, for example, it is known to be useful as a raw material for producing alkyl methacrylate. For example, a method for producing alkyl methacrylate in which carbon monoxide and an alcohol compound are reacted with methylacetylene in the presence of a catalyst has been proposed (for example, Patent Document 1).

  Methylacetylene and propadiene are usually obtained as by-products together with ethylene and propylene in an olefin production facility (steam cracking method) by thermal decomposition of naphtha. In other words, naphtha is introduced into a thermal cracking furnace together with steam, and the obtained hydrocarbons are rapidly cooled and then led to a rectifying column to obtain tar from the tower bottom, gas oil from the tower side, and hydrocarbons from the tower top. In the process, methylacetylene and propadiene are by-produced as part of the overhead fraction. The obtained propadiene is isomerized to methylacetylene by an isomerization reaction.

  However, since methylacetylene and propadiene are by-products of the steam cracking method, the supply amount varies depending on the operation status of the naphtha pyrolysis plant, and there is a concern that it cannot be stably supplied. Therefore, there is a need for a technique capable of producing methylacetylene and propadiene other than the steam cracking method.

JP 2007-269707 A

  Therefore, an object of the present invention is to provide a method for producing methyl acetylene and propadiene, which can produce methyl acetylene and propadiene with higher yield.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the presence of a catalyst, a raw material gas containing propane and / or propylene is converted into a gas containing halogenated propane and / or propylene halide, and then The inventors have found that a method for obtaining methylacetylene and propadiene by carrying out dehydrohalogenation in the presence of a catalyst is effective, and have completed the present invention.

  That is, the method for producing methylacetylene and propadiene according to the present invention includes the presence of a catalyst containing at least one selected from the group consisting of Group 7 metals, Group 8 metals, Group 11 metals, and compounds of these metals. A halogenation step of reacting propane and / or propylene with hydrogen halide and oxygen or with a halogen molecule to produce a halogenated propane and / or propene halide, and a group 4 metal compound In the presence of at least one catalyst selected from the group consisting of a catalyst, a catalyst comprising a Group 7 metal and / or a compound of the metal, and a catalyst comprising a Group 13 metal compound, by a dehydrohalogenation reaction, Methylacetylene obtained from the halogenated propane and / or halogenated propene obtained in the halogenation step. It is characterized in that comprises a dehydrohalogenation process of manufacturing the propadiene and.

  The present invention has an effect that methylacetylene and propadiene can be produced in a high yield in the presence of a catalyst using propane and / or propylene as a raw material.

In this invention, it is a figure which shows an example of the manufacturing flow at the time of performing reaction using hydrogen halide and oxygen in a halogenation process. In this invention, it is a figure which shows an example of the manufacturing flow at the time of reacting using a chlorine molecule as a halogen molecule in a halogenation process.

Hereinafter, embodiments of the present invention will be described in detail.
The method for producing methylacetylene and propadiene according to the present invention includes at least a halogenation step and a dehydrohalogenation step.

(Halogenation process)
In the halogenation step of the present invention, (1) using an oxyhalogenation reaction in which propane and / or propylene is reacted with hydrogen halide and oxygen in the presence of a catalyst to form a halogen substitution product of propane, or ( 2) Propane and / or propylene is reacted with a halogen molecule in the presence of a catalyst to produce a halogenated propane and / or a halogenated propene using a halogenation reaction in which a halogen substitution product of propane is produced.

  Here, specific examples of the halogenated propane and / or halogenated propene, which are the products of the halogenation process, include the following compounds. That is, as the halogenated propane, monohalogenated propane such as 1-chloropropane, 2-chloropropane, 1-bromopropane, 2-bromopropane, 1-fluoropropane, 2-fluoropropane, 1,2-dichloropropane, 1 , 1-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1,2-dibromopropane, 1,1-dibromopropane, 1,3-dibromopropane, 2,2-dibromopropane, 1, Dihalogenated propane such as 2-difluoropropane, 1,1-difluoropropane, 1,3-difluoropropane, 2,2-difluoropropane, 1,2,3-trichloropropane, 1,1,2-trichloropropane, 1 , 1,3-Trichloropropane, 1,2,2-trichloropropane, 1,2 3-tribromopropane, 1,1,2-tribromopropane, 1,1,3-tribromopropane, 1,2,2-tribromopropane, 1,2,3-trifluoropropane, 1,1, Examples thereof include trihalogenated propane such as 2-trifluoropropane, 1,1,3-trifluoropropane, and 1,2,2-trifluoropropane. Examples of the halogenated propene include 1-chloro-1-propene, 2-chloro-1-propene, 3-chloro-1-propene, 1-bromo-1-propene, 2- Monohalogenation of bromo-1-propene, 3-bromo-1-propene, 1-fluoro-1-propene, 2-fluoro-1-propene, 3-fluoro-1-propene, etc. Examples include propene and dihalogenated propene. Preferably, the halogenated propane is a dihalogenated propane and the halogenated propene is a monohalogenated propene in that methylacetylene and propadiene are obtained in high yield. More preferably, the halogenated propane is dichloropropane, and the halogenated propene is monochloropropene.

  Propane, which is a raw material used in this step, can be, for example, propane obtained from natural gas, petroleum fractionation, petroleum refining, alkane cracking, or the like. Propylene, which is a raw material used in this step, can be, for example, propylene obtained from natural gas, petroleum fractionation, petroleum refining, propane dehydrogenation, olefin metathesis reaction, alcohol or ether conversion, and the like. Propane and / or propylene may be a gas mainly composed of propane and / or propylene, in which hydrocarbon such as methane, ethane, ethylene, butane, butene, nitrogen, carbon dioxide, monoxide Gases such as carbon and water vapor may be contained. From the viewpoint of reaction efficiency, the content of propane and / or propylene in the gas mainly composed of propane and / or propylene is 50% by volume or more, preferably 60% by volume or more, more preferably 70% by volume or more. It is. When a gas mainly composed of propane and propylene is used, the total content of propane and propylene in the gas may be in the above range.

  In addition, what is collect | recovered from the refinement | purification process mentioned later can be used as propane and / or propylene.

  As the hydrogen halide, hydrogen chloride, hydrogen bromide, hydrogen fluoride, or a mixture thereof can be used. Hydrogen chloride or hydrogen bromide is preferable, and hydrogen chloride is more preferable. When using hydrogen chloride, hydrogen chloride produced by the reaction of hydrogen and chlorine, hydrogen chloride generated by heating hydrochloric acid, pyrolysis reaction and combustion reaction of chlorine compounds, carbonylation reaction of organic compounds with phosgene, chlorine Chlorine recovered from by-product hydrogen chloride generated by the chlorination reaction of organic compounds, production of chlorofluoroalkane, oxidation of hydrogen chloride to chlorine, and production of chlorinated alkane by reaction of hydrogen chloride and alkene Hydrogen, hydrogen chloride recovered from combustion exhaust gas generated from an incinerator, or the like can be used. When hydrogen chloride is used, hydrogen chloride may be used as a mixture with unreacted raw materials and reaction products that can be recovered together with hydrogen chloride by the above reactions. Moreover, the hydrogen halide collect | recovered from the refinement | purification process mentioned later can be used as a hydrogen halide. Further, the hydrogen halide may be used as a gas containing hydrogen halide diluted with a gas such as nitrogen, carbon dioxide, carbon monoxide, or water vapor.

  Examples of the halogen molecule include a chlorine molecule, a bromine molecule, an iodine molecule, or a mixture thereof. Preferred are a chlorine molecule and a bromine molecule, and more preferred is a chlorine molecule. When chlorine molecules are used, chlorine molecules recovered from hydrogen chloride oxidation reaction, electrolysis of hydrochloric acid or sodium chloride or the like can be used, and chlorine molecules obtained from a recycling step described later can be used. When chlorine molecules are used, the chlorine molecules may be used as a mixture with unreacted raw materials and reaction products that can be recovered together with the chlorine molecules by the above reactions. Further, as the halogen molecule, a gas containing a halogen molecule diluted with a gas such as nitrogen, carbon dioxide, carbon monoxide, or water vapor may be used.

  As oxygen, an oxygen-containing gas can be used. As the oxygen-containing gas, pure oxygen, pure oxygen diluted with nitrogen, carbon dioxide, carbon monoxide, water vapor, or the like, or air Can be used. Pure oxygen can be obtained by ordinary industrial methods such as air pressure swing method or cryogenic separation.

The catalyst used in this step contains, as a metal component, at least one selected from the group consisting of Group 7 metals, Group 8 metals, Group 11 metals and compounds of these metals, and has good catalytic activity. From the viewpoint of having a catalyst life, at least one selected from the group consisting of a Group 11 metal and a compound of the metal is preferred, and a Group 11 metal compound is more preferred. Hereinafter, these metal components are referred to as catalyst metal components.
The catalyst can be used for both the oxyhalogenation reaction (1) and the halogenation reaction (2). The halogenation reaction (2) can proceed even without a catalyst.

Group 7 metals include manganese and rhenium. Manganese is preferable. As manganese, metal manganese, an inorganic manganese compound, or an organic manganese compound can be used. Examples of the inorganic manganese compound include manganese oxide, manganese halide, manganese nitrate, manganese sulfate, and manganese hydroxide. Examples of the organic manganese compound include manganese acetate. In addition, you may use the hydrate of those compounds. Specific examples of manganese oxide include MnO and MnO ₂ . A specific example of the manganese halide is MnCl ₂ . A specific example of manganese nitrate is Mn (NO ₃ ) ₂ . A specific example of manganese sulfate is MnSO ₄ .

Examples of Group 8 metals include iron, ruthenium, and osmium. Iron or ruthenium is preferable. As iron, metallic iron, inorganic iron compound, or organic iron compound can be used. Examples of the inorganic iron compound include iron oxide, iron halide, iron nitrate, iron sulfate, and iron oxide. Moreover, iron acetate can be mentioned as an organic iron compound. In addition, you may use the hydrate of those compounds. Specific examples of iron oxide include FeO and Fe ₂ O ₃ . Specific examples of the iron halide include FeCl ₂ and FeCl ₃ . A specific example of iron nitrate is Fe (NO ₃ ) ₃ . Specific examples of iron sulfate include FeSO ₄ and Fe ₂ (SO ₄ ) ₃ .

As ruthenium, metallic ruthenium, inorganic ruthenium compound, or organic ruthenium compound can be used. Examples of inorganic ruthenium compounds include ruthenium oxide, ruthenium chloride, chlororuthenate, chlororuthenate hydrate, ruthenate, ruthenium oxychloride, ruthenium oxychloride salt, ruthenium ammine complex, ruthenium ammine complex. Mention may be made of chlorides and bromides, ruthenium bromides, ruthenium carbonyl complexes, ruthenium nitrosyl complexes and ruthenium phosphine complexes. Examples of the organic ruthenium compound include a ruthenium organic amine complex, a ruthenium acetylacetonate complex, and a ruthenium organic acid salt. Specific examples of ruthenium oxide include RuO ₂ . Specific examples of the ruthenium chloride can be exemplified RuCl ₃ and RuCl ₃ hydrate. Specific examples of the chlororuthenate include K ₃ RuCl ₆ and K ₂ RuCl ₆ . Specific examples of the chlororuthenate hydrate include K ₂ RuCl ₅ (H ₂ O) ₄ and KRuCl ₂ (H ₂ O) ₄ . A specific example of ruthenate is K ₂ RuO ₄ . Specific examples of ruthenium oxychloride include Ru ₂ OCl ₄ , Ru ₂ OCl ₅ and Ru ₂ OCl ₆ . Specific examples of the ruthenium oxychloride salt include K ₂ Ru ₂ OCl ₁₀ and Cs ₂ Ru ₂ OCl ₄ . Specific examples of the ruthenium ammine complex include [Ru (NH ₃ ) ₆ ] ²⁺ , [Ru (NH ₃ ) ₆ ] ³⁺ and [Ru (NH ₃ ) 5 H ₂ O] ²⁺ . Specific examples of the ruthenium ammine complex chloride and bromide include [Ru (NH ₃ ) ₅ Cl] ²⁺ , [Ru (NH ₃ ) ₆ ] Cl ₂ , [Ru (NH ₃ ) ₆ ] Cl ₃ and [Ru ( NH ₃ ) ₆ ] Br ₃ can be mentioned. Specific examples of the ruthenium bromide, may be mentioned RuBr ₃ and RuBr ₃ hydrate. Specific examples of the ruthenium carbonyl complex include Ru (CO) ₅ and Ru ₃ (CO) ₁₂ . Specific examples of the ruthenium nitrosyl complex include K ₂ [RuCl ₅ (NO)], [Ru (NH ₃ ) ₅ (NO)] Cl ₃ , [Ru (OH) (NH ₃ ) ₄ (NO)] ( NO ₃ ) ₂ and Ru (NO) (NO ₃ ) ₃ may be mentioned. Further, specific examples of the ruthenium organic acid salt _{[Ru 3 O (OCOCH 3)} 6 (H 2 O) 3] OCOCH 3 _{hydrate, Ru 2 (RCOO) 4 Cl} (R is alkyl of 1-3 carbon atoms Group). Preferable examples include ruthenium halide compounds such as metal ruthenium, ruthenium oxide, ruthenium chloride and ruthenium bromide.

Examples of Group 11 metals include copper, gold, and silver. Copper is preferred. As copper, metal copper, an inorganic copper compound, or an organic copper compound can be used. Among these, metal copper or an inorganic copper compound is preferable, and an inorganic copper compound is more preferable. Examples of the inorganic copper compound include copper halide, copper oxide, copper phosphate, copper thiocyanate, copper nitrate and copper sulfate, among which copper halide or copper oxide is preferable, and copper oxide is more preferable. Examples of the organic copper compound include copper formate, copper acetate, copper oxalate, and copper terephthalate. In addition, you may use the hydrate of those compounds. Specific examples of the copper halide include CuCl, CuCl ₂ , CuBr, CuF ₂ and CuI. Specific examples of copper oxide, may be mentioned CuO and Cu ₂ O. Further, specific examples of copper phosphate can be exemplified _Cu 2 _P 2 _{O 7.} A specific example of copper nitrate is Cu (NO ₃ ) ₂ . A specific example of copper sulfate is CuSO ₄ . Preferably, metallic copper, _CuO, Cu 2 O, CuCl or CuCl _2, more preferably CuO.

The catalyst used in this step preferably contains an alkali metal compound and / or an alkaline earth metal compound as the second component in addition to the above catalyst metal component. By including an alkali metal compound and / or an alkaline earth metal compound, the catalytic activity and the selectivity of the halogenated propane in the oxyhalogenation reaction are improved, and the catalyst metal component is prevented from evaporating and the life of the catalyst can be extended. Become. Of these, alkali metal compounds are preferred. Examples of the alkali metal compound include alkali metal halides, alkali metal carbonates, sulfates, nitrates and oxides. Among these, alkali metal halides are preferable. Specific examples of the alkali metal halide include NaCl, NaBr, KCl, KBr, CsCl, CsBr, RbCl and RbBr, preferably NaCl, KCl or CsCl, more preferably KCl or CsCl, and further preferably KCl. . Examples of the alkaline earth metal compound include alkaline earth metal halides, alkaline earth metal carbonates, sulfates, nitrates and oxides. Among these, alkaline earth metal halides are preferable. Examples of the alkaline earth metal halide _can include _{MgCl 2, MgBr 2, CaCl 2} , CaBr 2, SrCl 2, SrBr 2, BaCl 2 and BaBr _2.

As a preferable combination of the catalytic metal component and the second component, a combination of a copper compound and an alkali metal compound and / or an alkaline earth metal compound can be exemplified, and a combination of a copper compound and an alkali metal compound is more preferable. . Copper compounds are inorganic copper compounds such as copper halide, copper oxide, copper phosphate, copper thiocyanate, copper nitrate, copper sulfate, and copper formate, copper acetate, copper oxalate, copper terephthalate, etc. It is an organic copper compound. A more preferred combination is a copper compound and an alkali metal halide. More preferably, it is a combination of copper chloride CuCl ₂ or copper oxide CuO and an alkali metal halide.

  The ratio of the catalyst metal component to the second component is 1: 0.1 to 1:10, preferably 1: 0.1 to 1: 3, in terms of a molar ratio of catalyst metal component: second component. This is because if the molar ratio of the second component is less than 0.1, the selectivity for the halogenated propane is not improved, and if the molar ratio is greater than 10, the activity of the catalyst decreases.

  The catalytic metal component and the second component, if included, are preferably supported on a carrier and used as a catalyst. An impregnation method, a coprecipitation method, a kneading method, or the like can be used to support the catalyst metal component and the second component, if included, on the support. For example, it can be prepared by supporting the catalyst metal component and the second component, if included, on a support by an impregnation method, a coprecipitation method, a kneading method, or the like, for example, heating to 50 ° C. to 700 ° C. and drying. . Further, the supported catalytic metal component can be oxidized and used as a supported oxide. Further, the supported catalytic metal component can be reduced and used as a supported metal catalyst. Oxidation is performed, for example, by carrying a catalytic metal component on a carrier and firing in an atmosphere of an oxidizing gas. 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. As the oxygen source, air or pure oxygen is usually used, and diluted with an inert gas as necessary. Of these, air is preferable as the oxidizing gas. A calcination temperature is 100-1000 degreeC normally, Preferably it is 200-650 degreeC. The reduction is performed, for example, by carrying a catalytic metal component on a carrier and then firing in a reducing gas atmosphere. The reducing gas is a gas containing a reducing substance, and examples thereof include a hydrogen-containing gas, a carbon monoxide-containing gas, and a hydrocarbon-containing gas. The concentration is usually about 1 to 30% by volume, and the concentration is adjusted with, for example, an inert gas or water vapor. Among them, the reducing gas is preferably a hydrogen-containing gas or a carbon monoxide-containing gas. Moreover, a calcination temperature is 100-1000 degreeC normally, Preferably it is 200-500 degreeC.

  As the carrier, alumina such as γ-alumina, θ-alumina, and α-alumina, silica, titania, zirconia, zeolite, niobium oxide, tin oxide, activated carbon, and the like can be used. Moreover, those composite oxides, such as a silica alumina, or each mixture can also be used. Alumina or silica is preferred.

  When the catalytic metal component is supported on the support, the supported concentration of the catalytic metal component is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 20% by weight as the metal weight with respect to the support. It is preferable that 15% by weight is supported.

The BET specific surface area of the supported catalyst (referring to a catalyst metal component supported on a carrier, including the carrier and the catalyst metal component) is 1 to 400 m ² / g, preferably 5 to 100 m ² / g. This is because when the BET specific surface area is smaller than 1 m ² / g, the degree of dispersion of the supported catalytic metal component is lowered. Moreover, it is because the thermal stability of a supported catalyst will fall when a BET specific surface area is larger than 400 m < ² > / g. Here, the BET specific surface area is a value obtained by measurement using a specific surface area measuring apparatus based on the nitrogen adsorption method. In addition, it is a case where a metal oxide is used for a catalyst, Comprising: The BET specific surface area when not using a support | carrier means the BET specific surface area of this metal oxide.

  The pore volume of the supported catalyst is 0.05 to 1.5 ml / g, preferably 0.1 to 1.0 ml / g. This is because if the pore volume is smaller than 0.05 ml / g, the pore diameter becomes too small and the activity may be lowered. Further, if the pore volume is larger than 1.5 ml / g, the strength of the carrier is lowered and the catalyst is likely to be deteriorated. The pore volume is a value obtained by measurement by the Hg intrusion method.

  The catalyst used in this step is preferably used as a molded body. Examples of the shape include a spherical particle shape, a columnar shape, a pellet shape, an extruded shape, a ring shape, a honeycomb shape, and a granule shape having an appropriate size crushed after forming. At this time, the diameter of the molded body is preferably 5 mm or less. If the diameter of the molded body is too large, the conversion rate of propane and / or propylene may be lowered. The lower limit of the diameter of the molded body is not particularly limited, but if it becomes excessively small, pressure loss in the catalyst layer increases, so that a diameter of 0.5 mm or more is usually used. In addition, the diameter of a molded object here means the diameter of a sphere for spherical particles, the diameter of a circular cross section for a cylindrical shape, and the maximum diameter of the cross section for other shapes.

  In this step, the reaction temperature is 200 to 1200 ° C, preferably 250 to 500 ° C, more preferably 300 to 450 ° C. This is because when the reaction temperature is lower than 200 ° C., the activity of the catalyst decreases. On the other hand, when the reaction temperature is higher than 1200 ° C., the activity of the catalyst is deteriorated.

The reaction pressure is preferably 0.01 to 5 MPa, more preferably 0.01 to 2 MPa, still more preferably 0.05 to 0.3 MPa, and most preferably 0.1 to 0.2 MPa. This is because if the reaction pressure is lower than 0.01 MPa, the productivity is lowered, and if it is higher than 5 MPa, a high pressure resistant reaction vessel is required, resulting in an increase in equipment cost. Further, the reaction pressure is because results tend to cause generation of a high enough CO and CO _2.

  The reaction method in this step can be carried out by various methods such as a fixed bed method, a fluidized bed method, and a moving bed method, but a fixed bed or a fluidized bed method is preferable. The raw materials propane and / or propylene, hydrogen halide and oxygen are supplied to the reactor by supplying propane and / or propylene-based gas, hydrogen halide-containing gas and oxygen-containing gas, respectively (so-called common use). Feeding), or by supplying a mixed gas containing propane and / or propylene, hydrogen halide, and oxygen. In the case of co-feeding, an inert gas such as nitrogen, carbon dioxide, carbon monoxide, and water vapor may be further co-feeded. Further, the mixed gas may contain an inert gas such as nitrogen, carbon dioxide, carbon monoxide, and water vapor.

When the reaction is performed in a fixed bed system, the supply rate of propane and / or propylene (L / h; 0 ° C., 0.1 MPa conversion) is the gas supply rate per 1 L of catalyst, that is, GHSV (Gas Hourly Space Velocity). expressed in, 10~20000hr ^-1, preferably 100~10000hr ^-1. From the viewpoint of productivity, the proportion of hydrogen halide used relative to the raw material propane and / or propylene is 1: 0.1 to 1:10, preferably 1: 1, in terms of molar ratio, propane and / or propylene: hydrogen halide. 1-1: 3. Further, the ratio of oxygen to the raw material propane and / or propylene is, as a molar ratio, propane and / or propylene: oxygen is 1: 0.1 to 1:10, preferably 1: 0. 5 to 1: 5.

(Dehydrohalogenation process)
In the dehydrohalogenation step of the present invention, methylacetylene and propadiene are produced by a dehydrohalogenation reaction from the halogenated propane and / or halogenated propene obtained in the above halogenation step in the presence of a catalyst. The halogenated propane and / or halogenated propene obtained in the halogenation step used in the dehydrohalogenation step is an unreacted raw material that can be recovered together with the halogenated propane and / or halogenated propene in the halogenation step. Or a reaction product or a mixture with a diluent gas, and the halogenated propane obtained by purifying the halogenated propane and / or halogenated propene obtained in the halogenation step described above by the purification step described later. And / or a halogenated propene. Other components contained in the halogenated propane and / or halogenated propene supplied to the dehydrohalogenation process include hydrogen chloride, oxygen, carbon monoxide, carbon dioxide, ethane, methane, propane, propylene, nitrogen, and water vapor. However, it is preferable to supply oxygen after removing it. Further, the halogenated propane and / or halogenated propene obtained in the above-described halogenation step may be used after being diluted with a gas such as nitrogen, carbon dioxide, carbon monoxide, water vapor, or a solvent.
The catalyst used in the dehydrohalogenation step is selected from the group consisting of a catalyst containing a Group 4 metal compound, a catalyst containing a Group 7 metal and / or a compound of the metal, and a catalyst containing a Group 13 metal compound. At least one catalyst.

  Examples of Group 4 metals include titanium, zirconium, and hafnium. Titanium is preferable. Titanium oxide can be used as the titanium compound.

Group 7 metals include manganese and rhenium. Manganese is preferable. As manganese, metal manganese or a manganese compound can be used. Examples of manganese compounds include manganese oxides such as MnO and MnO ₂ , manganese halides such as MnCl ₂ , manganese nitrates such as Mn (NO ₃ ) ₂ , manganese sulfates such as MnSO ₄ , manganese acetate, manganese hydroxide, or those Hydrates can be used.

  Examples of the Group 13 metal include aluminum, gallium, and indium. Aluminum is preferable. Aluminum oxide (alumina) can be used as the aluminum compound.

In the dehydrohalogenation step, the catalyst was selected from the group consisting of Group 4 metal oxides, Group 7 metal halides, Group 7 metal oxides, and Group 13 metal oxides. Preferably it contains at least one compound. Specific examples include titanium oxide, manganese oxide, manganese halide, and alumina. Preferably, it is manganese oxide or alumina. As the manganese oxide, MnO ₂ is preferable. Examples of alumina include γ-alumina, θ-alumina, α-alumina, and boehmite, and γ-alumina or θ-alumina is preferable. When titanium oxide or alumina is used, they can also serve as a carrier.

  The catalyst can be used by being supported on a carrier. An impregnation method, a coprecipitation method, a kneading method, or the like can be used to support the catalyst on the carrier. For example, it can be prepared by supporting a metal compound on a support by an impregnation method, a coprecipitation method, a kneading method, or the like, and heating and drying at 50 ° C. to 700 ° C., for example. Further, the supported compound can be oxidized to be used as a supported oxide. Further, the supported compound can be reduced and used as a supported metal.

  As the carrier, alumina such as γ-alumina, θ-alumina, and α-alumina, silica, titania, zirconia, zeolite, niobium oxide, tin oxide, activated carbon, and the like can be used. Moreover, those composite oxides, such as a silica alumina, or each mixture can also be used. Alumina, silica and titania are preferable, and alumina is more preferable.

  When the catalyst is supported on the support, the catalyst is supported by 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight as the metal weight with respect to the support. It is preferable.

  When at least one metal selected from Group 7 elements and / or a compound of the metal is used as a catalyst, an alkali metal compound and / or an alkaline earth metal compound may be added to the catalyst.

The BET specific surface area of a supported catalyst (referring to a catalyst supported on a carrier, including a carrier and a catalyst) is 1 to 400 m ² / g, preferably 5 to 300 m ² / g. This is because when the BET specific surface area is smaller than 1 m ² / g, the degree of dispersion of the supported catalyst is lowered. Moreover, it is because the thermal stability of a catalyst will fall when a BET specific surface area is larger than 400 m < ² > / g. Here, the BET specific surface area is a value obtained by measurement using a specific surface area measuring apparatus based on the nitrogen adsorption method. In addition, it is a case where a metal oxide is used for a catalyst, Comprising: The BET specific surface area when not using a support | carrier means the BET specific surface area of this metal oxide.

  The pore volume of the supported catalyst is 0.05 to 1.5 ml / g, preferably 0.1 to 1.0 ml / g. This is because if the pore volume is smaller than 0.05 ml / g, the pore diameter becomes too small and the activity may be lowered. Further, if the pore volume is larger than 1.5 ml / g, the strength of the carrier is lowered and the catalyst is likely to be deteriorated. The pore volume is a value obtained by measurement by the Hg intrusion method.

  The catalyst used in this step is preferably used as a molded body. Examples of the shape include a spherical particle shape, a columnar shape, a pellet shape, an extruded shape, a ring shape, a honeycomb shape, and a granule shape having an appropriate size crushed after forming. At this time, the diameter of the molded body is preferably 5 mm or less. If the diameter of the molded body is too large, the conversion rate of halogenated propane and / or halogenated propene may be lowered. The lower limit of the diameter of the molded body is not particularly limited, but if it becomes excessively small, pressure loss in the catalyst layer increases, so that a diameter of 0.5 mm or more is usually used. In addition, the diameter of a molded object here means the diameter of a sphere for spherical particles, the diameter of a circular cross section for a cylindrical shape, and the maximum diameter of the cross section for other shapes.

  The reaction temperature in the dehydrohalogenation step is 200 to 1200 ° C, preferably 250 to 800 ° C, more preferably 300 to 600 ° C. This is because when the reaction temperature is lower than 200 ° C., the activity of the catalyst decreases. On the other hand, when the reaction temperature is higher than 1200 ° C., the activity of the catalyst is deteriorated.

  The reaction pressure is 0.01 to 5 MPa, preferably 0.01 to 0.5 MPa. This is because if the reaction pressure is lower than 0.01 MPa, the productivity is low, and if it is higher than 5 MPa, the equilibrium conversion rate in the reaction is low.

  The reaction system of the dehydrohalogenation process can be carried out by various systems such as a fixed bed system, a fluidized bed system, and a moving bed system, but a fixed bed or fluidized bed system is preferred.

When the reaction is carried out in a fixed bed system, the supply rate of halogenated propane and / or propylene halide is the gas supply rate per liter of catalyst (L / h; 0 ° C., converted to 1 atm), that is, GHSV (Gas Hourly Space Velocity), which is ¹ to 20000 hr ⁻¹ , preferably 10 to 10000 hr ⁻¹ .

  The present invention may include a purification step for purifying the target product from the reaction gas and a recycling step for collecting and reusing unreacted components in the reaction gas, if necessary.

  The purification step includes, for example, a halide purification step for separating hydrogen halide, oxygen, propane and / or propylene from a gas obtained in the halogenation step, and a gas obtained in the dehydrohalogenation step. Separating gases mainly composed of halogenated propene and dihalogenated propane, gas mainly composed of propane and / or propylene and hydrogen halide, and gas mainly composed of monohalogenated propyne and dihalogenated propene And methylacetylene and propadiene purification steps.

  In the recycling process, for example, regarding the use of the recovered material from the reaction gas from the halogenation process, unreacted propane and / or light boiling components such as propylene, oxygen, inert gas, etc. separated from the reaction gas from the halogenation process. Examples thereof include a step of recovering a part and supplying it to the halogenation step, and a step of supplying unreacted hydrogen halide recovered from the reaction gas from the halogenation step to the halogenation step. In addition, regarding the utilization of the recovered product from the purification process of methylacetylene and propadiene, a process of supplying a gas mainly composed of monohalogenated propene and dihalogenated propane to the dehydrohalogenation process, propane and / or propylene and hydrogen halide Monohalogenation obtained by hydrogenating monohalogenated propyne and dihalogenated propene in a gas mainly containing monohalogenated propyne and dihalogenated propene. Examples include a step of supplying a gas mainly composed of propene and dihalogenated propane to the dehalogenation step.

(Production flow example 1)
FIG. 1 is a diagram showing an example of a production flow when a reaction is carried out using hydrogen halide and oxygen in the halogenation step.

1. Halogenation Step A gas 1 containing propane and / or propylene, a gas 2 containing hydrogen halide, and a gas 3 containing oxygen are mixed, and propane and / or propylene are subjected to an oxyhalogenation reaction in an oxyhalogenation reaction apparatus 4.

2. First purification step (halide purification step)
The obtained reaction gas 10 is sent to a first purification device (halide purification device) 5. The first purification device 5 purifies the reaction gas 10 to obtain halogenated propanes (monohalogenated propane, dihalogenated propane and trihalogenated propane) and halogenated propenes (monohalogenated propene and dihalogenated propene). A gas 11 as a main component is obtained.
By purifying the reaction gas 10, unreacted hydrogen halide, unreacted oxygen, unreacted propane and / or propylene are separated.

3. First Recycling Step A part of the light boiling component 15 such as unreacted propane and / or propylene, unreacted oxygen, inert gas, etc. separated from the reaction gas 10 in the first purification apparatus 5 is recovered and transferred to the oxyhalogenation reaction apparatus 4 Supply. The remaining portion 21 of the light boiling portion is discharged.
In the first purification apparatus 5, unreacted hydrogen halide water 17 recovered by washing the reaction gas with water is supplied to the hydrogen halide diffusion apparatus 8. In the hydrogen halide stripping device 8, the obtained hydrogen halide 19 is supplied to the oxyhalogenation reactor 4 by stripping, and at the same time, the water 18 generated by dehydration is removed.

4). Dehydrohalogenation Step The dehydrohalogenation reaction device 6 performs a dehydrohalogenation reaction on the gas 11 mainly composed of halogenated propanes and halogenated propenes supplied from the first purification device 5.

5. Second purification step (methylacetylene and propadiene purification step)
The second purifier 7 purifies the reaction gas 12 from the dehydrohalogenation reactor 6 to obtain a gas 13 mainly composed of methylacetylene and propadiene. Purification of the reaction gas 12 separates monohalogenated propene, dihalogenated propane, propane and / or propylene, hydrogen halide, monohalogenated propyne and dihalogenated propene.

6). Second Recycling Step The gas 15 mainly composed of monohalogenated propene and dihalogenated propane recovered from the second purifier 7 is supplied to the dehydrohalogenation reactor 6. Further, the gas 20 mainly composed of propane and / or propylene and hydrogen halide recovered from the second purification apparatus is supplied to the oxyhalogenation reaction apparatus 4. The gas 16 mainly composed of monohalogenated propyne and dihalogenated propene recovered by the second purifier is mixed with hydrogen 22 and supplied to the hydrogenation reactor 9. A gas 23 mainly composed of monohalogenated propene and dihalogenated propane obtained in the hydrogenation reactor 9 is supplied to the first purifier 5.
The heavy component 14 separated by the second refining device 7 is recovered as waste oil.

(Manufacturing flow example 2)
FIG. 2 is a diagram showing an example of a production flow when a reaction is performed using chlorine molecules as halogen molecules in the halogenation step.

1. Halogenation Step A gas 31 containing propane and / or propylene and a gas 32 containing chlorine molecules are mixed, and propane and / or propylene are chlorinated by the halogenation reactor 34.

2. First Purification Step The obtained reaction gas 41 is sent to the first purification device 35. The first purifier 35 purifies the reaction gas 41, and uses chloropropanes (such as the exemplified 1-chloropropane, 1,2-dichloropropane, 1,2,3-trichloropropane, etc. as the product of the halogenation step described above). A gas 42 mainly composed of (chloropropane) and chloropropenes (chloropropenes such as 1-chloro-1-propene and dichloropropene exemplified as the product of the above-mentioned halogenation step) are supplied to the next step.

3. First Recycling Step A part of light boiling components 54 such as unreacted propane and / or propylene, chlorine molecules, inert gas and the like separated from the reaction gas in the first purifier 35 is recovered and supplied to the halogenation reactor 34.
In addition, the hydrochloric acid water 53 recovered by washing the reaction gas with water in the first refining device 35 is supplied to a hydrogen halide absorption / dissipation device 38 described later.

4). Dehydrohalogenation Step The dehydrohalogenation reaction device 36 performs a dehydrochlorination reaction on the gas 42 mainly containing chloropropanes and chloropropenes supplied from the first purification device 35.

5. Second purification step (methylacetylene and propadiene purification step)
The second purifier 37 purifies the reaction gas 43 from the dehydrohalogenation reactor 36 to obtain a gas 44 mainly composed of methylacetylene and propadiene.

6). Second Recycling Step A gas 54 mainly composed of propane and / or propylene recovered from the second purification device 37 is supplied to the halogenation reaction device 34.
The gas 52 mainly composed of monochloropropene and dichloropropane recovered from the second purification device 37 is supplied to the dehydrohalogenation reaction device 35.

7). Third Recycling Step A gas 46 mainly composed of hydrochloric acid 53 recovered from the first purifier 35 and hydrogen chloride recovered from the second purifier 37 is supplied to the hydrogen halide absorption / dispersion device 38. In the hydrogen halide absorption / dispersion device 38, hydrogen chloride 47 is obtained by diffusion from the obtained hydrochloric acid water and supplied to the hydrogen chloride oxidation device 39, and at the same time, the water 55 is removed by dehydration. In the hydrogen chloride oxidizer 39, the hydrogen chloride 47 is converted into chlorine 48 using oxygen 51 and supplied to the chlorine refining device 40.
Further, in the chlorine refining device 40, unreacted oxygen 50 is supplied to the hydrogen chloride oxidizing device 39, and simultaneously, hydrochloric acid water 56 recovered by washing the unreacted hydrogen chloride with water is supplied to the hydrogen halide absorption / dispersion device 38. Purified chlorine 49 is supplied to the halogenation reactor 34.
The heavy component 45 separated by the second refining device 37 is recovered as waste oil.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example.

  Examples of the halogenation step are shown in Examples 1 to 37, and examples of the dehydrohalogenation step are shown in Examples 38 to 49. Moreover, the comparative example about a dehydrohalogenation process is shown to Comparative Examples 1-6. In the following examples, the parts and% representing the content or amount used are based on weight unless otherwise specified. In the following examples, the gas supply rate (ml / min) is a converted value of 0 ° C. and 0.1 MPa unless otherwise specified.

Example 1.
(Preparation of carrier)
100 parts of titania powder (“F-1R” manufactured by Showa Titanium Co., Ltd., rutile-type titania ratio 93%) and 2 parts of organic binder (“YB-152A” manufactured by Yuken Industry Co., Ltd.) were mixed, and then purified water 29 And 12.5 parts of titania sol [“CSB” manufactured by Sakai Chemical Industry Co., Ltd., titania content 40%] were added and kneaded to obtain a mixture.

This mixture was extruded into a noodle shape having a diameter of 3.0 mmφ, dried at 60 ° C. for 2 hours, and then a rotary non-bubbling kneader (“NBK-1” manufactured by Nippon Seiki Seisakusho) was used as a crusher, The compact was obtained by crushing to about 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. A solution prepared by dissolving 31.9 g of tetraethyl orthosilicate (“Si (OC ₂ H ₅ ) ₄ ” manufactured by Wako Pure Chemical Industries, Ltd.) in 137.7 g of ethanol in 900.0 g of the obtained fired product. Impregnated.

  This white solid was put into a container, and dried at 25 ° C. for 2.3 hours while rotating the container under a flow of nitrogen 8 L / min containing 2.3 vol% of water and 0.3 vol% of ethanol. The obtained solid (946.9 g) was heated from room temperature to 300 ° C. in an air atmosphere over 0.8 hours and then calcined by holding at the same temperature for 2 hours, so that the silica content was 1.0%. A white titania carrier was obtained.

(Manufacture of catalyst)
In 90.0 g of the obtained titania carrier, 2.16 g of ruthenium chloride hydrate [“RuCl ₃ · nH ₂ O” manufactured by NE Chemcat, Ru content 40.0%] was dissolved in 20.5 g of pure water. The obtained solid solution was impregnated, and the obtained solid was put into a container and dried while rotating the container at 35 ° C. for 6.2 hours under an air flow of 2 L / min. 92.7 g of the obtained dried product was heated from room temperature to 250 ° C. over 1.3 hours under air flow, and then held at the same temperature for 2 hours and calcined. As a result, a blue-gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Catalyst filling)
A quartz reaction tube with an inner diameter of 14 mm provided with a thermometer sheath tube with an outer diameter of 4 mm was filled with quartz wool as a partitioning agent, and then 5.4 g of the obtained catalyst was added to a 2 mmφ α-alumina ball [Nikkato Corporation. “SSA995” manufactured by the manufacturer was diluted with 18 g and filled from the top of the reaction tube.

(Production of halogenated propane)
The filled reactor was heated in an electric furnace, and the temperature of the reaction tube was increased while supplying nitrogen gas from the reaction tube inlet at a rate of 120 ml / min.

Then, the supply of nitrogen gas was 78.5 ml / min, hydrogen chloride gas (manufactured by Tsurumi Soda Co., Ltd.) was 42 ml / min (0.11 mol / hr), and propane (manufactured by Sumitomo Seika Co., Ltd., purity> 99%) was circulated at 20 ml / min (0.054 mol / hour, GHSV = 300 hr ⁻¹ ), then oxygen gas was supplied at 56 ml / min (0.15 mol / hour), and halogen was reacted at a reaction pressure of 0.1 MPa. Production of propane was started.

  After the start of the reaction, the hot spot temperature of the catalyst layer was maintained at 250 ° C. ± 2 ° C. due to heat generation. When 60 minutes passed from the start of the reaction, the reactor outlet gas was absorbed in 30% KI water, and the unabsorbed gas was analyzed by gas chromatography having a TCD detector to quantify each product. The absorbing solution was quantified by analyzing unreacted hydrogen chloride by neutralization titration and oxidation-reduction titration. Once sampling is completed, 10% caustic soda, carbon tetrachloride, and carbon tetrachloride are absorbed in a 3-stage trap in contact with 10% caustic soda, carbon tetrachloride, and carbon tetrachloride. The first 10% caustic soda is extracted with carbon tetrachloride. In the second and third stages, the absorbing solution was directly analyzed by gas chromatography having an FID detector to quantify the halogenated propanes. The results are shown in Table 1.

The conversion rate (%) of hydrogen chloride was calculated using the following formula (I).
Conversion rate of hydrogen chloride (%) = [(ab) / a] × 100 (I)
a: Supply flow rate of hydrogen chloride (mol / h)
b: Hydrogen chloride flow rate in the reaction tube outlet gas (mol / h)

Moreover, the selectivity (%) of each product was calculated using the following formula (II).
Selectivity of each product (%) = [Production rate of each product (mol / h) ÷ Total production rate of all products (mol / h)] × 100 (II)

Example 2
(Preparation of carrier)
100 parts of titania powder (“F-1R” manufactured by Showa Titanium Co., Ltd., rutile-type titania ratio 93%) and 2 parts of organic binder (“YB-152A” manufactured by Yuken Industry Co., Ltd.) were mixed, and then purified water 29 And 12.5 parts of titania sol [“CSB” manufactured by Sakai Chemical Industry Co., Ltd., titania content 40%] were added and kneaded to obtain a mixture.

  This mixture was extruded into a noodle shape having a diameter of 3.0 mmφ, dried at 60 ° C. for 2 hours, and then a rotary non-bubbling kneader (“NBK-1” manufactured by Nippon Seiki Seisakusho) was used as a crusher, The compact was obtained by crushing to about 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.

(Manufacture of catalyst)
In 20.0 g of the obtained titania carrier, 0.48 g of ruthenium chloride hydrate (“RuCl ₃ · nH ₂ O” manufactured by NE Chemcat, Ru content 40.0%) was dissolved in 4.6 g of pure water. The aqueous solution prepared above was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 250 ° C. over 1.3 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a blue-gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor filled in the same manner as in Example 1 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 300 hr ⁻¹ ). The results are shown in Table 1.

Example 3
(Preparation of carrier)
60 parts of zirconia powder ("RC-100" manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) and 1.2 parts of organic binder ("65SH-4000" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and then purified water 21 And 11.9 parts of zirconyl nitrate [“Zircosol ZN” manufactured by Daiichi Rare Element Chemical Industries, Ltd., zirconium oxide content 25%] were added and kneaded to obtain a mixture.

  This mixture was extruded into a noodle shape having a diameter of 3.0 mmφ, dried at 60 ° C. for 2 hours, and then a rotary non-bubbling kneader (“NBK-1” manufactured by Nippon Seiki Seisakusho) was used as a crusher, By crushing to about 5 mm, a molded body of 62.5 g was obtained. 25.1 g of the obtained molded body was heated from room temperature to 600 ° C. in air over 1.7 hours and then calcined by holding at that temperature for 3 hours to obtain 22.8 g of zirconium oxide support. Obtained.

(Manufacture of catalyst)
Prepared by dissolving 0.24 g of ruthenium chloride hydrate (“RuCl ₃ · nH ₂ O” manufactured by NE Chemcat, Ru content 40.0%) in pure water in 10.0 g of the obtained zirconium oxide support. The obtained aqueous solution was impregnated and air-dried at 20-30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 350 ° C. over 1 hour under air flow, and then held at the same temperature for 3 hours and calcined. As a result, a gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor filled in the same manner as in Example 1 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 300 hr ⁻¹ ). The results are shown in Table 1.

Example 4
(Manufacture of catalyst)
5% Ru / TiO ₂ (1-2 mm sphere) (manufactured by NE Chemcat) impregnated with 22 g of 2 mol / l KCl aqueous solution in 50 g, evaporated to dryness, dried at 60 ° C., then 350 ° C. for 3 hours in air The excess KCl was washed with 1 l of pure water and dried at 60 ° C. for 4 hours to obtain a black ruthenium oxide catalyst. The content of ruthenium oxide was 6.6% (5% in terms of metal weight).

(Production of halogenated propane)
The reactor filled in the same manner as in Example 1 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 300 hr ⁻¹ ). The results are shown in Table 1.

Example 5 FIG.
(Manufacture of catalyst)
γ-alumina sphere (2-4 mm sphere) [Sumitomo Chemical Co., NKHD-24] 10 g ruthenium chloride hydrate [NE Chemcat “RuCl ₃ · nH ₂ O”, Ru content 40.0%] 0 An aqueous solution prepared by dissolving .24 g in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 350 ° C. over 1 hour under air flow, and then held at the same temperature for 3 hours and calcined. As a result, a blue-gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 1 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 222 hr ⁻¹ ). The results are shown in Table 1.

Example 6
(Manufacture of catalyst)
20 g of silica powder [Nippil E-200A, manufactured by Nippon Silica Kogyo Co., Ltd.] 0.48 g of ruthenium chloride hydrate [“RuCl ₃ · nH ₂ O” manufactured by NE Chemcat, Ru content 40.0%] It was impregnated with an aqueous solution prepared by dissolving it in 20 to 30 ° C. and air-dried for 15 hours or more. The obtained solid was heated from room temperature to 250 ° C. over 1.3 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained. The obtained powder was molded by a tableting machine, and then crushed and classified into 1.4 to 2 mm with a sieve having an opening of 1.4 and 2 mm.

(Production of halogenated propane)
A reactor filled with the same method as in Example 1 except that the amount of alumina for dilution was changed to 6 g was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 1. The results are shown in Table 1.

Example 7
(Manufacture of catalyst)
An aqueous solution prepared by dissolving 0.48 g of ruthenium chloride hydrate (“RuCl ₃ · nH ₂ O” manufactured by NE Chemcat, Ru content 40.0%) in 20 g of the carrier used in Example 2 in pure water. Was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under a nitrogen stream, and then calcined by maintaining at the same temperature for 2 hours. As a result, a gray catalyst having a ruthenium chloride content of 1.95% (0.95% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor filled in the same manner as in Example 1 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 300 hr ⁻¹ ). The results are shown in Table 1.

Example 8 FIG.
(Manufacture of catalyst)
α alumina sphere (2-4 mm sphere) [Sumitomo Chemical Co., HA-24] 10 g ruthenium chloride hydrate [NE Chemcat “RuCl ₃ · nH ₂ O”, Ru content 40.0%] 0 An aqueous solution prepared by dissolving .24 g in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 350 ° C. over 1 hour under air flow, and then held at the same temperature for 3 hours and calcined. As a result, a blue-gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 1 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 1 (propane GHSV = 198 hr ⁻¹ ). The results are shown in Table 1.

In Table 1, the abbreviation CP is monochloropropane composed of 1-chloropropane and 2-chloropropane, and DCP is 1,2-dichloropropane, 1,1-dichloropropane, 2,2-dichloropropane, 1,3-diphenyl. Dichloropropanes composed of chloropropane, TCP represents trichloropropanes composed of 1,2,3-trichloropropane, 1,1,2-trichloropropane and 1,1,3-trichloropropane, CP ′ represents 1-chloro- In the chloropropenes composed of 1-propene, 2-chloro-1-propene and 3-chloro-1-propene, COX represents CO and CO ₂ . In Table 1 and the following table, the supported concentration indicates the ratio of the weight of the metal compound to the support. Moreover, when using a 2nd component, the ratio of the 2nd component weight with respect to a support | carrier is shown.

  In Examples 1 to 8, the influence of the carrier was examined. Titania, zirconia, alumina, and silica were used as the carrier. Regardless of which carrier was used, chloropropanes were produced. A large amount of COX component indicates that propane is easily oxidized. It was found that when silica or alumina was used as the support, complete oxidation of propane was suppressed.

Example 9
(Manufacture of catalyst)
Silica spheres (1.7 to 4.0 mm spheres) (Fuji Silysia Chemical Co., Ltd., Q-50) 20.0 g, ruthenium chloride hydrate [NE Chemcat Co., Ltd. “RuCl ₃ · nH ₂ O”, Ru contained (Amount 40.0%) An aqueous solution prepared by dissolving 0.48 g in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 380 ° C. over 1 hour under air flow, and then held at the same temperature for 2 hours and calcined. As a result, a gray catalyst having a ruthenium oxide content of 1.25% (0.95% in terms of metal weight) was obtained.

(Catalyst filling)
At the bottom of a quartz reaction tube with an inner diameter of 14 mm provided with a thermometer sheath tube with an outer diameter of 4 mm, quartz wool is filled as a partitioning agent, and then 1.0 g of the obtained catalyst is added with 3 g of 2 mmφ α-alumina balls [Nikkato It diluted with "SSA995" made from a company, and filled from the upper part of the reaction tube.

(Production of halogenated propane)
The filled reactor was heated in an electric furnace, and the temperature of the reaction tube was increased while supplying nitrogen gas from the reaction tube inlet to the reaction tube at a rate of 42 ml / min.

Then, the supply of nitrogen gas was stopped, and hydrogen chloride gas (manufactured by Tsurumi Soda Co., Ltd.) was added to the reaction tube at 42 ml / min (0.11 mol / hour), and propane (manufactured by Sumitomo Seika Co., Ltd., purity> 99%). After flowing 20 ml / min (0.054 mol / hour, GHSV = 540 hr ⁻¹ ), oxygen gas was supplied at 14 ml / min (0.0375 mol / hour) to produce a halogenated propane at a reaction pressure of 0.1 MPa. Started.

  After the start of the reaction, the hot spot temperature of the catalyst layer was maintained at 400 ° C. ± 2 ° C. due to heat generation. When 60 minutes passed from the start of the reaction, analysis was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 10
(Manufacture of catalyst)
Silica spheres (1.7 to 4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 20.0 g, manganese chloride tetrahydrate [Wako Pure Chemical Industries, Ltd. “MnCl ₂ .4H ₂ O” An aqueous solution prepared by dissolving 1.55 g in pure water was impregnated and air-dried at 20-30 ° C. for 15 hours or longer. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a black catalyst having a manganese oxide content of 3.0% (1.9% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 2.

Example 11
(Manufacture of catalyst)
Silica spheres (1.7～4.0Mm sphere) [Fuji Silysia Chemical Ltd., Q-50] to 20.0 g, iron chloride hexahydrate [manufactured by Wako Pure Chemical Industries, Ltd. of "FeCl ₃ · 6H ₂ O" It was impregnated with an aqueous solution prepared by dissolving 2.09 g in pure water and air-dried at 20-30 ° C. for 15 hours or longer. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a reddish brown catalyst having an iron oxide content of 3.0% (2.1% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 2.

Example 12
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 20.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. "CuCl ₂ · 2H ₂ O" It was impregnated with an aqueous solution prepared by dissolving 1.33 g in pure water and air-dried at 20-30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light green catalyst having a copper oxide content of 3.0% (2.4% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 2.

Example 13
(Manufacture of catalyst)
Silica sphere (1.7-4.0 mm sphere) [Fuji Silysia Chemical Co., Ltd., Q-50] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” ] An aqueous solution prepared by dissolving 0.68 g and 0.30 g of potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light green copper oxide / potassium chloride catalyst was obtained. The contents of copper oxide and potassium chloride are 3.0% (2.4% in terms of metal weight) and 2.8%, respectively. The molar ratio of copper oxide to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 2.

  In Examples 9 to 13, the influence of the metal species of the catalyst was examined. When copper oxide CuO was used, the highest value was obtained for any of propane conversion, HCl conversion, and chloropropane selectivity. Furthermore, in Example 15 using potassium chloride as the second component, all of propane conversion, HCl conversion, and chloropropane selectivity were further improved.

Example 14
(Manufacture of catalyst)
To gamma alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., GO-24] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” It was impregnated with an aqueous solution prepared by dissolving 2.38 g in pure water and air-dried at 20-30 ° C. for 15 hours or longer. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light green catalyst having a copper oxide content of 10.0% (8.0% in terms of metal weight) was obtained.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

Example 15.
(Manufacture of catalyst)
20.0 g of γ-alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., Ltd., GO-24] was added to copper chloride dihydrate [“CuCl ₂ · 2H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd. It was impregnated with an aqueous solution prepared by dissolving 5.19 g and 1.78 g of sodium chloride (“NaCl” manufactured by Wako Pure Chemical Industries, Ltd.) in pure water, and air-dried at 20-30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. This obtained the light green catalyst whose content of copper oxide and sodium chloride is 10.0% (8.0% in metal weight conversion) and 7.36%, respectively. The molar ratio of copper oxide to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

Example 16
(Manufacture of catalyst)
20.0 g of γ-alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., Ltd., GO-24] was added to copper chloride dihydrate [“CuCl ₂ · 2H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd. ] 5.32 g and potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) 2.32 g dissolved in pure water were impregnated, and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light brown green catalyst in which the contents of copper oxide and potassium chloride were 10.0% (8.0% in terms of metal weight) and 9.36%, respectively, was obtained. The molar ratio of copper oxide to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

Example 17.
(Manufacture of catalyst)
To gamma alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., GO-24] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” ] 2.70 g and cesium chloride [“CsCl” manufactured by Wako Pure Chemical Industries, Ltd.] 1.35 g dissolved in pure water were impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, yellow-green catalysts having copper oxide and cesium chloride contents of 10.0% (8.0% in terms of metal weight) and 10.68%, respectively, were obtained. The molar ratio of copper oxide to cesium chloride is copper oxide: cesium chloride = 1: 0.5.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

Example 18
(Manufacture of catalyst)
To gamma alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., GO-24] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” ] 2.74 g and magnesium chloride (“MgCl ₂ · 6H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) impregnated with an aqueous solution prepared by dissolving 3.26 g in pure water and air-dried at 20 to 30 ° C. for 15 hours or more did. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. This obtained the catalyst whose content of copper oxide and magnesium chloride is 10.0% (8.0% in metal weight conversion) and 11.91%, respectively. The molar ratio of copper oxide to magnesium chloride is copper oxide: magnesium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

Example 19.
(Manufacture of catalyst)
To gamma alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., GO-24] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” ] 2.82 g and calcium chloride (“CaCl ₂ · 2H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) impregnated with an aqueous solution prepared by dissolving 2.42 g in pure water and air-dried at 20 to 30 ° C. for 15 hours or more did. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, green catalysts in which the contents of the oxide layer and calcium chloride were 10.0% (8.0% in terms of metal weight) and 13.9%, respectively, were obtained. The molar ratio of copper oxide to calcium chloride is copper oxide: calcium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 960 hr ⁻¹ ). The results are shown in Table 3.

  Examples 14 to 19 examine the influence of the second component. It was found that when sodium chloride, potassium chloride, or cesium chloride, which is an alkali metal compound, was used as the second component, high values were obtained for any of the propane conversion, HCl conversion, and chloropropane selectivity.

Example 20.
(Manufacture of catalyst)
θ alumina sphere (2.0-4.0 mm sphere) [Sumitomo Chemical Co., Ltd., HT-24] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ .2H ₂ O” An aqueous solution prepared by dissolving 0.68 g and 0.30 g of potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) in pure water was impregnated, and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. Thereby, the light green catalyst whose content of copper oxide and potassium chloride is 3.0% (2.4% in metal weight conversion) and 2.8%, respectively was obtained. The molar ratio of copper oxide to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 912 hr ⁻¹ ). The results are shown in Table 4.

Example 21.
(Manufacture of catalyst)
Alpha alumina spheres (2.0-4.0 mm spheres) (Sumitomo Chemical Co., Ltd., HA-24) 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ · 2H ₂ O” ] An aqueous solution prepared by dissolving 0.22 g and potassium chloride [“KCl” manufactured by Wako Pure Chemical Industries, Ltd.] in 0.10 g in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. Thereby, the light green catalyst whose content of copper oxide and potassium chloride is 1.0% (0.8% in terms of metal weight) and 0.94%, respectively, was obtained. The molar ratio of copper oxide to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 996 hr ⁻¹ ). The results are shown in Table 4.

  Examples 20 and 21 compare the cases where θ alumina and α alumina are used for the carrier. The proportions of the produced species are different between θ alumina and α alumina, and the use of θ alumina increases the selectivity for trichloropropanes and decreases the selectivity for monochloropropanes compared to when α alumina is used. all right.

Example 22.
(Production of halogenated propane)
The same conditions as in Example 9 except that the reactor filled in the same manner as in Example 9 using the catalyst of Example 13 was heated in an electric furnace, the reaction pressure was 0.2 MPa, and the reaction tube was made of Ni. Then, the production of halogenated propane was started (GHSV of propane = 540 hr ⁻¹ ). The results are shown in Table 5.

Example 23.
(Production of halogenated propane)
The same conditions as in Example 9 except that the reactor filled in the same manner as in Example 9 using the catalyst of Example 13 was heated in an electric furnace, the reaction pressure was 0.4 MPa, and the reaction tube was made of Ni. Then, the production of halogenated propane was started (GHSV of propane = 540 hr ⁻¹ ). The results are shown in Table 5. It was found that the lower the reaction pressure, the more COX formation can be suppressed.

Example 24.
(Production of halogenated propane)
The catalyst of Example 13 was charged by the method of Example 9, the charged reactor was heated in an electric furnace, and nitrogen gas was supplied from the inlet of the reaction tube into the reaction tube at a rate of 42 ml / min. The temperature rose.

Then, the supply of nitrogen gas was stopped, and hydrogen chloride gas (manufactured by Tsurumi Soda Co., Ltd.) was added to the reaction tube at 42 ml / min (0.11 mol / hour), and propane (manufactured by Sumitomo Seika Co., Ltd., purity> 99%). After flowing 20 ml / min (0.054 mol / hour, GHSV = 540 hr ⁻¹ ), oxygen gas was supplied at 14 ml / min (0.0375 mol / hour) to produce a halogenated propane at a reaction pressure of 0.1 MPa. Started.

  After the start of the reaction, the hot spot temperature of the catalyst layer was maintained at 400 ° C. ± 10 ° C. due to heat generation. Table 6 shows the analysis results of the reactor outlet gas when 80 hours, 236 hours, and 653 hours had elapsed from the start of the reaction.

Example 25.
(Production of halogenated propane)
The catalyst of Example 13 was charged by the method of Example 9, the charged reactor was heated in an electric furnace, and nitrogen gas was supplied from the inlet of the reaction tube into the reaction tube at a rate of 42 ml / min. The temperature rose.

Then, the supply of nitrogen gas was stopped, hydrogen bromide gas (Sumitomo Seika Co., Ltd., purity> 99%) 42 ml / min (0.11 mol / hr), and propane (Sumitomo Seika Co., Ltd.) in the reaction tube. , Purity> 99%) was allowed to flow through 20 ml / min (0.054 mol / hour, GHSV = 540 hr ⁻¹ ), oxygen gas was then supplied at 14 ml / min (0.0375 mol / hour), and the reaction pressure was adjusted to 0. Production of halogenated propane was started at 1 MPa.

After the start of the reaction, the hot spot temperature of the catalyst layer was maintained at 300 ° C. ± 2 ° C. due to heat generation. When 60 minutes passed from the start of the reaction, analysis was performed in the same manner as in Example 1. The results are shown in Table 7. The conversion rate (%) of hydrogen bromide was calculated using the following formula (III).
Conversion rate of hydrogen bromide (%) = [(cd) / c] × 100 (III)
c: Supply flow rate of hydrogen bromide (mol / h)
d: Hydrogen bromide flow rate in the reaction tube outlet gas (mol / h)

  In Table 7, the abbreviation BP represents monobromopropanes composed of 1-bromopropane and 2-bromopropane, DBP represents 1,2-dibromopropane, 1,1-dibromopropane, 2,2-dibromopropane, 1, Dibromopropanes consisting of 3-dibromopropane, TBP is tribromopropanes consisting of 1,2,3-tribromopropane, 1,1,2-tribromopropane, 1,1,3-tribromopropane, BP ′ represents bromopropenes composed of 1-bromo-1-propene, 2-bromo-1-propene and 3-bromo-1-propene.

Example 26.
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ · 2H ₂ O” ] 2.66 g and 1.16 g of potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in pure water were impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. Thereby, the light green catalyst whose content of copper oxide and potassium chloride is 10.0% (metal weight conversion 8.0%) and 9.4%, respectively was obtained. The molar ratio of copper chloride to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 8.

Example 27.
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ · 2H ₂ O” An aqueous solution prepared by dissolving 0.22 g and 0.096 g of potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) in pure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light green catalyst having copper oxide and potassium chloride contents of 1.0% (0.8% in terms of metal weight) and 0.94%, respectively, was obtained. The molar ratio of copper chloride to potassium chloride is copper oxide: potassium chloride = 1: 1.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 8.

Example 28.
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ · 2H ₂ O” It was impregnated with an aqueous solution prepared by dissolving 0.73 g and potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) 1.07 g in pure water, and air-dried at 20-30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. Thereby, the light green catalyst whose content of copper oxide and potassium chloride is 3.0% (2.4% of metal weight conversion) and 9.4%, respectively was obtained. The molar ratio of copper chloride to potassium chloride is copper oxide: potassium chloride = 1: 3.3.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 8.

Example 29.
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [Fuji Silysia Chemical Co., Ltd., Q-50] 10.0 g, copper chloride dihydrate [Wako Pure Chemical Industries, Ltd. “CuCl ₂ · 2H ₂ O” An aqueous solution prepared by dissolving 0.67 g and potassium chloride (“KCl” manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 0.10 g in impure water was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours. As a result, a light green catalyst having a content of copper oxide and potassium chloride of 3.0% (2.4% in terms of metal weight) and 0.94%, respectively, was obtained. The molar ratio of copper chloride to potassium chloride is copper oxide: potassium chloride = 1: 0.3.

(Production of halogenated propane)
The reactor charged in the same manner as in Example 9 was heated in an electric furnace, and production of halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 540 hr ⁻¹ ). The results are shown in Table 8.

Example 30. FIG.
(Production of halogenated propane)
Except that the catalyst amount of the catalyst produced in Example 8 was changed to 5.4 g, the reactor charged in the same manner as in Example 9 was heated in an electric furnace to produce a halogenated propane under the same conditions as in Example 9. Started (propane GHSV = 198 hr ⁻¹ ). The results are shown in Table 9.

Example 31.
(Production of halogenated propane)
Except that the catalyst amount of the catalyst produced in Example 8 was changed to 5.4 g, the reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the reaction temperature was changed to 350 ° C., as in Example 9. Production of halogenated propane was started under the conditions (GHSV of propane = 198 hr ⁻¹ ). The results are shown in Table 9.

Example 32.
(Production of halogenated propane)
Except that the catalyst amount of the catalyst produced in Example 8 was changed to 5.4 g, the reactor charged in the same manner as in Example 9 was heated in an electric furnace, and the reaction temperature was changed to 300 ° C., as in Example 9. Production of halogenated propane was started under the conditions (GHSV of propane = 198 hr ⁻¹ ). The results are shown in Table 9.

Example 33.
(Production of halogenated propane)
The same conditions as in Example 9 except that the reactor filled with the catalyst produced in Example 8 was heated in an electric furnace in the same manner as in Example 9 and the oxygen flow rate was 7 ml / min (0.0188 mol / hour). Started production of halogenated propane (GHSV of propane = 1067 hr ⁻¹ ). The results are shown in Table 10.

Example 34.
(Production of halogenated propane)
A reactor charged with the catalyst produced in Example 8 in the same manner as in Example 9 was heated in an electric furnace, and production of a halogenated propane was started under the same conditions as in Example 9 (propane GHSV = 1067 hr ⁻¹ ). . The results are shown in Table 10.

Example 35.
(Production of halogenated propane)
The same conditions as in Example 9 except that the reactor filled with the catalyst produced in Example 8 was heated in an electric furnace in the same manner as in Example 9 and the oxygen flow rate was 19 ml / min (0.0509 mol / hour). Started production of halogenated propane (GHSV of propane = 1067 hr ⁻¹ ). The results are shown in Table 10.

Example 36.
(Production of halogenated propane)
A reactor filled with the same catalyst as in Example 1 was heated in an electric furnace in the same manner as in Example 1, except that propane was propylene and the reaction temperature was 280 ° C. Production started. The results are shown in Table 11.

Example 37.
(Production of halogenated propane)
A reactor filled with the same catalyst as in Example 1 was heated in an electric furnace in the same manner as in Example 9, and the halogen was changed under the same conditions as in Example 9 except that chlorine was replaced with 21 ml / min instead of hydrogen chloride and oxygen. Production of propane was started. The results are shown in Table 12.

Example 38.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) [manufactured by Sumitomo Chemical Co., Ltd., GO-24] were used as the carrier. The support was heated from room temperature to 800 ° C. over 2.2 hours, and then calcined while maintaining the same temperature for 3 hours. 10.0 g of the carrier was impregnated with an aqueous solution prepared by dissolving 0.79 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 5.87 g of pure water, It air-dried at 20-30 degreeC for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Catalyst filling)
Quartz wool was filled as a partitioning agent in a lower part of a quartz reaction tube having an inner diameter of 14 mm provided with a thermometer sheath tube having an outer diameter of 4 mm, and then 1.0 g of the obtained catalyst was charged from the upper part of the reaction tube.

(Dehydrochlorination reaction)
The filled reactor was heated in an electric furnace, and the temperature of the reaction tube was increased while supplying nitrogen gas from the reaction tube inlet at a rate of 50 ml / min.

  Then, 1,2-dichloropropane (manufactured by Wako Pure Chemical Industries, Ltd.) is charged into a gas absorption bottle and cooled to 0 ° C., and then nitrogen gas is supplied to the gas absorption bottle at a rate of 50 ml / min. Is supplied from the reaction tube inlet in place of the supply nitrogen gas at the time of temperature rise (1,2-diethylene). Chloropropane supply rate: 0.002 mol / h, GHSV = 46), and the reaction was started at a reaction pressure of 0.1 MPa.

  After the start of the reaction, the temperature of the catalyst layer is maintained at 500 ° C. ± 2 ° C. When 90 minutes have elapsed from the start of the reaction, the reactor outlet gas is absorbed in 30% KI water, Each product was quantified by analysis by gas chromatography. Once sampling is completed, 10% caustic soda, carbon tetrachloride, and carbon tetrachloride are absorbed in a 3-stage trap in contact with 10% caustic soda, carbon tetrachloride, and carbon tetrachloride. The first 10% caustic soda is extracted with carbon tetrachloride. In the liquid, the second stage, and the third stage, the absorption liquid was directly analyzed by gas chromatography having an FID detector to quantify the halogenated propanes. The results are shown in Table 13.

Here, the conversion rate (%) of 1,2-dichloropropane was calculated using the following formula (IV).
Conversion of 1,2-dichloropropane (%) = [(e−f) / e] × 100 (IV)
e: Feed rate of 1,2-dichloropropane (mol / h)
f: 1,2-dichloropropane flow rate (mol / h) in the reaction tube outlet gas
The supply rate of 1,2-dichloropropane was calculated from the change in the weight of the gas absorption bottle from the start to the end of supply.

Moreover, the selectivity (%) of each product was calculated using the following formula (V).
Selectivity of each product (%) = [Production rate of each product (mol / h) ÷ Total production rate of all products (mol / h)] × 100 (V)
Here, the product means methylacetylene; propadiene; propylene; chloropropenes composed of 1-chloro-1-propene, 2-chloro-1-propene and 3-chloro-1-propene; and 1-chloropropane and 2 -Refers to chloropropanes composed of chloropropane.

Example 39.
(Manufacture of catalyst)
Titania sphere (1.0-2.0 mm sphere) [manufactured by Sakai Chemical Industry Co., Ltd., SC300S-12]
Was used. 10.0 g of a carrier was impregnated with an aqueous solution prepared by dissolving 0.79 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 4.24 g of pure water, Air-dried at ~ 30 ° C for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Example 40.
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [manufactured by Fuji Silysia, Q-50] were used as the carrier. 10.0 g of carrier was impregnated with an aqueous solution prepared by dissolving 0.79 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 9.56 g of pure water, Air-dried at ~ 30 ° C for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Example 41.
(Manufacture of catalyst)
Activated carbon (granular) [manufactured by Nippon Enviro Chemicals, WH2C] was used as a carrier. 10.0 g of a carrier is impregnated with an aqueous solution prepared by dissolving 0.79 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 5.02 g of pure water, Air-dried at ~ 30 ° C for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under a nitrogen flow, then held at the same temperature for 2 hours and calcined to obtain a manganese chloride-supported activated carbon catalyst.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Example 42.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) (GO-24 manufactured by Sumitomo Chemical Co., Ltd.) were heated from room temperature to 800 ° C. over 2.2 hours, then held at the same temperature for 3 hours and fired. A γ alumina catalyst was obtained.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Example 43.
(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that titania spheres (1.0 to 2.0 mm spheres) [manufactured by Sakai Chemical Co., Ltd., SC300S-12] were used as the catalyst. The analysis results are shown in Table 13.

Example 44.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) [manufactured by Sumitomo Chemical Co., Ltd., GO-24] were used as the carrier. Without baking the carrier at 800 ° C., 0.78 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10.0 g of the carrier in 10.6 g of pure water. The aqueous solution prepared above was impregnated and air-dried at 20 to 30 ° C. for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Example 45.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) [manufactured by Sumitomo Chemical Co., Ltd., GO-24] were used as the carrier. 10.0 g of the carrier was impregnated with an aqueous solution prepared by dissolving 4.28 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 9.8 g of pure water, It air-dried at 20-30 degreeC for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38, except that the catalyst produced above was used and the catalyst filling amount was 0.2 g (GHSV = 230). The analysis results are shown in Table 13.

Example 46.
(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38 except that the catalyst produced in Example 38 was used and the catalyst filling amount was 0.2 g (GHSV = 230). The analysis results are shown in Table 13.

Example 47.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) [manufactured by Sumitomo Chemical Co., Ltd., GO-24] were used as the carrier. 10.0 g of the carrier was impregnated with an aqueous solution prepared by dissolving 0.18 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 7.1 g of pure water, It air-dried at 20-30 degreeC for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38, except that the catalyst produced above was used and the catalyst filling amount was 0.2 g (GHSV = 230). The analysis results are shown in Table 13.

Example 48.
(Manufacture of catalyst)
Alumina spheres (2.0-4.0 mm spheres) [manufactured by Sumitomo Chemical Co., Ltd., GO-24] were used as the carrier. 10.0 g of the carrier was impregnated with an aqueous solution prepared by dissolving 0.036 g of manganese chloride tetrahydrate (“MnCl ₂ .4H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 8.1 g of pure water, It air-dried at 20-30 degreeC for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38, except that the catalyst produced above was used and the catalyst filling amount was 0.2 g (GHSV = 230). The analysis results are shown in Table 13.

Example 49.
(Catalyst filling)
A quartz reaction tube with an inner diameter of 14 mm provided with a thermometer sheath tube with an outer diameter of 4 mm is filled with quartz wool as a partitioning agent, and then alumina spheres (2.0 to 4.0 mm spheres) [Sumitomo Chemical Co., Ltd. , GO-24] 0.2 g was charged from the top of the reaction tube.

(Dehydrochlorination reaction)
The filled reactor was heated in an electric furnace, and the temperature of the reaction tube was increased while supplying nitrogen gas from the reaction tube inlet at a rate of 50 ml / min.

  Then, 1-chloro-1-propene (manufactured by Tokyo Chemical Industry Co., Ltd.) is charged into a gas absorption bottle and cooled to 0 ° C., and then nitrogen gas is supplied to the gas absorption bottle at a rate of 50 ml / min. Nitrogen gas entrained with 1-chloro-1-propene obtained by flowing through 1-chloro-1-propene is supplied from the reaction tube inlet instead of the supply nitrogen gas at the time of temperature rise (1-chloro- 1-propene supply rate: 0.041 mol / h, GHSV = 914), reaction was started at a reaction pressure of 0.1 MPa.

  After the start of the reaction, the temperature of the catalyst layer is maintained at 500 ° C. ± 2 ° C. When 90 minutes have elapsed from the start of the reaction, the reactor outlet gas is absorbed in 30% KI water, Each product was quantified by analysis by gas chromatography. Once sampling is completed, 10% caustic soda, carbon tetrachloride, and carbon tetrachloride are absorbed in a 3-stage trap in contact with 10% caustic soda, carbon tetrachloride, and carbon tetrachloride. The first 10% caustic soda is extracted with carbon tetrachloride. In the liquid, the second stage, and the third stage, the absorption liquid was directly analyzed by gas chromatography having an FID detector to quantify the halogenated propanes. The results are shown in Table 14.

Here, the conversion rate (%) of 1-chloro-1-propene was calculated using the following formula (VI).
Conversion of 1-chloro-1-propene (%) = [i / j] × 100 (VI)
i: Feed rate of 1-chloro-1-propene (mol / h)
j: Total production rate of all products (mol / h)

Moreover, the selectivity (%) of each product was calculated using the following formula (VII).
Selectivity of each product (%) = [Production rate of each product (mol / h) ÷ Total production rate of all products (mol / h)] × 100 (VII)
Here, the product refers to methylacetylene; propadiene; propylene; chloropropenes composed of 2-chloro-1-propene and 3-chloro-1-propene; and chloropropanes composed of 1-chloropropane and 2-chloropropane. .

Comparative Example 1
(Manufacture of catalyst)
Activated carbon (granular) [manufactured by Nippon Enviro Chemicals, WH2C] was used as a carrier. 30.0 g of the carrier was put into an aqueous solution prepared by dissolving 22.40 g of iron sulfate heptahydrate [“FeSO ₄ · 7H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.] and 500 ml of pure water. .65 g was dissolved, and iron hydroxide, which is a hydrolyzate of iron sulfate, was precipitated and supported on activated carbon. The obtained solid was dried after filtration and washing with pure water. The dried product was heated from room temperature to 500 ° C. over 1.1 hours under a nitrogen flow, then held at the same temperature for 2 hours and calcined to obtain an iron oxide-supported activated carbon catalyst.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Comparative Example 2
(Manufacture of catalyst)
Activated carbon (granular) [manufactured by Nippon Enviro Chemicals, WH2C] was used as a carrier. 10.0 g of the carrier was impregnated with 1.08 g of iron chloride hexahydrate (“FeCl ₃ · 6H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) and 5.22 g of pure water and impregnated with an aqueous solution prepared by dissolving 20 g Air-dried at ~ 30 ° C for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under nitrogen flow, and then calcined by holding at the same temperature for 2 hours to obtain an iron chloride-supported activated carbon catalyst.

(Dehydrochlorination reaction)
The medium was charged and reacted in the same manner as in Example 38 except that the produced catalyst was used. The analysis results are shown in Table 13.

Comparative Example 3
(Manufacture of catalyst)
Silica spheres (1.7-4.0 mm spheres) [manufactured by Fuji Silysia, Q-50] were used as the carrier. 10.0 g of carrier was impregnated with an aqueous solution prepared by dissolving 0.95 g of nickel chloride hexahydrate (“NiCl ₂ .6H ₂ O” manufactured by Wako Pure Chemical Industries, Ltd.) in 9.57 g of pure water, Air-dried at ~ 30 ° C for 15 hours or more. The obtained solid was heated from room temperature to 400 ° C. over 1.1 hours under air flow, and then calcined by maintaining at the same temperature for 2 hours.

(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that the produced catalyst was used. The analysis results are shown in Table 13.

Comparative Example 4
(Dehydrochlorination reaction)
The catalyst was charged and reacted in the same manner as in Example 38, except that silica spheres (1.7 to 4.0 mm spheres) (Fuji Silysia, Q-50) were used as the catalyst. The analysis results are shown in Table 13.

Comparative Example 5
(Manufacture of catalyst)
Chromium oxide (manufactured by Aldrich, Cr ₂ O ₃ , nanopowder) was pressed with a hydraulic jack, and the particle size was adjusted to 1 to 2 mm mesh.

(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38, except that the above prepared catalyst was used and the catalyst filling amount was 0.2 g. The analysis results are shown in Table 13.

Comparative Example 6
(Manufacture of catalyst)
Niobium oxide (Nb ₂ O ₃ ) was pressed with a hydraulic jack, and the particle size was adjusted to 1 to 2 mm mesh.

(Dehydrochlorination reaction)
The reaction was carried out in the same manner as in Example 38, except that the above prepared catalyst was used and the catalyst filling amount was 0.2 g. The analysis results are shown in Table 13.

  In Table 13, the abbreviation 1,2-DCP is 1,2-dichloropropane, MA is methylacetylene, PD is propadiene, C3 ′ is propylene, CP ′ is 1-chloro-1-propene, 2- Chloropropenes composed of chloro-1-propene and 3-chloro-1-propene, and CP represent chloropropanes composed of 1-chloropropane and 2-chloropropane.

As shown in Table 13, as the conversion rate of dichloropropane, high values exceeding about 90% were obtained in all Examples and Comparative Examples. In Comparative Examples 1 to 3, the selectivity for propylene was 90% or more, while the selectivity for methylacetylene was 1.9% or less, and the selectivity for propadiene was 0.5% or less. In Comparative Example 4, the selectivity for chloropropenes was high, and the selectivity for methylacetylene and propadiene was 0.1%. On the other hand, in Examples 38 to 48, the selectivity of methylacetylene was 2.0% or more and the selectivity of propadiene was 0.5% or more, and a high selectivity was obtained as compared with the comparative example. In particular, in Examples 38 and 44 in which MnO ₂ was used as a catalyst and supported on alumina, and Example 42 in which alumina was used as a catalyst, the selectivity for methylacetylene was about 20% and the selectivity for propadiene was about 6%. Thus, a very high selectivity was obtained as compared with the conventional iron oxide-supported activated carbon catalyst of Comparative Example 1.

Further, when a group 6 metal oxide Cr ₂ O ₃ or a group 5 metal oxide Nb ₂ O ₃ was used as a catalyst, methylacetylene and propadiene were not detected.

  In Table 14, the abbreviation 1CP ′ is 1-chloro-1-propene, MA is methylacetylene, PD is propadiene, C3 ′ is propylene, CP ′ is 2-chloro-1-propene and 3-chloro- CP represents chloropropenes composed of 1-propene, and CP represents chloropropanes composed of 1-chloropropane and 2-chloropropane.

  As shown in Table 14, when 1-chloro-1-propene is used as the raw material and only alumina is used as the catalyst, methylacetylene and propadiene are produced, and particularly high selectivity of 19.3% is obtained for methylacetylene. It was.

  As described above, according to the present invention, a halogenated propane and / or a halogenated propene can be produced from propane and / or propylene in a high yield by a halogenation step. In the dehydrohalogenation step, methylacetylene and propadiene can be produced in high yield from halogenated propane and / or halogenated propene.

  The present invention is useful as an industrial process for producing methylacetylene and propadiene because methylacetylene and propadiene can be produced from propane and / or propylene in high yield.

    1 Gas containing propane and / or propylene, 2 Gas containing hydrogen halide, 3 Gas containing oxygen, 4 Oxyhalogenation reaction apparatus, 5 First purification apparatus, 6 Dehydrohalogenation reaction apparatus, 7 Second purification apparatus , 8 Hydrogen halide diffusion apparatus, 9 Hydrogenation reaction apparatus, 10 Reactive gas from oxyhalogenation reaction apparatus, 11 Gas mainly composed of halogenated propanes and halogenated propenes, 12 From dehydrohalogenation reaction apparatus Reaction gas, 13 gas mainly composed of methylacetylene and propadiene, 14 heavy component, 15 light boiling component, 16 gas composed mainly of monohalogenated propyne and dihalogenated propene, 17 unreacted hydrogen halide water, 18 water, 19 hydrogen halide, 20 propane and / or propylene and halogen Gas mainly containing hydrogen halide, 21 Light-boiling residue, 22 Hydrogen, 23 Gas mainly containing monohalogenated propene and dihalogenated propane, 31 Gas containing propane and / or propylene, Gas containing 32 chlorine molecules 34 Halogenation reaction device, 35 First purification device, 36 Dehydrohalogenation reaction device, 37 Second purification device, 38 Hydrogen halide absorption and emission device, 39 Hydrochloric acid oxidation device, 40 Chlorine purification device, 41 Halogenation reaction Reaction gas from the apparatus, gas mainly composed of 42 chloropropanes and chloropropenes, 43 Reaction gas from the dehydrohalogenation reactor, gas mainly composed of 44 methylacetylene and propadiene, 45 heavy fraction, 46 Gas mainly composed of hydrogen chloride, 47 hydrogen chloride, 48 chlorine, 49 Chlorine, 50 unreacted oxygen, 51 oxygen, 52 Gas mainly composed of monochloropropene and dichloropropane, 53 Hydrochloric acid recovered from the first purifier, 54 Light boiling point, 55 Water, 56 Hydrochloric acid.

Claims (8)

Reacting propane and / or propylene with hydrogen halide and oxygen in the presence of a catalyst comprising at least one selected from the group consisting of Group 7 metals, Group 8 metals, Group 11 metals and compounds of these metals Or reacting with a halogen molecule to produce a halogenated propane and / or a halogenated propene,
In the presence of at least one catalyst selected from the group consisting of a catalyst comprising a Group 4 metal compound, a Group 7 metal and / or a catalyst comprising the metal compound, and a catalyst comprising a Group 13 metal compound. A process for producing methylacetylene and propadiene, which comprises a dehydrohalogenation process for producing methylacetylene and propadiene from the halogenated propane and / or halogenated propene obtained in the halogenation process by a dehydrohalogenation reaction.   The production method according to claim 1, wherein the catalyst used in the halogenation step contains a Group 11 metal or a compound of the metal.   The production method according to claim 2, wherein the catalyst used in the halogenation step contains a copper compound and an alkali metal compound.   The process according to claim 3, wherein the alkali metal compound is potassium chloride.   The catalyst used in the dehydrohalogenation step is at least selected from the group consisting of Group 4 metal oxides, Group 7 metal halides, Group 7 metal oxides, and Group 13 metal oxides The manufacturing method of Claim 1 containing 1 type of compounds.   The process according to claim 1, wherein the halogenated propane is dichloropropane and the halogenated propene is monochloropropene. A halide purification step for separating hydrogen halide, oxygen, propane and / or propylene from the gas obtained in the halogenation step;
The manufacturing method of Claim 1 including the recycling process which returns the hydrogen halide, oxygen, propane, and / or propylene isolate | separated at the halide refinement | purification process to a halogenation process. A methylacetylene and propadiene purification step for separating propane and / or propylene and hydrogen halide from the gas obtained in the dehydrohalogenation step;
The process according to claim 1, further comprising a recycling step of returning the propane and / or propylene and the hydrogen halide separated in the methylacetylene and propadiene purification step to the halogenation step.

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