Catalyst for halogen production, package, and method for producing the package

Abstract

A halogen production catalyst for producing a halogen by oxidizing hydrogen halide by means of oxygen, wherein the volume of the water content contained in the halogen production catalyst is 4% or less of the pore volume of the halogen production catalyst in such a state where the halogen production catalyst is sealed in a package. A package in which a halogen production catalyst for producing a halogen by oxidizing hydrogen halide by means of oxygen is sealed, wherein the volume of the water content contained in the halogen production catalyst is 4% or less of the pore volume of the halogen production catalyst.

Description

Catalyst for producing halogen, packaging and method for manufacturing packaging

[0001] The present invention relates to a catalyst for producing halogen, a package containing the catalyst for producing halogen, and a method for producing the package.

[0002] As a method for producing a catalyst for producing halogen, for example, a method for producing a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a titania carrier is known, in which the titania carrier is contact-treated with a solution containing a ruthenium compound and a solvent, then dried until the solvent content reaches a predetermined amount, and the catalyst is maintained in a state containing the predetermined amount of solvent, and then calcined in an oxidizing gas atmosphere (see Patent Document 1). Also known is a mode in which a catalyst for producing methacrylic acid is stored in a container having a predetermined moisture permeability in order to suppress fluctuations in activity, selectivity, etc. due to moisture absorption during storage (see Patent Document 2).

[0003] JP 2013-169516 A Japanese Patent No. 3797147 A

[0004] Even if the catalyst is calcined to remove the solvent, as in the technology of Patent Document 1, depending on the subsequent packaging method and packaging state, the catalyst may absorb moisture (water), which may result in a loss of the catalyst's original activity and selectivity. Furthermore, even if the catalyst is stored in a container, if the catalyst absorbs moisture and absorbs a large amount of water, the water may leak out of the catalyst, causing corrosion at the contact points between the catalyst and the metal container in particular, and damaging the container, which may further reduce the activity and selectivity of the catalyst.

[0005] The present inventors conducted extensive research to solve the above-mentioned problems, and discovered that the above-mentioned problems can be solved by controlling the volume of moisture contained in the halogen production catalyst within a predetermined range when the catalyst is sealed in a package. This led to the completion of the present invention. Specifically, the present invention provides the following [1] to [7]. [1] A halogen production catalyst for producing halogen by oxidizing hydrogen halide with oxygen, wherein the volume of moisture contained in the halogen production catalyst when sealed in a package is 4% or less of the pore volume of the halogen production catalyst. [2] The halogen production catalyst according to [1], wherein the concentration of halogen contained in the halogen production catalyst is in the range of 0.01% by mass to 0.5% by mass when the total mass of the halogen production catalyst is 100% by mass. [3] The halogen production catalyst according to [1] or [2], wherein the halogen production catalyst is a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier. [4] A package containing a catalyst for producing halogen by oxidizing hydrogen halide with oxygen to produce halogen, wherein the volume of moisture contained in the catalyst for producing halogen is 4% or less of the pore volume of the catalyst for producing halogen. [5] The package according to [4], wherein the concentration of halogen contained in the catalyst for producing halogen is in the range of 0.01% by mass to 0.5% by mass when the total mass of the catalyst for producing halogen is taken as 100% by mass. [6] The package according to [4] or [5], wherein the catalyst for producing halogen is a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier. [7] A method for producing a package containing a sealed catalyst for producing halogen, comprising the steps of: preparing the catalyst for producing halogen and a packaging container; and circulating an inert gas at 50°C or less through the packaging container to reduce the volume of moisture contained in the catalyst for producing halogen to 4% or less of the pore volume of the catalyst for producing halogen, and sealing the catalyst in the packaging container to produce the package.

[0006] According to the packaging body and the method for manufacturing the packaging body of the present invention, it is possible to effectively suppress moisture absorption of the catalyst for producing halogen in the packaging body, the outflow of moisture to the catalyst, and corrosion of the container, particularly made of metal, and thus it is possible to effectively suppress a decrease in the activity and selectivity of the catalyst in the production of halogen.

[0007] FIG. 1 is a graph showing the relationship between pit depth and the percentage of water relative to the pore volume.

[0008] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following description.

[0009] The halogen production catalyst according to this embodiment is a catalyst for producing halogen by oxidizing hydrogen halide with oxygen, and the volume of moisture contained in the halogen production catalyst when sealed in a package is 4% or less of the pore volume of the halogen production catalyst.

[0010] 1. Catalyst for producing halogen and method for producing catalyst for producing halogen The catalyst for producing halogen of this embodiment is a catalyst used to produce halogen from hydrogen halide. Specifically, chlorine is produced by oxidizing hydrogen chloride with oxygen in the presence of the catalyst for producing halogen.

[0011] The catalyst for producing halogen according to this embodiment may be in the form of, for example, a powder, a molded body formed into a predetermined shape (for example, spherical particles or a cylindrical shape), or a supported body supported on a carrier.

[0012] The catalyst for producing halogen in this embodiment is preferably in the form of a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier.

[0013] The catalyst for producing halogen according to this embodiment will be specifically described below, taking a preferred supported ruthenium oxide catalyst as an example.

[0014] (1) Support Titania is a preferred support for the supported ruthenium oxide catalyst, which is the catalyst for producing halogen of this embodiment. Examples of titania suitable for use as a support for the supported ruthenium oxide catalyst of this embodiment include rutile titania (titania having a rutile crystal structure), anatase titania (titania having an anatase crystal structure), and amorphous titania. Furthermore, the titania suitable for use as a support for the supported ruthenium oxide catalyst of this embodiment may be a mixture of these titanias.

[0015] The support used in the supported ruthenium oxide catalyst of this embodiment is preferably a titania support made of rutile titania and / or anatase titania. Among these, a titania support having a ratio of rutile titania to rutile titania and anatase titania in the titania support (hereinafter referred to as the rutile titania ratio) of 50% or more is preferred, a titania support having a rutile titania ratio of 70% or more is more preferred, and a titania support having a rutile titania ratio of 90% or more is even more preferred. The higher the rutile titania ratio, the more likely the thermal stability is to be improved, resulting in better activity. The rutile titania ratio can be measured by X-ray diffraction (hereinafter referred to as the XRD method). The rutile titania ratio can be calculated using the following formula (1):

[0016] Rutile titania ratio [%] = [I Ｒ / (I Ａ +I Ｒ ) × 100 (1)

[0017] In formula (1), I Ｒ represents the intensity of the diffraction line representing the rutile titania (110) plane, and I Ａ represents the intensity of the diffraction line representing the anatase titania (101) plane.

[0018] In the supported ruthenium oxide catalyst of this embodiment, the sodium content in the titania carrier is preferably 200 ppm by weight or less, and the calcium content is preferably 200 ppm by weight or less. Furthermore, the total alkali metal element content in the titania carrier is preferably 200 ppm by weight or less, and the total alkaline earth metal element content in the titania carrier is preferably 200 ppm by weight or less. The contents of these alkali metal elements and alkaline earth metal elements can be measured, for example, by inductively coupled plasma atomic emission spectroscopy (hereinafter referred to as ICP analysis), atomic absorption spectroscopy, ion chromatography analysis, etc., with ICP analysis being preferred. In the supported ruthenium oxide catalyst of this embodiment, the titania carrier may contain an oxide such as alumina, zirconia, or niobium oxide.

[0019] In the supported ruthenium oxide catalyst of this embodiment, the specific surface area of ​​the titania support can be measured by the nitrogen adsorption method (BET method). The specific surface area of ​​the titania support is usually 5 to 300 m ２ / g, preferably 5 to 50m ２ / g.

[0020] The titania support in the supported ruthenium oxide catalyst of this embodiment may be a titania support in which silica is previously supported on titania.

[0021] (2) Method for producing supported ruthenium oxide catalyst The catalyst for producing halogen in this embodiment is preferably a supported ruthenium oxide catalyst as described above. Therefore, hereinafter, an example of a method for producing a supported ruthenium oxide catalyst in which ruthenium oxide is supported on the titania carrier already described will be specifically described.

[0022] Ruthenium oxide can be supported on a titania support by, for example, contacting the titania support with a solution containing a ruthenium compound and a solvent, drying the support until the solvent content is 0.10 to 15% by weight based on the weight of the titania support, and then calcining the support in an oxidizing gas atmosphere.

[0023] Ruthenium compounds that can be suitably used in the method for producing a supported ruthenium oxide catalyst of this embodiment include, for example, RuCl ３ , RuBr ３ Ruthenium halides such as K ３ RuCl ６ , K. ２ RuCl ６ Ruthenium halide salts such as K ２ RuO ４ , Na ２ RuO ４ Ruthenium oxoacid salts such as Ru ２ OCl ４ , Ru ２ OCl ５ , Ru ２ OCl ６ Ruthenium oxyhalides such as K ２ [RuCl ５ (H ２ O) ４ ], [RuCl ２ (H ２ O) ４ ]Cl, K ２ [Ru ２ OCl １０ ], Cs ２ [Ru ２ OCl ４ ], halocomplexes of ruthenium such as [Ru(NH ３ ) ５ H ２ O]Cl ２ [Ru(NH ３ ) ５ Cl]Cl ２ [Ru(NH ３ ) ６ ]Cl ２ [Ru(NH ３ ) ６ ]Cl ３ [Ru(NH ３ ) ６ ]Br ３ Ruthenium ammine complexes such as Ru(CO) ５ , Ru ３ (CO) １２ Ruthenium carbonyl complexes such as [Ru ３ O (OCOCH ３ )６ (H ２ O) ３ ]OCOCH ３ , [Ru ２ (OCOR １ ) ４ ]Cl(R １ = alkyl group having 1 to 3 carbon atoms), ２ [RuCl ５ (NO)], [Ru(NH ３ ) ５ (NO)]Cl ３ , [Ru(OH)(NH ３ ) ４ (NO) ] (NO ３ ) ２ [Ru(NO)](NO ３ ) ３ Examples of the ruthenium compounds include nitrosyl complexes of ruthenium, phosphine complexes of ruthenium, amine complexes of ruthenium, and acetylacetonato complexes of ruthenium. Among these, ruthenium halides, which are halides, are preferably used as the ruthenium compound, and chlorides, i.e., ruthenium chloride, are particularly preferably used. Note that, as the ruthenium compound, its hydrate may also be used as necessary. Furthermore, in producing the supported ruthenium oxide catalyst of this embodiment, two or more types of ruthenium compounds may be used.

[0024] In producing the supported ruthenium oxide catalyst of this embodiment, the proportions of the titania support and the ruthenium compound used may be appropriately adjusted so that the weight ratio of ruthenium oxide to titania support (ruthenium oxide / titania support) in the supported ruthenium oxide catalyst obtained after calcination, which will be described later, is preferably 0.1 / 99.9 to 20.0 / 80.0, more preferably 0.3 / 99.7 to 10.0 / 90.0, and even more preferably 0.5 / 99.5 to 5.0 / 95.0.

[0025] When a titania carrier in which silica is supported on titania is used as the carrier, the ratio of the ruthenium compound to the titania carrier is preferably adjusted so that the ruthenium oxide content is 0.10 to 20 moles, more preferably 0.20 to 10 moles, per mole of silica supported on the titania carrier.

[0026] The ruthenium compound is supported on the titania support by contacting the titania support with a solution containing a ruthenium compound and a solvent. Examples of the solvent used in this contact treatment include water, alcohol, and nitrile. Two or more solvents may be used as needed. From the viewpoint of enhancing catalytic activity, it is preferable to use highly pure water such as distilled water, ion-exchanged water, and ultrapure water as the solvent.

[0027] Examples of alcohols that can be used as solvents include alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, hexanol, and cyclohexanol.

[0028] Examples of nitriles that can be used as solvents include nitriles having 1 to 6 carbon atoms, such as acetonitrile, propionitrile, and benzonitrile.

[0029] The amount (volume) of the solvent contained in the solution is preferably 70% by volume or more of the total pore volume of the titania support minus the volume of the ruthenium compound to be supported. There is no particular upper limit, but it is preferably 120% by volume or less.

[0030] The temperature in the contact treatment is usually 0 to 100° C., preferably 0 to 50° C. The pressure in the contact treatment is usually 0.1 to 1 MPa, preferably atmospheric pressure.

[0031] The contact treatment can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen gas, helium gas, argon gas, or carbon dioxide gas, and in this case, the atmosphere may contain water vapor.

[0032] Examples of the contact treatment include impregnation treatment, immersion treatment, etc. Specifically, methods for contacting a titania support with a solution containing a ruthenium compound and a solvent include (i) a method of impregnating a titania support with a solution containing a ruthenium compound and a solvent, and (ii) a method of immersing a titania support in a solution containing a ruthenium compound and a solvent, with the method (i) being preferred.

[0033] In the contact treatment, the amount of the solvent used relative to the titania support may be adjusted so that the content of the solvent in the titania support containing the ruthenium compound and the solvent obtained after the contact treatment exceeds 15% by weight based on the weight of the titania support.

[0034] After the titania support is contact-treated with the solution containing the ruthenium compound and the solvent, a drying step is carried out in which the resulting titania support containing the ruthenium compound and the solvent is dried until the content of the solvent reaches 0.10 to 15 wt % based on the weight of the titania support.

[0035] In the drying step, the temperature is preferably 10°C to 100°C, the pressure is preferably 0.01 to 1 MPa, and atmospheric pressure is more preferable. The drying time can be adjusted appropriately in consideration of the content of the solvent.

[0036] The drying step can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen gas, helium gas, argon gas, or carbon dioxide gas, which may contain water vapor. Alternatively, the drying step can be carried out by circulating air, an inert gas, or a mixed gas of air and an inert gas, which may contain water vapor.

[0037] When the drying step is carried out under a flow of a gas containing water vapor, the concentration of water vapor (water) in the gas containing water vapor may be set within a range less than the saturated water vapor amount under the drying conditions.

[0038] When drying is performed under gas flow in the drying step, the gas flow rate, as the gas hourly space velocity (GHSV) in the titania carrier, is preferably 10 to 10,000 / h, more preferably 100 to 5,000 / h, under standard conditions (0°C, converted to 0.1 MPa). Here, the hourly space velocity can be determined by dividing the amount of gas (L / h) passing through the drying apparatus by the capacity (L) of the titania carrier in the drying apparatus.

[0039] The drying rate in the drying step can be appropriately set. For example, from the viewpoint of productivity, the evaporation rate of the solvent per 1 g of the titania support is preferably 0.01 g / h or more, more preferably 0.02 g / h or more, and even more preferably 0.03 g / h or more.

[0040] The upper limit of the drying rate can be set as appropriate, and is preferably 0.50 g / h or less in terms of the evaporation rate of the solvent per 1 g of the titania support.

[0041] The drying rate can be controlled by adjusting conditions such as temperature, pressure, time, gas flow rate, etc. The drying rate may be changed by appropriately changing the above conditions during the drying process.

[0042] The content of the solvent contained in the dried product obtained after the drying step is 0.10 to 15 wt %, preferably 1.0 to 13 wt %, and more preferably 2.0 to 7.0 wt %, based on the weight of the titania carrier. The content of the solvent in the dried product based on the weight of the titania carrier can be calculated by the following formula (2).

[0043] Solvent content (wt%) based on the weight of the titania carrier in the dried product = [Remaining solvent amount (g) in the dried product] / [Titania carrier content (g) in the dried product] × 100 (2)

[0044] When the contact treatment of the titania support with a solution containing a ruthenium compound and a solvent is carried out by impregnation, the amount of solvent remaining in the dried product can be determined by subtracting the change in weight before and after drying from the amount of solvent used in the contact treatment.

[0045] The drying step is preferably carried out while stirring the solution. Note that drying while stirring means that the solution containing the ruthenium compound and the solvent and / or the titania support is dried in a fluidized state rather than in a static state.

[0046] Examples of the stirring method include a method of rotating the drying container used in the drying step itself, a method of vibrating the drying container itself, and a method of stirring with a stirrer provided in the drying container.

[0047] The dried product obtained by the drying step is preferably kept in a state containing 1.0 to 15% by weight of the solvent based on the weight of the titania carrier.

[0048] Such retention is carried out in a state in which evaporation of the solvent contained in the dried material is suppressed, and the evaporation rate of the solvent is preferably less than 0.01 g / h per 1 g of titania carrier, and more preferably 0.001 g / h or less.

[0049] The temperature during such holding is preferably 0 to 80°C, more preferably 5 to 50°C.

[0050] The time for such retention can be appropriately set taking into consideration the content of the solvent and the retention temperature, and is preferably 10 hours or more, and more preferably 15 hours or more.

[0051] The titania support may be kept in a closed condition, an open condition, or a gas stream, as long as the titania support contains 1.0 to 15% by weight of the solvent based on the weight of the titania support. The titania support may be kept in the same apparatus as that used for the drying treatment, or may be transferred to a different container after the drying treatment and kept therein.

[0052] If the content of the solvent based on the weight of the titania carrier during the drying step is 0.10% by weight or more but less than 1.0% by weight, the dried product may be contacted with a gas containing vaporized solvent by circulating it before the drying step, or if the solvent is water, the dried product may be left in the air so that the content of the solvent in the dried product falls within the range of 1.0 to 15% by weight based on the weight of the titania carrier, and then the dried product may be kept.

[0053] After the above-mentioned holding, a calcination step is carried out in an oxidizing gas atmosphere, whereby the ruthenium compound (ruthenium halide) supported on the titania carrier is converted to ruthenium oxide, producing a supported ruthenium oxide catalyst in which ruthenium oxide is supported on the titania carrier.

[0054] Here, the oxidizing gas is a gas containing an oxidizing substance, such as an oxygen-containing gas, whose oxygen concentration is usually 1 to 30% by volume.

[0055] The oxygen source of the oxygen-containing gas may be air or pure oxygen. The oxygen source may be diluted with an inert gas or water vapor as needed. Air is preferably used as the oxidizing gas.

[0056] The firing temperature in the firing step is usually 100 to 500°C, preferably 200 to 400°C.

[0057] The calcination step may be carried out after further drying until the solvent content in the dried product becomes less than 1.0 wt % based on the weight of the titania support, or after the above-mentioned keeping and reduction treatment, or after further drying until the solvent content in the dried product becomes less than 1.0 wt % based on the weight of the titania support and then reduction treatment.

[0058] As the drying method, a conventionally known drying method can be used. The temperature in the drying method is usually from room temperature (25°C) to about 100°C, and the pressure is usually from 0.001 to 1 MPa, preferably atmospheric pressure. The drying can be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen gas, helium gas, argon gas, or carbon dioxide gas, and in this case, the atmosphere may further contain water vapor.

[0059] In the supported ruthenium oxide catalyst obtained by the calcination step, the oxidation number of ruthenium in the ruthenium oxide supported on the titania support is usually +4, and the ruthenium oxide is usually ruthenium dioxide (RuO ２ However, ruthenium oxide may include ruthenium in other oxidation states or other forms of ruthenium oxide.

[0060] When the resulting supported ruthenium oxide is a supported ruthenium oxide in which ruthenium oxide is supported on a titania carrier in which silica is supported on titania, the silica content in the supported ruthenium oxide varies depending on the physical properties of the titania used and the ruthenium oxide content in the resulting supported ruthenium oxide. The silica content is preferably 0.01 to 10 wt %, more preferably 0.1 to 5 wt %.

[0061] The supported ruthenium oxide catalyst obtained by the calcination step is preferably formed into a molded body. Examples of the shape of the supported ruthenium oxide catalyst molded body include spherical particles, cylinders, pellets, extruded shapes, ring shapes, honeycomb shapes, and granules of appropriate size obtained by crushing and classifying the molded product, with pellets being preferred. In this case, the diameter of the molded body is preferably 5 mm or less. There is no particular lower limit to the diameter of the molded body. The lower limit of the diameter of the molded body is preferably 0.5 mm or more.

[0062] The diameter of the molded product referred to here means the diameter of the sphere in the case of a spherical particle, the diameter of the circular cross section in the case of a cylindrical shape, and the maximum diameter of the cross section in the case of other shapes.

[0063] When the supported ruthenium oxide catalyst is formed into a molded body, the molding step for forming the molded body may be carried out in advance when the titania support is prepared, or may be carried out after the ruthenium compound or ruthenium oxide is supported on the titania support. The molding step is preferably carried out when the titania support is prepared.

[0064] When using a titania carrier in which silica is supported on titania, if a molding step is carried out during the preparation of the titania carrier, it may be carried out before or after the silica is supported. The molding step is preferably carried out before the silica is supported. When molding is carried out during the preparation of the titania carrier, it can be carried out by any suitable method known in the art. For example, powdery or sol-like titania can be kneaded and molded, and then heat-treated to form the titania carrier into a molded body of a predetermined shape.

[0065] Specifically, the shaped body of the titania support can be prepared, for example, by kneading titania powder or titania sol with a molding aid such as an organic binder and water, extruding the mixture into a noodle shape, drying the mixture, crushing it into a predetermined shape, and then heat-treating the mixture in an oxidizing gas atmosphere such as air.

[0066] Examples of the oxidizing gas include oxygen-containing gases, and the oxygen concentration of the oxygen-containing gas is usually about 1 to 30% by volume. Air or pure oxygen is usually used as the oxygen source for the oxygen-containing gas, and the oxygen source can be diluted with an inert gas or water vapor as needed. Of these, air is preferred as the oxidizing gas. Examples of inert gases include nitrogen gas, helium gas, argon gas, and carbon dioxide gas, and the inert gas can be diluted with water vapor as needed. Of these, nitrogen gas and carbon dioxide gas are preferred as the inert gas. The treatment temperature in this case is usually 400 to 900°C, and preferably 500 to 800°C.

[0067] The pore volume of the supported ruthenium oxide catalyst molded body is preferably 0.15 to 0.40 mL / g, and more preferably 0.15 to 0.30 mL / g. The pore volume of the molded body can be adjusted by adjusting the composition of the raw materials subjected to the molding step and the heat treatment temperature of the molded body.

[0068] The pore volume of the supported ruthenium oxide catalyst can be measured, for example, by mercury intrusion porosimetry. Specifically, using a pore volume measuring device (for example, "Autopore III9420" manufactured by MICROMERITICS), the amount of mercury intrusion at each pressure step is measured while increasing the pressure applied to the supported ruthenium oxide catalyst, and the total amount of mercury intrusion (mL) is divided by the sample weight (g) to determine the amount of mercury intrusion per 1 g of the supported ruthenium oxide catalyst (molded body), which can be used as the pore volume (mL / g).

[0069] According to the method for manufacturing a package of this embodiment, the moisture content of the catalyst for halogen production in the package can be reliably kept within the above-mentioned predetermined range, and as a result, it is possible to effectively suppress the outflow of moisture from the catalyst for halogen production and corrosion due to the moisture at the contact points between the catalyst for halogen production and the container, particularly made of metal.

[0070] 2. Method for Producing Halogen The method for producing halogen according to the present embodiment can be a method for oxidizing hydrogen chloride with oxygen in the presence of the catalyst for producing halogen according to the present embodiment, i.e., the supported ruthenium oxide catalyst, produced as described above. According to this method for producing halogen, halogen can be produced efficiently.

[0071] Examples of halogens produced by the halogen production method of the present embodiment include chlorine, bromine, and iodine, with chlorine being preferred.

[0072] The reaction system in the halogen production method of this embodiment may be, for example, a fluidized bed system, a fixed bed system, or a moving bed system. As the reaction system, a fixed bed system is preferred, and it is preferable to use an adiabatic or heat exchange fixed bed reactor.

[0073] When an adiabatic fixed-bed reactor is used, either a single-tubular fixed-bed reactor or a multi-tubular fixed-bed reactor can be used, with the use of a single-tubular fixed-bed reactor being preferred.

[0074] When a heat exchange type fixed bed reactor is used, either a single-tubular fixed bed reactor or a multi-tubular fixed bed reactor can be used, with the multi-tubular fixed bed reactor being preferred.

[0075] The oxidation reaction in the halogen production method of this embodiment is an equilibrium reaction. The reaction temperature in the halogen production method of this embodiment is usually 100 to 500°C, and preferably 200 to 450°C. Because a high reaction temperature may decrease the equilibrium conversion rate, it is preferable to adjust the reaction temperature to a relatively low temperature within the above temperature range.

[0076] The reaction pressure in the method for producing halogen according to this embodiment is usually about 0.1 to 5 MPa.

[0077] The oxygen source used in the halogen production method of this embodiment may be air or pure oxygen. The theoretical molar amount of oxygen relative to the hydrogen halide is 1 / 4 mole, and oxygen is usually used in an amount 0.1 to 10 times this theoretical molar amount.

[0078] The supply rate of hydrogen halide in the halogen production method of this embodiment is the gas supply rate per 1 L of catalyst (L / h; 0 ° C, 0.1 MPa equivalent), that is, expressed in GHSV, and is usually 10 to 20,000 h －１ It can be about.

[0079] In the catalyst for producing halogen of this embodiment, when the total mass of the catalyst for producing halogen is taken as 100 mass%, the concentration of halogen contained in the catalyst for producing halogen is preferably 0.5 mass% or less from the viewpoint of enhancing catalytic activity, and preferably 0.01 mass% or more from the viewpoint of productivity. The concentration of halogen contained in the catalyst for producing halogen is preferably in the range of 0.01 mass% to 0.4 mass%, and more preferably in the range of 0.01 mass% to 0.3 mass%.

[0080] The halogen concentration in the catalyst for producing halogen of this embodiment can be measured by a conventionally known method. The halogen concentration can be measured, for example, by ion chromatography. Alternatively, the halogen concentration can be calculated by immersing the catalyst for producing halogen in an aqueous potassium iodide solution and then analyzing the aqueous potassium iodide solution by neutralization titration and iodometric titration.

[0081] 3. Package and Manufacturing Method of Package (1) Package The package according to this embodiment is a package that contains a catalyst for producing halogen for oxidizing hydrogen halide with oxygen to produce halogen, and the volume of moisture contained in the catalyst for producing halogen is 4% or less of the pore volume of the catalyst for producing halogen.

[0082] As already explained, the catalyst for producing halogen enclosed in the packaging of this embodiment is preferably a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier, and more specifically, is preferably a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a titania carrier.

[0083] Furthermore, in the halogen production catalyst of this embodiment, as already explained, the volume of moisture contained in the halogen production catalyst when sealed in a package is 4% or less of the pore volume of the halogen production catalyst, preferably 2.5% or less, and more preferably 2.0% or less of the pore volume of the halogen production catalyst.

[0084] Here, the moisture content (wt%), which is the volume of moisture contained in the catalyst for producing halogen of this embodiment, can be calculated from the weight (g) after the calcination step or before and after the drying treatment further performed after the calcination step, the weight loss, which is the difference between the weight before and after the calcination step or the drying treatment, and the weight after the treatment, using the following calculation formula: Moisture content (wt%) = 100 × weight loss (g) / weight after calcination step or drying treatment (g).

[0085] Specific aspects of the packaging body of this embodiment will be described below. The packaging body of this embodiment is a packaging body in which a catalyst for producing halogen, such as the supported ruthenium oxide catalyst already described, is enclosed, and includes the catalyst for producing halogen and an enclosure container, with the catalyst for producing halogen enclosed in the enclosure container.

[0086] The sealed container of this embodiment is a container capable of sealing the halogen production catalyst therein, as already explained.

[0087] The material of the enclosure is not particularly limited, provided that the volume of water contained in the catalyst for producing halogen can be maintained at 4% or less of the pore volume of the catalyst for producing halogen.

[0088] That is, the sealed container is preferably made of a material that is airtight and moisture-proof, and more preferably made of a material that is flexible.

[0089] In order to satisfy the above conditions, the sealed container of this embodiment has a moisture permeability of 1.0 g / m at 25°C. 2 The moisture permeability can be measured by a method in accordance with JIS Z0208.

[0090] Specific examples of the material for the sealed container include low-density polyethylene (LDPE), metal laminate films such as aluminum laminate films, LCP (liquid crystal polymer) films, and metal (films). From the viewpoint of productivity, low-density polyethylene is preferably used as the material for the sealed container.

[0091] The shape of the container is not particularly limited, provided that the container can contain (seal) the catalyst for producing halogen while maintaining the volume of water contained in the catalyst for producing halogen at 4% or less of the pore volume of the catalyst for producing halogen. The container is preferably bag-shaped.

[0092] More specifically, the container is preferably a bag-shaped body made of low-density polyethylene, as described above. The capacity (size) of the packaging container can be set to any suitable capacity (size) taking into consideration the properties of the catalyst for halogen production to be enclosed and the amount to be enclosed.

[0093] When such a particularly flexible bag-shaped body (or sheet-shaped body) is used, a plurality of bags may be stacked to form an enclosed container.

[0094] The sealed container of this embodiment may further include a sealing member such as a string-shaped member, a tape-shaped member, a seal-shaped member, or a lid-shaped member for enclosing and sealing the catalyst for producing halogen.

[0095] The packaging of this embodiment can effectively prevent moisture absorption by the catalyst for halogen production in the packaging, the outflow of moisture to the outside of the catalyst, and corrosion of the container, particularly that made of metal.

[0096] (2) Manufacturing method of package The manufacturing method of the package of this embodiment is a manufacturing method of a package in which a catalyst for producing halogen is sealed, and includes the steps of preparing a catalyst for producing halogen and an enclosed container, and circulating an inert gas at 50° C. or less inside the enclosed container to reduce the volume of moisture contained in the catalyst for producing halogen to 4% or less of the pore volume of the catalyst for producing halogen, and then enclosing the catalyst in the enclosed container to manufacture the package. This will be described in detail below.

[0097] <Step of Preparing a Catalyst for Producing Halogen and a Sealing Container> In this step, the catalyst for producing halogen that has already been described and a sealing container having the configuration that has already been described for producing a package are prepared.

[0098] As the sealing container, any suitable type (shape, size) of sealing container may be prepared in the required number, taking into consideration the properties (shape, size, weight) of the catalyst for halogen production to be enclosed and the amount (weight) to be enclosed.

[0099] It is preferable that the volume of the sealed container, i.e., the amount of the catalyst for halogen production sealed in the sealed container, is made to match, for example, the amount of the catalyst for halogen production filled in a reactor in the halogen production process. In this way, it is not necessary to reweigh the catalyst for halogen production taken out of the package in the halogen production process, and therefore the halogen production process can be carried out more efficiently.

[0100] <A process for producing a package by circulating an inert gas at 50°C or less inside the sealed container, adjusting the volume of moisture contained in the halogen production catalyst to 4% or less of the pore volume of the halogen production catalyst, and sealing the halogen production catalyst in the sealed container> In this process, first, a predetermined amount of halogen production catalyst is weighed and filled into the prepared sealed container.

[0101] Next, the sealed container is sealed to seal the halogen production catalyst in the sealed container. In this embodiment, when sealing the sealed container, an inert gas at 50°C or less is circulated inside the sealed container, and the volume of water contained in the halogen production catalyst is set to 4% or less of the pore volume of the halogen production catalyst.

[0102] The method for flowing the inert gas is not particularly limited. The method for flowing the inert gas can be selected from any suitable conventionally known method, taking into consideration the material, volume, and shape of the selected sealed container, the properties of the selected catalyst for producing halogen, and the like. The method for flowing the inert gas may, for example, use a nozzle or the like for directly introducing the inert gas into the sealed container, or may involve separating the entire device for filling the sealed container with the catalyst for producing halogen with a partition wall and flowing the inert gas into the separated space.

[0103] Examples of inert gases that can be used in this step include air, nitrogen gas, helium gas, argon gas, and carbon dioxide gas. From the viewpoint of productivity, air is preferred as the inert gas.

[0104] In this step, the temperature of the inert gas to be passed through is set to 50° C. or less. From the viewpoint of reducing the moisture concentration in the inert gas, the temperature of the inert gas to be passed through is preferably set to 40° C. or less, and more preferably set to 30° C. or less.

[0105] In this step, the sealed container can be sealed by any suitable method depending on the material, size, and shape of the selected sealed container.

[0106] When a container made of a resin such as low-density polyethylene, as described above, is used as the sealed container, heat sealing (thermocompression bonding) can be performed by taking advantage of the properties of the material of the sealed container. By performing heat sealing in this manner, the catalyst for producing halogen can be easily and reliably sealed in the sealed container. Furthermore, sealing can be performed, for example, with an adhesive, or with any suitable conventionally known sealing member, such as a string-like member, tape-like member, seal-like member, or lid-like member, as described above. The package of this embodiment can be manufactured by the above steps.

[0107] (3) Other components that can house the package When storing or transporting the package of this embodiment manufactured as described above, the package may be housed inside additional components to protect it from moisture, stress that is inevitably applied from the outside, and the like.

[0108] Such additional components include, for example, a storage container, which is a bag-like body made of the same material as the enclosed container already described and which is capable of containing one or more packages.

[0109] When a particularly flexible bag-like body is used as the storage container, the storage container may be constructed by stacking a plurality of sheets, similar to the sealed container.

[0110] The storage container can be sealed in the same manner as the sealed container, for example, by heat sealing or any suitable sealing member known in the art, such as an adhesive, string-like member, tape-like member, seal-like member, or lid-like member.

[0111] Furthermore, as an additional member, for example, a holding container having superior strength may be used in order to more effectively protect the package from external stress, impact, etc. When using such a holding container, one or more packages may be directly stored inside, or a storage container containing one or more packages may be stored inside.

[0112] Here, the embodiment of the holding container will be described. The holding container is, for example, a container consisting of a lid-like body and a main body. The holding container is a container having a higher strength than the sealed container and the storage container already described.

[0113] Examples of materials for the holding container include various metals and plastics. Specifically, the holding container may be, for example, a pail made of metal or plastic.

[0114] The capacity of the holding container is not particularly limited, provided that it can accommodate and airtightly seal one or more predetermined number of packages according to this embodiment or storage containers containing the packages.

[0115] The lid and the main body can be fixed together using, for example, an airtight tape-like member or a seal-like member so as to seal the inside airtight.

[0116] The holding container preferably has air cushion members made of flexible foam or the like on the inner surface of the lid and the inner bottom surface of the main body, which can more effectively protect the package from external stress, impact, etc.

[0117] <Preparation of Catalyst for Producing Halogen> 50 parts by weight of titanium oxide (100% rutile type, "STR-60R" manufactured by Sakai Chemical Industry Co., Ltd.), 100 parts by weight of α-alumina (AES-12 manufactured by Sumitomo Chemical Co., Ltd.), 13.2 parts by weight of titania sol (CSB manufactured by Sakai Chemical Industry Co., Ltd., titania content 38% by weight), and 2 parts by weight of methylcellulose (Metolose 65SH-4000 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and then pure water was added and the mixture was kneaded to obtain a kneaded mixture.

[0118] This kneaded material was extruded into a cylindrical shape with a diameter of 3.0 mm, dried, and then crushed to obtain a compact having a length of about 4 to 6 mm in the direction perpendicular to the diameter.

[0119] The resulting molded body was calcined in air at 800° C. for 3 hours to obtain a support consisting of a mixture of titanium oxide and α-alumina.

[0120] Next, 20.0 g of this support was dissolved in ruthenium chloride hydrate (RuCl ３ ・nH ２ The resulting product was immersed in an aqueous solution prepared by dissolving 1.583 g of ZnO (O, Ru content 40.0 mass%) in 3.5 g of pure water, and then allowed to stand at 25° C. for 15 hours to dry, thereby obtaining a solid.

[0121] Next, the obtained solid was heated from room temperature to 250°C under air flow, and then further calcined at 250°C for 2 hours, to obtain a supported ruthenium oxide catalyst in which ruthenium oxide was supported on the above-mentioned carrier at a loading rate of 4% by weight, as a catalyst for producing halogen.

[0122] Approximately 0.1 g of the obtained catalyst for producing halogen was weighed out and crushed. The crushed sample was mixed with 10 mL of ultrapure water and 1 mL of a 1 mmol / L aqueous solution of sodium carbonate to obtain a mixed solution. The obtained mixed solution was subjected to extraction at 230°C for 16 hours, and the obtained extract was filtered to obtain a test solution. The Cl content in the test solution was － was measured by ion chromatography and converted into the amount eluted per unit mass of the sample. The converted halogen concentration in the catalyst for halogen production was 0.15 wt %.

[0123] <Production Example of Package of Catalyst for Producing Halogen> 500 g of the above-mentioned catalyst for producing halogen was filled into a sealed container, a bag-shaped body (thickness: 0.1 mm) made of low-density polyethylene, while circulating dry air at 25°C, and the opening of the sealed container was sealed by heat sealing.

[0124] Similarly, 40 packages in which the catalyst for halogen production had been sealed were placed together in a bag-shaped container (thickness: 0.1 mm) made of low-density polyethylene, and the opening of the container was sealed with a tape-shaped member.

[0125] As described above, the storage container containing 40 packages was placed in a metal holding container (a lidded 18L can) with air cushion members placed above and below the storage container, and the holding container body and the lid were sealed with a tape-like member to obtain a holder containing packages of catalyst for halogen production.

[0126] The package (support) thus prepared was stored at room temperature for 7 years, and then opened. The moisture content of the catalyst for halogen production was measured and found to be 0.43%. The ratio of the moisture content to the pore volume of the catalyst was calculated as described above and found to be 2.0%.

[0127] <Measurement of pore volume of supported ruthenium oxide catalyst> To be used for measurement, 0.6 to 1.2 g of the obtained supported ruthenium oxide catalyst was weighed out and dried in a dryer at 110°C for 4 hours, and the dried weight was precisely weighed to obtain a sample. This sample was placed in the cell of a pore volume measuring device (MICROMERITICS "Autopore III 9420"), and after the pressure inside the cell was adjusted to 50 μmHg or less, mercury was filled into the cell. Next, pressure was applied so that the pressure inside the cell was increased in stages, with a waiting time of 10 seconds for mercury intrusion equilibration, and the amount of mercury intrusion at each pressure stage was measured. The total amount of mercury intrusion (mL) when pressures from 0.007 MPa to 207 MPa were applied was divided by the sample weight (g) to determine the amount of mercury intrusion per 1 g of sample, and this was taken as the pore volume (mL / g). As a result, the pore volume (VP) of the supported ruthenium oxide catalyst according to this example was 0.22 mL / g.

[0128] <Measurement of the amount of water contained in the supported ruthenium oxide catalyst> Approximately 40 g of the above supported ruthenium oxide catalyst was weighed out and dried at 110°C for 1 hour (h). The dried catalyst was weighed out and the weight (g) before and after drying and the weight loss (g), which is the difference between the weights before and after drying, were measured. The water content (wt%) was calculated from the weight loss and the weight after drying using the following formula: Water content (wt%) = 100 × weight loss (g) / weight after drying (g)

[0129] <Ratio of Water Amount to Pore Volume> The ratio of water amount to pore volume was calculated by converting the water amount (weight) (g / g) per unit weight of the supported ruthenium oxide catalyst to the water amount (volume) per unit weight (mL / g) and dividing the converted amount by the pore volume (mL / g). The conversion of the water amount (weight) (g / g) to the water amount (volume) (mL / g) was performed using the density of water at room temperature and normal pressure as 1 g / cm ３ I went as.

[0130] Example 1 Corrosion Test of Nickel (Ni) Test Piece (Measurement of Pit Depth) The supported ruthenium oxide catalyst was placed on the entire upper surface of a nickel test piece (a 25 mm square low-carbon nickel plate, alloy number NW2201, JIS H4551), and the piece was allowed to stand in an air atmosphere in a thermo-hygrostat at 25°C and 40% relative humidity for 672 hours.

[0131] The water content of the supported ruthenium oxide catalyst after the standing treatment was measured as described above and found to be 0.43 wt %. The ratio of the water content to the pore volume of the supported ruthenium oxide catalyst was calculated as described above and found to be 2.0%.

[0132] The test specimen was washed with water to remove the supported ruthenium oxide catalyst, and the pitting depth of the nickel test specimen was measured by 3D measurement using a digital microscope (Keyence Corporation, VHX-1000), which was found to be 22.00 μm. The results are shown in Table 1 and Figure 1.

[0133] Example 2 A corrosion test was carried out in the same manner as in Example 1, except that the humidity in the thermo-hygrostat chamber was set to 50% relative humidity. After the standing treatment, the moisture content of the supported ruthenium oxide catalyst was measured to be 0.56 wt %, and the ratio of the moisture content to the pore volume of the supported ruthenium oxide catalyst was 2.5%. The pitting depth of the test piece was 60.00 μm. The results are shown in Table 1 and Figure 1.

[0134] Example 3 A corrosion test was carried out in the same manner as in Example 1, except that the temperature in the thermo-hygrostat chamber was 40°C and the humidity was 70% relative humidity. After the standing treatment, the moisture content of the supported ruthenium oxide catalyst was measured and found to be 0.86 wt%, and the ratio of the moisture content to the pore volume of the supported ruthenium oxide catalyst was 3.9%. The pitting depth of the test piece was 109.00 μm. The results are shown in Table 1 and Figure 1.

[0135] Comparative Example 1 A corrosion test was carried out in the same manner as in Example 1, except that the temperature in the thermo-hygrostat chamber was 50°C and the humidity was 80% relative humidity. After the static treatment, the moisture content of the supported ruthenium oxide catalyst was measured and found to be 1.03 wt%, and the ratio of the moisture content to the pore volume of the supported ruthenium oxide catalyst was 4.7%. The pitting depth of the test piece was 364.50 μm. The results are shown in Table 1 and FIG. 1.

[0136] Comparative Example 2 A corrosion test was carried out in the same manner as in Example 1, except that the temperature in the thermo-hygrostat chamber was 50°C and the humidity was 95% relative humidity. After the static treatment, the moisture content of the supported ruthenium oxide catalyst was measured and found to be 1.39 wt%, and the ratio of the moisture content to the pore volume of the supported ruthenium oxide catalyst was 6.3%. The pitting depth of the test piece was 416.2 μm. The results are shown in Table 1 and FIG. 1.

[0137]

Claims

1. A catalyst for producing halogen by oxidizing hydrogen halide with oxygen to produce halogen, wherein the volume of moisture contained in the catalyst for producing halogen when sealed in a package is 4% or less of the pore volume of the catalyst for producing halogen.

2. The catalyst for producing halogen according to claim 1, wherein the concentration of halogen contained in the catalyst for producing halogen is in the range of 0.01% by mass to 0.5% by mass when the total mass of the catalyst for producing halogen is taken as 100% by mass.

3. The catalyst for producing halogen according to claim 1 or 2, which is a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier.

4. A package containing a catalyst for producing halogen by oxidizing hydrogen halide with oxygen, wherein the volume of moisture contained in the catalyst for producing halogen is 4% or less of the pore volume of the catalyst for producing halogen.

5. The package according to claim 4, wherein the concentration of halogen contained in the catalyst for producing halogen is in the range of 0.01% by mass to 0.5% by mass when the total mass of the catalyst for producing halogen is taken as 100% by mass.

6. The package according to claim 4 or 5, wherein the catalyst for producing halogen is a supported ruthenium oxide catalyst in which ruthenium oxide is supported on a carrier.

7. A method for manufacturing a package containing a catalyst for producing halogen, comprising the steps of: preparing the catalyst for producing halogen and an enclosure; and circulating an inert gas at 50°C or lower inside the enclosure to reduce the volume of moisture contained in the catalyst for producing halogen to 4% or less of the pore volume of the catalyst for producing halogen, and then enclosing the catalyst in the enclosure to manufacture the package.

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