KR20220109106A - Catalyst for hydrogen chloride oxdidation reaction process including inorganic additive and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a catalyst for a hydrogen chloride oxidation process containing inorganic additives and a manufacturing method thereof. More specifically, the catalyst improves the oxidation reaction activity of hydrogen chloride by further containing the inorganic additives. Provided is the catalyst for the hydrogen chloride oxidation process containing a carrier; and ruthenium oxide and inorganic additives supported on the carrier.

Description

Catalyst for hydrogen chloride oxidation process containing inorganic additive and manufacturing method thereof

The present invention relates to a catalyst for a hydrogen chloride oxidation process containing an inorganic additive and a method for preparing the same, and more particularly, the catalyst is characterized in that the oxidation reaction activity of hydrogen chloride is improved by further including an inorganic additive.

The Deacon process, a catalytic vapor phase oxidation reaction of hydrogen chloride developed in 1868 by Henry Deacon, is an eco-friendly and energy-efficient process that regenerates hydrogen chloride, a by-product generated in the production process of polyurethane and polycarbonate, into chlorine. However, the CuO/CuCl ₂ catalyst used in the early Deacon process has very low activity and must be carried out at a reaction temperature of 400° C. or higher. There was a problem of low catalyst durability as it was lost afterward.

Then, in 1999, Sumitomo Chemical developed a new type of Deacon process catalyst in which ruthenium oxide, an active material, was supported in an epitaxial direction on a rutile-type titania carrier. It has the characteristic of producing chlorine. However, the hydrogen chloride oxidation reaction is an exothermic reaction, and a temperature higher than the reaction temperature is locally formed in the hot-spot inside the reaction tube, which causes a sintering phenomenon that reduces the dispersion of ruthenium oxide, an active material, and is a catalyst during long-term reaction operation. There was a problem that the activity of the continuously decreased.

As can be seen, it is very difficult to satisfy the durability, activity, and lifespan of the catalyst in the Deacon process. In addition, most of these catalysts have many restrictions on their use due to difficult reactor types and operating conditions. In particular, in the case of powder form, when used in a fixed bed reactor, a differential pressure is generated at the front and rear ends of the catalyst bed, which may cause a problem that operation is impossible. Therefore, in order to solve the various problems mentioned above, research on various catalysts is currently in progress.

For example, Korean Patent Application Laid-Open No. 10-2012-0040701 relates to a method for producing chlorine by vapor phase oxidation with a supported catalyst based on ruthenium, wherein the catalyst carrier has a pore diameter of greater than 50 nm. Disclosed is a nanoparticle having a plurality of pores and containing ruthenium and a ruthenium compound as a catalytically active component.

Korean Patent Application Laid-Open No. 10-2011-0107350 relates to a gas phase reaction catalyst comprising one or more active metals on a support comprising aluminum oxide and having high mechanical stability, wherein the aluminum oxide component of the support is substantially alpha-aluminum. The inclusion of oxides is disclosed. In particular, based on the total weight of the catalyst, on a support made of α-Al ₂ O ₃ a) 0.001 to 10% by weight of ruthenium, copper and/or gold, b) 0.1 to 10% by weight of nickel, c ) from 0 to 5% by weight of one or more alkaline earth metals, d) from 0 to 5% by weight of one or more alkali metals, e) from 0 to 5% by weight of one or more rare earth elements, f) selected from palladium, platinum, iridium and rhenium It is characterized in that it comprises a, and the catalyst is mentioned to be used for the oxidation of hydrogen chloride (Deacon reaction).

Korean Patent Application Laid-Open No. 10-2013-0100282 discloses a catalyst for the production of chlorine by catalytic gas phase oxidation of hydrogen chloride using oxygen containing calcined tin dioxide and at least one halogen-containing ruthenium compound as a catalyst and Disclosed is its use.

Lastly, non-patent literature A CeO2/ZrO2-TiO2 Catalyst for the Selective Catalytic Reduction of NOx with NH3 (Catalysts, pp.592. 2018.08.) relates to a catalyst for the selective catalytic reduction of NOx by NH ₃ Oxidation reaction A Ce-Zr-Ti oxide catalyst is mentioned as a catalyst for use.

Accordingly, the present inventors discovered that the oxidation reaction activity of hydrogen chloride is improved when the catalyst is prepared by including ruthenium oxide and inorganic additives while researching the catalyst used for the oxidation reaction of hydrogen chloride as described above, thereby completing the present invention. became

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a catalyst for the hydrogen chloride oxidation process including an inorganic additive.

Another object of the present invention is to provide a method for preparing a catalyst for the hydrogen chloride oxidation process.

Another object of the present invention is to provide a method for producing chlorine using the catalyst for the hydrogen chloride oxidation process.

As a technical means for achieving the above-described technical problem, one aspect of the present invention is,

carrier; And it provides a catalyst for the hydrogen chloride oxidation reaction comprising a ruthenium oxide and an inorganic additive supported on the carrier.

The carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof.

The catalyst may further include a metal oxide supported on the carrier, and the metal oxide may include a metal oxide represented by Formula 1 below.

[Formula 1]

MO ₂

In Formula 1, M is Ti, Ce, or Zr.

Based on 100 parts by weight of the carrier, the content of the ruthenium oxide may be 1 part by weight to 10 parts by weight, and the content of the metal oxide may be 0.5 parts by weight to 10 parts by weight.

The inorganic additive may include hydrochloric acid (HCl).

The molar ratio (Cl ⁻ /Ru) of the ruthenium element (Ru) of the ruthenium oxide and the chloride ion (Cl ⁻ ) of hydrochloric acid may be 1 to 10.

The molar ratio (Cl ⁻ /Ru) of elemental ruthenium (Ru) of the ruthenium oxide and chloride (Cl ⁻ ) of hydrochloric acid may be 3 to 5.

The catalyst may be in a form selected from the group consisting of powder, particles, pellets, and combinations thereof.

When the catalyst is in the form of pellets, the diameter of the pellets may be 1 mm to 10 mm.

The catalyst may have a publicly available yield (STY) calculated by the following Equation (1) of 1.4 or more.

[Equation 1]

In Equation 1, the reaction time is 22 hours (hr).

The catalyst may have a public yield (STY) calculated by Equation 1 above 1.8 or more.

In addition, another aspect of the present invention,

It provides a method for producing a catalyst for a hydrogen chloride oxidation reaction comprising a; supporting a ruthenium precursor and an inorganic additive on a carrier.

The carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof.

The inorganic additive may include hydrochloric acid (HCl).

The method for preparing the catalyst for the hydrogen chloride oxidation process may further include a step of supporting a metal oxide on a carrier before the supporting of the ruthenium precursor and the inorganic additive.

The metal oxide may include a metal oxide represented by the following formula (1).

[Formula 1]

MO ₂

In Formula 1, M is Ti, Ce, or Zr.

The method for preparing the catalyst for the hydrogen chloride oxidation process includes the steps of supporting the ruthenium precursor and an inorganic additive; Thereafter, drying and calcining the carrier; may further include.

The drying may be performed at a temperature of 10° C. to 120° C. for 3 hours to 5 hours, and the calcination may be performed at a temperature of 350° C. to 700° C. for 2 hours to 6 hours.

In addition, another aspect of the present invention,

It provides a method for producing chlorine through the hydrogen chloride oxidation reaction in the presence of the catalyst for the hydrogen chloride oxidation reaction process.

The hydrogen chloride oxidation reaction may be carried out at a temperature of 280 ℃ to 380 ℃.

The catalyst according to the present invention as described above solves the sintering phenomenon of ruthenium oxide occurring in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, so that the initial catalyst activity can be maintained despite the long-time catalyst operation.

In addition, since the catalyst further includes an inorganic additive in addition to ruthenium oxide, the oxidation reaction activity of hydrogen chloride may be very excellent.

In addition, the catalyst is provided as a catalyst in the form of pellets in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, and can provide high mechanical strength so that they are not crushed in the process.

Finally, the catalyst provides high catalytic activity and durability, so that it is not limited by the shape of the reactor, operating conditions, etc., so there is no restriction in use and ease in handling.

1 is a graph showing oxidation reaction activity according to an embodiment and a comparative example of the present invention.
2 is a graph showing oxidation reaction activity according to another Example and Comparative Example of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

carrier; And it provides a catalyst for the hydrogen chloride oxidation reaction comprising a ruthenium oxide and an inorganic additive supported on the carrier.

Hereinafter, the catalyst for the hydrogen chloride oxidation process according to the first aspect of the present application will be described in detail.

In one embodiment of the present application, the carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and may preferably include titania.

In one embodiment of the present application, the titania carrier may be, for example, anatase-type titania or rutile-type titania, amorphous titania, or a mixture thereof. In addition, the titania carrier may include an oxide such as alumina, zirconia or niobium oxide. Preferably, a rutile-type titania is provided, for example, titania manufactured by Sakai Corporation may be provided, but is not limited thereto. Meanwhile, the specific surface area of the titania carrier may be measured by a commonly used BET method, and the specific surface area may be 5 to 300 m ² /g, preferably 5 to 50 m ² /g. If the specific surface area exceeds the above range, it may be difficult to secure thermal stability of ruthenium oxide, and if it is less than the above range, there may be problems in which dispersion stability and catalytic activity are lowered.

In addition, the aluminum carrier may be preferably provided with alpha-alumina. In this case, since the alpha-alumina has a low BET specific surface area, it may be preferable in that absorption of other impurities is difficult to occur. Meanwhile, the specific surface area of the aluminum carrier may be 10 to 500 m ² /g, preferably 20 to 350 m ² /g.

In addition, the zirconia carrier has pores in the range of 0.05 to 10 μm, and the specific surface area may be the same as the above.

In one embodiment of the present application, the catalyst may further include a metal oxide supported on the carrier, and the metal oxide may include a metal oxide represented by Formula 1 below.

[Formula 1]

MO ₂

In Formula 1, M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO ₂ ), ceria (CeO ₂ ), or zirconia (ZrO ₂ ), and may include a metal oxide selected from the group consisting of combinations thereof.

In one embodiment of the present application, the metal oxide may be preferably ceria and zirconia, and the weight content ratio of ceria and zirconia may be 1: 0.5 to 1, preferably 1: 1. have. When the weight content ratio of ceria and zirconia satisfies the above values, the catalyst for the hydrogen chloride oxidation reaction including the same has excellent mechanical strength and catalyst durability, and thus may be suitable for long-term catalyst operation.

In one embodiment of the present application, the metal oxide may be provided in the form of a precursor thereof. For example, the cerium precursor may exist in the form of a complex salt, and may include a cerium compound, particularly metal salts such as cerium nitrate, cerium acetate, or cerium chloride. Preferably, it may include cerium nitrate, and after being impregnated in a carrier in the form of a precursor, it may be provided as a final catalyst through drying and calcination.

In one embodiment of the present application, based on 100 parts by weight of the carrier, the content of the ruthenium oxide may be 1 part by weight to 10 parts by weight, and the content of the metal oxide may be 0.5 parts by weight to 10 parts by weight.

In one embodiment of the present application, the inorganic additive may include hydrochloric acid (HCl). That is, the catalyst for the hydrogen chloride oxidation reaction process may include an inorganic additive as described above to improve the oxidation reaction activity of hydrogen chloride. In this case, the molar ratio (Cl ⁻ /Ru) of the ruthenium element (Ru) of the ruthenium oxide and the chloride ion (Cl ⁻ ) of hydrochloric acid may be 1 to 10, preferably 3 to 5. When the molar ratio (Cl ^- /Ru) is less than 1, the amount of the inorganic additive is too small to improve the oxidation reaction activity according to the input, and when it exceeds 10, the content of the added inorganic additive is too much. Rather, the oxidation reaction activity may be reduced.

In one embodiment of the present application, the catalyst may have a common yield (STY) calculated by the following Equation 1 of 1.4 or more, preferably 1.8 or more.

[Equation 1]

In Equation 1, the reaction time may be 22 hours (hr). That is, the catalyst may have a high yield (STY) by including the inorganic additive, and through this, it may be confirmed that the catalyst has excellent oxidation activity.

In one embodiment of the present application, the catalyst may be in a form selected from the group consisting of powder, particles, pellets, and combinations thereof, preferably in the form of pellets. For example, when the catalyst is in the form of a pellet, the diameter of the pellet may be 1 mm to 10 mm.

The second aspect of the present application is

It provides a method for producing a catalyst for a hydrogen chloride oxidation reaction comprising a; supporting a ruthenium precursor and an inorganic additive on a carrier.

Although detailed descriptions of parts overlapping with the first aspect of the present application are omitted, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect.

Hereinafter, the method for preparing the catalyst for the hydrogen chloride oxidation process according to the second aspect of the present application will be described in detail step by step.

First, in one embodiment of the present application, the method for preparing the catalyst for the hydrogen chloride oxidation reaction process may include a step of forming the carrier before the ruthenium precursor and the inorganic additive are supported.

In one embodiment of the present application, the carrier may include a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and may preferably include titania.

In one embodiment of the present application, the molding of the carrier may be performed by mixing the carrier with an organic binder, an inorganic binder, and water. The carrier molded as described above may be applicable to a fixed-bed reactor, and may be easily handled without restrictions on use regardless of the shape of the reactor, operating conditions, and the like. In particular, when applied to a fixed bed reactor, it may be used without generating a differential pressure, and may provide improved durability and mechanical strength by increasing catalytic activity and enhancing thermal stability.

In one embodiment of the present application, the organic binder is methyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, purified starch, dextrin, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyethylene glycol, paraffin, It may include a material selected from the group consisting of a wax emulsion, microcrystalline wax, and combinations thereof, and the moldability of the carrier may be improved by including the organic binder.

In one embodiment of the present application, the inorganic binder is a material selected from the group consisting of alumina sol, silica sol, titania sol, zirconia sol, and combinations thereof. may include, and the mechanical properties of the carrier may be improved by including the inorganic binder.

Next, in one embodiment of the present application, the method for preparing the catalyst for the hydrogen chloride oxidation reaction process may include a step of supporting a ruthenium precursor and an inorganic additive on a carrier.

In one embodiment of the present application, the ruthenium precursor may be preferably provided as a halide, and most preferably as ruthenium chloride containing a chloride. In addition, the ruthenium precursor may be provided as a hydrate of the ruthenium precursor in some cases.

In one embodiment of the present application, the ruthenium precursor may be mixed in a solvent in the form of a powder, and a solid carrier is suspended in the solvent to form a precipitate, and the ruthenium precursor is deposited and supported on the solid carrier. The temperature provided during the immersion is 0° C. to 100° C., preferably 0° C. to 50° C., and the pressure may be provided at 0.1 Mpa to 1 Mpa, preferably atmospheric pressure. The loading may be performed under an air atmosphere or an inert gas atmosphere such as nitrogen, helium, argon, or carbon dioxide, and in this case, may include water vapor. Preferably, it may be carried out under an inert gas atmosphere.

In one embodiment of the present application, the solvent in which the ruthenium precursor is dissolved may include a solvent selected from the group consisting of water, alcohol, nitrile, and combinations thereof. In this case, the water may be distilled water, ion-exchange water, or high-purity water such as ultrapure water (DIW) used. . In the case of the alcohol, the organic solvent may be a monoalcohol, and may be a C3 or higher primary alcohol. Preferably, a C3 alcohol-based organic solvent may be used, and most preferably 1-propanol may be used. The solvent can support the ruthenium component only on the outer surface of the titania carrier in which a hydroxy group (-OH) exists by utilizing high wettability and hydrophobicity, It may be to provide an effect of improving the degree of dispersion. In addition, the content of the solvent is not significantly limited, but if it is excessively large, it takes a lot of drying time, so it may be freely adjusted at the level of a person skilled in the art.

In one embodiment of the present application, the inorganic additive may include hydrochloric acid (HCl). That is, the catalyst for the hydrogen chloride oxidation reaction process to be finally prepared may include the inorganic additive as described above, so that the oxidation reaction activity of hydrogen chloride is improved. In this case, the molar ratio (Cl ⁻ /Ru) of the ruthenium element (Ru) of the ruthenium precursor and the chloride ion (Cl ⁻ ) of hydrochloric acid may be 1 to 10, preferably 3 to 5. When the molar ratio (Cl ^- /Ru) is less than 1, the amount of the inorganic additive is too small to improve the oxidation reaction activity according to the input, and when it exceeds 10, the content of the added inorganic additive is too much. Rather, the oxidation reaction activity may be reduced.

In one embodiment of the present application, the method for preparing the catalyst for the hydrogen chloride oxidation process may further include a step of supporting a metal oxide on a carrier before the supporting of the ruthenium oxide and the inorganic additive.

In one embodiment of the present application, the metal oxide may include a metal oxide represented by the following formula (1).

[Formula 1]

MO ₂

In Formula 1, M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO ₂ ), ceria (CeO ₂ ), or zirconia (ZrO ₂ ), and may include a metal oxide selected from the group consisting of combinations thereof.

In one embodiment of the present application, the metal oxide may be provided in the form of a precursor thereof. For example, the cerium precursor may exist in the form of a complex salt, and may include a cerium compound, particularly metal salts such as cerium nitrate, cerium acetate, or cerium chloride. Preferably, it may include cerium nitrate, and after being impregnated in a carrier in the form of a precursor, it may be provided as a final catalyst through drying and calcination.

In one embodiment of the present application, the method for preparing the catalyst for the hydrogen chloride oxidation process comprises the steps of molding the carrier; supporting the ruthenium oxide and the inorganic additive; and/or supporting a metal oxide on a carrier; Thereafter, drying and calcining the carrier, respectively; may be further included.

In one embodiment of the present application, the carrier may be completed as a final molded carrier by performing drying and firing. In this case, the drying and firing may be alternatively performed as needed, and the order or number of times may be freely adjustable.

In one embodiment of the present application, the drying may be performed at a temperature of 10 °C to 120 °C for 3 hours to 5 hours. The drying may be performed through rotation and stirring, and specifically, may be performed by vibrating a drying container or using a stirrer provided in the container. On the other hand, the drying temperature may be usually about room temperature to 100 ℃, the pressure is 0.1 to 1 MPa is usually applied, preferably atmospheric pressure may be provided.

In one embodiment of the present application, the sintering may be performed at a temperature of 350° C. to 700° C. for 2 hours to 6 hours, and then cooled to room temperature. In addition, the oxidizing gas provided for the firing may be, for example, a gas containing oxygen. In this case, the oxygen concentration may be provided in the range of 1 to 30% by volume that is usually applied. As the oxygen source, air or pure oxygen may be generally provided, and an inert gas or water vapor may be further included if necessary. The oxidizing gas may preferably be provided with air, and may be cooled to room temperature after firing at a temperature of about 350° C. and 3 hours in an electric furnace under a flow of air.

The third aspect of the present application is

It provides a method for producing chlorine through hydrogen chloride oxidation in the presence of a catalyst for the hydrogen chloride oxidation process according to the first aspect of the present application.

Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect. .

Hereinafter, a method for producing chlorine according to the third aspect of the present application will be described in detail.

In one embodiment of the present application, the reaction for the production of chlorine may be provided in a fixed bed method or a fluidized bed method, a gas phase reaction, etc., and preferably a gas phase reaction may be provided. Since the hydrogen chloride oxidation reaction is an equilibrium reaction and the equilibrium conversion rate is lowered when it is performed at too high a temperature, it is preferably performed at a relatively low temperature. At this time, the reaction temperature may be usually 100 ℃ to 500 ℃, preferably 280 ℃ to 380 ℃. In addition, the reaction pressure may be about 0.1 Mpa to about 5 Mpa. As the oxygen source, air or pure oxygen may be used, and the theoretical molar amount of oxygen relative to hydrogen chloride is 1/4 mole, but typically 0.1 to 10 times oxygen may be provided.

In addition, the hydrogen chloride supply rate may be expressed as a gas supply rate per 1 L of catalyst (L/h; 0° C., converted to 1 atm), that is, GHSV, and may be usually about 10 to 20000 h ⁻¹ . However, at this time, the amount of the catalyst input may be slightly modified depending on the temperature, the amount of the catalyst, and the amount of the chlorine product to be produced.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example 1. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide (Cl ^- / Ru's molar ratio = 3)

A precursor solution obtained by dissolving 0.8 g of ruthenium chloride hydrate (KOJIMA) in 5.2 g of DIW and 1.2 g of a hydrochloric acid solution (HCl) were supported on 20.0 g of titania powder (SAKAI) and dried in an oven at 100° C. for 4 hours. Thereafter, the dried molded support was calcined in an electric furnace at 350° C. for 3 hours to obtain a catalyst for a hydrogen chloride oxidation process having a molar ratio (Cl ^- /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ^- ) of 3.

Example 2. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide (Cl ^- / Ru's molar ratio = 5)

In Example 1, 0.8 g of ruthenium chloride hydrate (KOJIMA) was dissolved in 4.7 g of DIW and 2.0 g of hydrochloric acid solution (HCl) was supported on 20.0 g of titania powder (SAKAI) using the same method. A catalyst for the hydrogen chloride oxidation process was prepared. At this time, the molar ratio (Cl ⁻ /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ⁻ ) of the prepared catalyst was 5.

Example 3. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide and metal oxide (Cl ^- / Ru's molar ratio = 3)

20g of titania powder (SAKAI), 0.4g of cellulose-based organic binder (YUKEN), 2.5g of TiO ₂ sol (SAKAI), and 9.0g of DIW were mixed evenly with a molded carrier extruded from the dough in an oven at 100°C for 4 hours. dried. The dried molded support was cut at intervals of 2-3 mm, and then fired in an electric furnace at 600° C. for 3 hours to complete the TiO ₂ molded support.

Thereafter, a precursor solution obtained by dissolving 1.3 g of cerium nitrate hydrate (Kanto) and 1.3 g of zirconium chloride hydrate (Kanto) in 6.0 g of DIW was impregnated into the TiO ₂ molding carrier and dried in an oven at 100° C. for 4 hours. The dried molded support was calcined in an electric furnace at 600° C. for 3 hours to obtain a molded support having a ceria content of 2.5% and a zirconia content of 2.5%.

Then, a precursor solution obtained by dissolving 0.8 g of ruthenium chloride hydrate (KOJIMA) in 6.0 g of DIW and 1.2 g of a hydrochloric acid solution (HCl) were impregnated into 20 g of the molding carrier, and then dried in an oven at 100° C. for 4 hours. Finally, the dried molded support was calcined in an electric furnace at 350° C. for 3 hours to obtain a catalyst for the hydrogen chloride oxidation process having a molar ratio (Cl ^- /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ^- ) of 3.

Example 4. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide and metal oxide (Cl ^- / Ru's molar ratio = 5)

In Example 3, a precursor solution obtained by dissolving 1.3 g of cerium nitrate hydrate (Kanto) and 1.3 g of zirconium chloride hydrate (Kanto) in 6.0 g of DIW was impregnated into a TiO ₂ molding carrier, and 0.8 g of ruthenium chloride hydrate (KOJIMA) was added. A catalyst for the hydrogen chloride oxidation process was prepared in the same manner except that 20 g of the molding carrier was impregnated with a precursor solution dissolved in 4.7 g of DIW and 2.0 g of a hydrochloric acid solution (HCl). At this time, the molar ratio (Cl ⁻ /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ⁻ ) of the prepared catalyst was 5.

comparative example 1. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide (Cl ^- / Ru's molar ratio = 0)

A catalyst for the hydrogen chloride oxidation process was prepared in the same manner as in Example 1, except that hydrochloric acid solution (HCl) was not supported.

comparative example 2. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide (Cl ^- / Ru's molar ratio = 10)

In Example 1, 0.8 g of ruthenium chloride hydrate (KOJIMA) was dissolved in 3.4 g of DIW and 4.0 g of hydrochloric acid solution (HCl) was supported on 20.0 g of titania powder (SAKAI) using the same method. A catalyst for the hydrogen chloride oxidation process was prepared. At this time, the molar ratio (Cl ⁻ /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ⁻ ) of the prepared catalyst was 10.

comparative example 3. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide and metal oxide (Cl ^- / Ru's molar ratio = 0)

A catalyst for the hydrogen chloride oxidation process was prepared in the same manner as in Example 3, except that hydrochloric acid solution (HCl) was not supported.

comparative example 4. Preparation of catalyst for hydrogen chloride oxidation process containing ruthenium oxide and metal oxide (Cl ^- / Ru's molar ratio = 10)

In Example 3, a precursor solution obtained by dissolving 1.3 g of cerium nitrate hydrate (Kanto) and 1.3 g of zirconium chloride hydrate (Kanto) in 6.0 g of DIW was impregnated into a TiO ₂ molding carrier, and 0.8 g of ruthenium chloride hydrate (KOJIMA) was added. A catalyst for the hydrogen chloride oxidation process was prepared using the same method except that the precursor solution dissolved in 3.4 g of DIW and 4.0 g of hydrochloric acid solution (HCl) were impregnated into 20.0 g of the molding carrier. At this time, the molar ratio (Cl ⁻ /Ru) of elemental ruthenium (Ru) and chlorine ions (Cl ⁻ ) of the prepared catalyst was 10.

Experimental example . Evaluation of catalyst oxidation activity

In order to evaluate the oxidation reaction activity of the catalyst for the hydrogen chloride oxidation reaction prepared in Examples and Comparative Examples, the hydrogen chloride oxidation reaction was carried out in a fixed-bed reaction tube made of Nickel 201 material.

Specifically, 1.35 g of each of the catalysts prepared in Examples and Comparative Examples was diluted with γ-alumina pellets in a volume ratio of 1:9, and then filled in a fixed-bed reaction tube with an outer diameter of 1 inch tube. Thereafter, the reaction temperature was set to 300° C. based on the catalyst bed, and hydrogen chloride and oxygen gas as reactants were supplied at a rate of GHSV 9,000 h ⁻¹ and 100 cc/min at atmospheric pressure in a 1:1 volume ratio to carry out the hydrogen chloride oxidation reaction.

After 22 hours had elapsed from the start of the reaction and the catalyst activity reached a sufficiently stable state, the gas at the rear end of the reaction tube was circulated through a 15% aqueous potassium iodide solution, and sampling was performed for 5 minutes. Then, the production amount of chlorine was measured by the iodine titration method to calculate the space time yield (STY) of hydrogen chloride by Equation 1 below. The results are shown in Tables 1 and 2 below. In addition, the oxidation reaction activity result according to Table 1 is shown as a graph in FIG. 1, and the oxidation reaction activity result according to Table 2 is shown as a graph in FIG. 2 .

[Equation 1]

[Table 1]

[Table 2]

As shown in Tables 1 and 2, respectively, the catalysts prepared according to the Examples of the present invention having a molar ratio of C ^-1 /Ru of 3 and 5 were added in Comparative Examples 1 and 3 or in excess of hydrochloric acid solution. As a result, it was confirmed that the oxidation reaction activity was more excellent than those of Comparative Examples 2 and 4 in which the molar ratio of C ^-1 /Ru was 10.

Therefore, it was confirmed that the catalyst according to the present invention is very suitable for a commercialization process because of its excellent oxidation activity.

Above, the present invention has been described in detail along with preferred embodiments with reference to the drawings, but the scope of the technical spirit of the present invention is not limited to these drawings and examples. Accordingly, various modifications or equivalent ranges of embodiments may exist within the scope of the technical spirit of the present invention. Therefore, the scope of the technical idea according to the present invention should be interpreted by the claims, and the technical idea within the equivalent or equivalent scope should be interpreted as belonging to the scope of the present invention.

Claims (18)

carrier; and
A catalyst for a hydrogen chloride oxidation process comprising ruthenium oxide and an inorganic additive supported on the carrier.
According to claim 1,
The carrier is a catalyst for the hydrogen chloride oxidation process comprising a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof.
According to claim 1,
The catalyst will further include a metal oxide supported on the carrier,
The metal oxide is a catalyst for the hydrogen chloride oxidation process comprising a metal oxide represented by the following formula (1):
[Formula 1]
MO ₂
(In Formula 1, M is Ti, Ce, or Zr.)
4. The method of claim 3,
Based on 100 parts by weight of the carrier,
The content of the ruthenium oxide is 1 part by weight to 10 parts by weight,
The content of the metal oxide is 0.5 parts by weight to 10 parts by weight of the catalyst for the hydrogen chloride oxidation process.
According to claim 1,
The inorganic additive is a catalyst for the hydrogen chloride oxidation process comprising hydrochloric acid (HCl).
6. The method of claim 5,
The molar ratio (Cl ^- /Ru) of the ruthenium element (Ru) of the ruthenium oxide and the chloride ion (Cl ^- ) of hydrochloric acid is 1 to 10, the catalyst for the hydrogen chloride oxidation process.
6. The method of claim 5,
The molar ratio (Cl ^- /Ru) of the ruthenium element (Ru) of the ruthenium oxide and the chloride (Cl ^- ) of hydrochloric acid is 3 to 5, the catalyst for the hydrogen chloride oxidation reaction.
According to claim 1,
The catalyst for the process is a catalyst for the hydrogen chloride oxidation reaction that is made in a form selected from the group consisting of powder, particles, pellets and combinations thereof.
9. The method of claim 8,
When the catalyst is in the form of a pellet, the diameter of the pellet is 1 mm to 10 mm of the catalyst for the hydrogen chloride oxidation process.
supporting a ruthenium precursor and an inorganic additive on a carrier;
A method for producing a catalyst for a hydrogen chloride oxidation process comprising a.
11. The method of claim 10,
The method for preparing a catalyst for the hydrogen chloride oxidation reaction process, wherein the carrier comprises a carrier selected from the group consisting of alumina, titania, zirconia, and combinations thereof.
11. The method of claim 10,
The inorganic additive is a method for producing a catalyst for the hydrogen chloride oxidation reaction comprising hydrochloric acid (HCl).
11. The method of claim 10,
The method for preparing the catalyst for the hydrogen chloride oxidation process,
The method of manufacturing a catalyst for hydrogen chloride oxidation reaction further comprising; supporting a metal oxide on a carrier before the supporting of the ruthenium precursor and the inorganic additive.
14. The method of claim 13,
The metal oxide is a method for preparing a catalyst for the hydrogen chloride oxidation process comprising a metal oxide represented by the following formula (1):
[Formula 1]
MO ₂
(In Formula 1, M is Ti, Ce, or Zr.)
11. The method of claim 10,
The method for preparing the catalyst for the hydrogen chloride oxidation process,
supporting the ruthenium precursor and an inorganic additive; Since the,
Drying and calcining the carrier; Method for producing a catalyst for the hydrogen chloride oxidation process further comprising a.
16. The method of claim 15,
The drying is to be carried out at a temperature of 10 ° C. to 120 ° C. for 3 hours to 5 hours,
The method for producing a catalyst for the hydrogen chloride oxidation reaction that the calcination is carried out at a temperature of 350 ° C. to 700 ° C. for 2 hours to 6 hours.
A method for producing chlorine through hydrogen chloride oxidation in the presence of the catalyst for the hydrogen chloride oxidation process according to claim 1 .
18. The method of claim 17,
The hydrogen chloride oxidation reaction is a method for producing chlorine that is carried out at a temperature of 280 ℃ to 380 ℃.

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