High-yield production method of chlorine by hydrogen chloride oxidation reaction

Abstract

The present invention relates to a method for producing chlorine in high yield by oxidation of hydrogen chloride, and more specifically, is characterized in that chlorine is produced in high yield by carrying out oxidation of hydrogen chloride with a mixed gas containing carbon oxides.

Description

[Technical Field]

[0001] The present invention relates to a method for producing chlorine in high yield by a hydrogen chloride oxidation reaction, and more specifically, is characterized by producing chlorine in high yield by carrying out an oxidation reaction of hydrogen chloride with a mixed gas containing carbon oxides. [Background technology]

[0002] The Deacon process, a catalytic gas-phase oxidation reaction of hydrogen chloride developed by Henry Deacon in 1868, is an environmentally friendly and energy-efficient process that regenerates hydrogen chloride, a by-product of the polyurethane and polycarbonate production process, into chlorine. However, the CuO / CuCl2 catalyst used in the Deacon process has very low activity and must be operated at a reaction temperature of 400°C or higher. During the reaction, copper oxide, the active substance, is converted into a highly volatile copper chloride-based substance and then disappears, resulting in low catalyst durability.

[0003] Subsequently, in 1999, Sumitomo Chemical developed a new type of Deacon process catalyst in which ruthenium oxide, the active material, is epitaxially supported on a rutile-type titania support. This catalyst has the characteristic of producing chlorine even at a low reaction temperature of 300°C. However, because the hydrogen chloride oxidation reaction is an exothermic reaction, hot spots inside the reaction tube can locally form at temperatures higher than the reaction temperature. This causes a sintering phenomenon that reduces the dispersion of ruthenium oxide, the active material, and results in a continuous decrease in catalyst activity over long-term reaction operation.

[0004] As we have seen, it is extremely difficult to achieve catalyst durability, activity, and lifespan in the Deacon process. Furthermore, most of these catalysts have many limitations in their use due to strict reactor configurations and operating conditions. In particular, when using powder catalysts in a fixed-bed reactor, they can cause blockages in the front and back of the catalyst layer, making operation impossible. Therefore, research into various catalysts is currently underway to address these issues.

[0005] For example, Korean Patent Publication No. 10-2012-0040701 relates to a method for producing chlorine by gas phase oxidation using a supported ruthenium-based catalyst, and discloses that the catalyst support has a plurality of pores with a pore diameter of more than 50 nm and supports nanoparticles containing ruthenium or a ruthenium compound as a catalytically active component.

[0006] Korean Patent Publication No. 10-2011-0107350 discloses a highly mechanically stable gas-phase reaction catalyst containing one or more active metals on an aluminum oxide support, where the aluminum oxide component of the support is substantially alpha-aluminum oxide. Specifically, the catalyst is characterized by containing, based on the total weight of the catalyst, a) 0.001 to 10 wt.% of ruthenium, copper, and / or gold, b) 0.1 to 10 wt.% of nickel, c) 0 to 5 wt.% of one or more alkaline earth metals, d) 0 to 5 wt.% of one or more alkali metals, e) 0 to 5 wt.% of one or more rare earth elements, and f) selected from palladium, platinum, iridium, and rhenium, on an α-Al2O3 support. The catalyst is used for the oxidation of hydrogen chloride (Deacon reaction).

[0007] Korean Patent Publication No. 10-2013-0100282 discloses a catalyst for producing chlorine by catalytic gas phase oxidation of hydrogen chloride with oxygen, the catalyst comprising calcined tin dioxide as a support and at least one halogen-containing ruthenium compound, and its use.

[0008] Finally, in the non-patent literature, A CeO2 / ZrO2-TiO2 Catalyst for the Selective Catalytic Reduction of NO x with NH3 (Catalysts, pp. 592, August 2018) x The paper is concerned with catalysts for the selective catalytic reduction of , and mentions Ce-Zr-Ti oxide catalyst as a catalyst for oxidation reaction.

[0009] In the course of research into the above-described hydrogen chloride oxidation reaction, the present inventors have found that when hydrogen chloride is oxidized in a mixed gas containing carbon oxides, the oxidation activity of hydrogen chloride is improved compared to when the oxidation reaction is carried out in the presence of oxygen alone, and that this has the potential to produce chlorine in a high yield, leading to the completion of the present invention. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Korean Patent Publication No. 10-2012-0040701 [Patent Document 2] Korean Patent Publication No. 10-2011-0107350 [Patent Document 3] Korean Patent Publication No. 10-2013-0100282 [Non-patent literature]

[0011] [Non-Patent Document 1] A CeO2 / ZrO2-TiO2 Catalyst for the Selective Catalytic Reduction of NOx with NH3(Catalysts,pp.592.2018.08.) Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been devised to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a method for producing chlorine in a high yield by carrying out an oxidation reaction of hydrogen chloride with a mixed gas containing carbon oxides.

[0013] Another object of the present invention is to provide a method for producing a shaped catalyst for the hydrogen chloride oxidation reaction step. [Means for solving the problem]

[0014] As a technical means for achieving the above technical object, one aspect of the present invention is to The present invention provides a method for producing chlorine by oxidation of hydrogen chloride, the method comprising: filling a reactor with a formed catalyst for a hydrogen chloride oxidation reaction process; and introducing hydrogen chloride and a mixed gas into the reactor to react with each other, wherein the mixed gas contains oxygen and carbon oxides.

[0015] The content of the mixed gas relative to 100 parts by weight of the hydrogen chloride may be 50 parts by weight to 150 parts by weight.

[0016] The content of the carbon oxides may be 0.1 to 10 parts by weight relative to 100 parts by weight of the total mixed gas.

[0017] The carbon oxides may include at least one selected from carbon monoxide (CO) and carbon dioxide (CO2).

[0018] The weight ratio of carbon monoxide (CO) and carbon dioxide (CO2) may be 1:1 to 1:20.

[0019] The shaped catalyst for the hydrogen chloride oxidation reaction step may comprise a support; and ruthenium oxide supported on the support.

[0020] The support may comprise a support selected from the group consisting of alumina, titania, zirconia, and combinations thereof.

[0021] The shaped catalyst further includes a metal oxide supported on the support, and the metal oxide may include a metal oxide represented by the following Chemical Formula 1:

[0022] [Chemical formula 1] MO2

[0023] In the above formula 1, M is Ti, Ce, or Zr.

[0024] The content of the ruthenium oxide may be 1 to 10 parts by weight, and the content of the metal oxide may be 0.5 to 10 parts by weight, relative to 100 parts by weight of the support.

[0025] The shaped catalyst may be in a form selected from the group consisting of powder, particles, pellets, and combinations thereof.

[0026] When the shaped catalyst is in the form of pellets, the diameter of the pellets may be 1 mm to 10 mm.

[0027] The chlorine yield of the chlorine production method may be a space-time yield (STY) calculated by the following Equation 1 of 1.35 or more.

[0028]

number

[0029] In the above mathematical formula 1, the reaction time is 50 hours (hr).

[0030] The formed catalyst may have a space-time yield (STY) calculated by Equation 1 above of 1.45 or more.

[0031] The flow rate of the hydrogen chloride and mixed gas may be 50 mL / min to 200 mL / min.

[0032] The reaction of the hydrogen chloride and the mixed gas may be carried out at a temperature of 280°C to 380°C.

[0033] Another aspect of the present invention is The method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step includes the steps of supporting a metal oxide on a support; and supporting a ruthenium precursor on the support on which the metal oxide is supported.

[0034] The method for preparing the shaped catalyst for the hydrogen chloride oxidation reaction step may further include the steps of supporting the ruthenium precursor; and then drying and calcining the support.

[0035] The drying may be carried out at a temperature of 50° C. to 150° C. for 3 hours, and the firing may be carried out at a temperature of 300° C. to 700° C. for 2 hours to 6 hours. [Effects of the Invention]

[0036] In the method for producing chlorine by oxidation of hydrogen chloride according to the present invention, the oxidation reaction of hydrogen chloride is carried out in a mixed gas containing carbon oxides, and thus the oxidation reaction activity of hydrogen chloride is improved compared to when the oxidation reaction is carried out in oxygen alone, making it possible to produce chlorine in a high yield.

[0037] In addition, the catalyst used in the oxidation reaction overcomes the sintering phenomenon of ruthenium oxide that occurs in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, and can maintain its initial catalytic activity even during long-term catalyst operation.

[0038] Furthermore, the catalyst can be provided as a pellet-shaped catalyst in the commercial production process of chlorine by oxidation of hydrogen chloride, and can provide high mechanical strength so that they do not break during the process.

[0039] Finally, the catalyst provides high catalytic activity and durability, is not affected by the reactor configuration, operating conditions, etc., has no restrictions on use, and is easy to handle. DETAILED DESCRIPTION OF THE INVENTION

[0040] The present invention will be described in more detail below. However, the present invention can be embodied in various different forms, and the present invention is not limited to the examples described herein, but is defined only by the claims that follow.

[0041] In addition, the terms used in the present invention are merely used to describe specific embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. Throughout the specification of the present invention, the term "comprise" a certain component does not mean to exclude other components, but means that other components may be further included, unless otherwise specified.

[0042] A first aspect of the present application is The method includes the steps of: filling a reactor with a formed catalyst for a hydrogen chloride oxidation reaction process; and introducing hydrogen chloride and a mixed gas into the reactor to react with each other; The mixed gas contains oxygen and carbon oxides. The present invention provides a method for producing chlorine by an oxidation reaction of hydrogen chloride.

[0043] Before describing the present invention in detail, it should be noted that carbon oxides are generally catalyst poisons and may be one of the impurities present in the feed during the hydrogen chloride oxidation reaction. That is, when a typical catalyst is used in the hydrogen chloride oxidation reaction, carbon oxides may act as an element that inhibits the oxidation reaction. However, when the formed catalyst for the hydrogen chloride oxidation reaction process according to the present invention is used, carbon oxides, which may act as impurities in the hydrogen chloride oxidation reaction, can instead act as an additive that increases the chlorine yield.

[0044] Hereinafter, the method for producing chlorine by oxidation of hydrogen chloride according to the first aspect of the present application will be described in detail step by step.

[0045] First, in one embodiment of the present application, the method for producing chlorine by oxidation of hydrogen chloride may include the step of filling a reactor with a formed catalyst for the hydrogen chloride oxidation reaction step.

[0046] In one embodiment of the present application, the shaped catalyst for the hydrogen chloride oxidation reaction step may include a support and ruthenium oxide supported on the support, wherein the support may include a support selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and preferably includes titania.

[0047] In one embodiment of the present application, the titania support may be, for example, anatase titania, rutile titania, amorphous titania, or a mixture thereof. The titania support may also contain oxides such as alumina, zirconia, or niobium oxide. Rutile titania is preferred, for example, titania from Sakai Co., Ltd., but is not limited thereto. Meanwhile, the specific surface area of the titania support can be measured by the commonly used BET method, and the specific surface area is 5 to 300 m. 2 / g, preferably 5 to 50m 2 If the specific surface area exceeds the above range, it becomes difficult to ensure the thermal stability of the ruthenium oxide, and if it is below the above range, problems such as a decrease in dispersion stability and a decrease in catalytic activity may occur.

[0048] The aluminum support is preferably alpha-alumina. Alpha-alumina is preferred because it has a low BET specific surface area and is therefore less likely to absorb other impurities. Meanwhile, the specific surface area of the aluminum support is 10 to 500 m 2 / g, preferably 20 to 350 m 2 / g is provided.

[0049] Furthermore, the zirconia support has pores in the range of 0.05 to 10 μm, and the specific surface area is the same as above.

[0050] In one embodiment of the present application, the shaped catalyst further includes a metal oxide supported on the support, and the metal oxide may include a metal oxide represented by the following Chemical Formula 1:

[0051] [Chemical formula 1] MO2

[0052] In Formula 1, M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO), ceria (CeO), zirconia (ZrO), or a combination thereof.

[0053] In one embodiment of the present application, the metal oxide may preferably be ceria and zirconia, and the weight ratio of the ceria and zirconia may be 1:0.5 to 1:1, preferably 1:1. When the weight ratio of the ceria and zirconia satisfies the above range, a formed catalyst for a hydrogen chloride oxidation reaction process containing the same may have excellent mechanical strength and catalytic durability, and may be suitable for long-term catalytic operation.

[0054] In one embodiment of the present application, the metal oxide may be provided in the form of its precursor. For example, in the case of a cerium precursor, it may exist in the form of a complex salt, and may include a cerium compound, particularly a metal salt such as cerium nitrate, cerium acetate, or cerium chloride. Preferably, it may include cerium nitrate, and may be impregnated in the precursor form onto a support, and then provided as a final formed catalyst after being subjected to drying and calcination steps.

[0055] In one embodiment of the present application, the content of the ruthenium oxide may be 1 to 10 parts by weight, and the content of the metal oxide may be 0.5 to 10 parts by weight, relative to 100 parts by weight of the support.

[0056] In one embodiment of the present application, the shaped catalyst may be in a form selected from the group consisting of powder, particles, pellets, and combinations thereof, and preferably in a pellet form. In this case, when the shaped catalyst is in a pellet form, the diameter of the pellet may be 1 mm to 10 mm.

[0057] Next, in one embodiment of the present application, the method for producing chlorine by oxidation of hydrogen chloride may include the step of introducing hydrogen chloride and a mixed gas into the reactor and reacting them.

[0058] In one embodiment of the present application, the carbon oxide may include at least one selected from carbon monoxide (CO) and carbon dioxide (CO2). Preferably, the carbon oxide may be carbon monoxide (CO) alone, and when carbon monoxide (CO) and carbon dioxide (CO2) are used together, the weight ratio thereof may be 1:1 to 1:20. Meanwhile, according to one embodiment of the present invention, the weight ratio of carbon monoxide (CO) to carbon dioxide (CO2) may be about 1:6 to 1:7.

[0059] In one embodiment of the present application, the content of the mixed gas relative to 100 parts by weight of hydrogen chloride may be 50 parts by weight to 150 parts by weight, and according to one embodiment of the present invention, it may be approximately 100 parts by weight. The mixed gas may also contain oxygen and carbon oxides, and the content of the carbon oxides relative to 100 parts by weight of the total mixed gas may be 0.1 parts by weight to 10 parts by weight, preferably 0.1 parts by weight to 5 parts by weight, and according to one embodiment of the present invention, it may be 1 part by weight to 4 parts by weight. If the content of the carbon oxides relative to 100 parts by weight of the total mixed gas is less than 0.1 parts by weight, it may be impossible to produce chlorine at a high yield, which is unique to the present invention, by adding carbon oxides. If the content of the carbon oxides is more than 10 parts by weight, the carbon oxides may act as impurities and reduce catalytic performance.

[0060] In one embodiment of the present application, the reaction for producing chlorine may be carried out in a fixed phase, a fluidized phase, or a gas phase, preferably a gas phase. The hydrogen chloride oxidation reaction is an equilibrium reaction, and if carried out at too high a temperature, the equilibrium conversion rate decreases, so it is preferably carried out at a relatively low temperature. In this case, the reaction temperature is typically 100°C to 500°C, preferably 280°C to 380°C. The reaction pressure may typically be about 0.1 MPa to 5 MPa.

[0061] The supply rate of hydrogen chloride can be expressed as the gas supply rate per liter of catalyst (L / h; 0°C, 1 atmosphere equivalent), i.e., GHSV, and is usually 10 to 20,000 h -1 However, the amount of catalyst to be added may vary depending mainly on the temperature, the amount of catalyst, and the amount of chlorine product to be produced. Preferably, the flow rates of the hydrogen chloride and mixed gas are 50 mL / min to 200 mL / min, and in one embodiment of the present invention, may be about 100 mL / min.

[0062] In one embodiment of the present application, the chlorine yield by the chlorine production method may be such that the space-time yield (STY) calculated by the following mathematical formula 1 is 1.35 or more, preferably 1.45 or more.

[0063]

number

[0064] In Equation 1, the reaction time may be 50 hours (hr). That is, the method for producing chlorine has a high space-time yield (STY) because the reaction is carried out in a mixed gas containing carbon oxides, and therefore, it can be confirmed that the produced chlorine can be obtained in high yield.

[0065] A second aspect of the present application is According to the first aspect of the present application, there is provided a method for producing a shaped catalyst for a hydrogen chloride oxidation reaction process, the method comprising the steps of: supporting a metal oxide on a support; and supporting a ruthenium precursor on the support on which the metal oxide is supported.

[0066] Detailed descriptions of parts that overlap with the first aspect of the present application have been omitted, but the contents described in the first aspect of the present application may be applied equally even if the description thereof is omitted in the second aspect.

[0067] Hereinafter, the method for preparing the shaped catalyst for the hydrogen chloride oxidation reaction process according to the second aspect of the present invention will be described in detail step by step.

[0068] First, in one embodiment of the present application, the method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step may include a step of shaping the support before supporting the metal oxide.

[0069] In one embodiment of the present application, the support may include a support selected from the group consisting of alumina, titania, zirconia, and combinations thereof, and preferably includes titania.

[0070] In one embodiment of the present application, the support may be formed by mixing the support with an organic binder, an inorganic binder, and water and then forming the support. The support formed in this manner is applicable to fixed-bed reactors and is easy to handle and can be used without restrictions, regardless of the reactor shape or operating conditions. In particular, when applied to fixed-bed reactors, the support can be used without seizure, and can provide improved catalytic activity, enhanced thermal stability, and improved durability and mechanical strength.

[0071] In one embodiment of the present application, the organic binder may include a substance selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, refined starch, dextrin, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyethylene glycol, paraffin, wax emulsion, microcrystalline wax, and combinations thereof, and the inclusion of the organic binder can improve the moldability of the carrier.

[0072] In one embodiment of the present application, the inorganic binder may include a material selected from the group consisting of alumina sol, silica sol, titania sol, zirconia sol, and combinations thereof, and the inclusion of the inorganic binder can improve the mechanical properties of the carrier.

[0073] Next, in one embodiment of the present application, the method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step may include a step of supporting a metal oxide on a support.

[0074] In one embodiment of the present application, the metal oxide may include a metal oxide represented by the following Chemical Formula 1:

[0075] [Chemical formula 1] MO2

[0076] In the above Chemical Formula 1, M may be Ti, Ce, or Zr. That is, the metal oxide may be titania (TiO), ceria (CeO), zirconia (ZrO), or a combination thereof.

[0077] In one embodiment of the present application, the metal oxide may be provided in the form of its precursor. For example, in the case of a cerium precursor, it may exist in the form of a complex salt, and may include a cerium compound, particularly a metal salt such as cerium nitrate, cerium acetate, or cerium chloride. Preferably, it may include cerium nitrate, and may be impregnated into a support in the form of a precursor, and then provided as a final formed catalyst after undergoing drying and calcination steps.

[0078] Next, in one embodiment of the present application, the method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step may include the step of supporting a ruthenium precursor on the support on which the metal oxide is supported.

[0079] In one embodiment of the present application, the ruthenium precursor is preferably provided as a halide, most preferably ruthenium chloride, including chloride, and may optionally be provided as a hydrate of the ruthenium precursor.

[0080] In one embodiment of the present application, the ruthenium precursor may be mixed in a powder form into a solvent, and a solid support may be suspended in the solvent to form a precipitate, which is then deposited on the solid support for loading. The temperature during the deposition is 0°C to 100°C, preferably 0°C to 50°C, and the pressure is typically 0.1 MPa to 1 MPa, preferably atmospheric pressure. The deposition may be carried out in an air atmosphere or an inert gas atmosphere such as nitrogen, helium, argon, or carbon dioxide, which may contain water vapor. Preferably, the deposition is carried out in an inert gas atmosphere.

[0081] 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. The water may be high-purity water, such as distilled water, ion-exchanged water, or ultrapure water (DIW). If the water contains impurities, the impurities may adhere to the catalyst, reducing the activity of the resulting catalyst. In the case of alcohol, the organic solvent may be a monoalcohol or a primary alcohol having a C3 or higher alcohol content. C3 alcohol-based organic solvents are preferred, with 1-propanol being most preferred. The solvent may utilize its high wettability and hydrophobicity to support the ruthenium component only on the outer surface of the titania support where hydroxyl groups (—OH) are present, and may also improve the dispersion of ruthenium supported on the surface of the titania molded support or powder support. The content of the solvent is not particularly limited, but if it is too high, drying time may increase, so it can be freely adjusted by those skilled in the art.

[0082] Next, in one embodiment of the present application, the method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step may further include the steps of shaping the support; supporting the metal oxide; and / or supporting a ruthenium precursor on the support; and then drying and calcining the support, respectively.

[0083] In one embodiment of the present application, the carrier may be completed as a final formed carrier by drying and calcining, where the drying and calcining may be performed alternatively as needed, and the order and number of times may be freely adjusted.

[0084] In one embodiment of the present application, the drying may be carried out at a temperature of 50°C to 150°C for 3 to 5 hours. The drying may be carried out by rotation and stirring, specifically by vibrating the drying container or by using a stirrer installed in the container. Meanwhile, the drying temperature may be typically room temperature to about 100°C, and the pressure is typically 0.1 to 1 MPa, preferably atmospheric pressure.

[0085] In one embodiment of the present application, the calcination is carried out at a temperature of 300°C to 700°C for 2 to 6 hours, followed by cooling to room temperature. The oxidizing gas used in the calcination may be, for example, a gas containing oxygen. The oxygen concentration may be a commonly used range of 1 to 30% by volume. Air or pure oxygen is typically used as the oxygen source, and an inert gas or water vapor may be further included as needed. Air is preferably used as the oxidizing gas, and the calcination may be carried out in an electric furnace under air flow at a temperature of about 350°C for 3 hours, followed by cooling to room temperature.

[0086] Although the present invention may be embodied in various different forms, it is to be understood that the invention is not limited to the embodiments set forth herein, and that the invention may be embodied in various different forms, and the invention may be embodied in various different forms, without departing from the spirit or scope of the present invention.

[0087] Manufacturing example: Manufacturing of molded catalyst for hydrogen chloride oxidation reaction process 20g of titania powder (SAKAI), 0.4g of cellulose-based organic binder (YUKEN), 2.5g of TiO2 sol (SAKAI), and 9.0g of DIW were uniformly mixed to form a paste, which was then extruded into a molded carrier and dried in an oven at 100°C for 4 hours. The dried molded carrier was cut into 2mm to 3mm intervals and fired in an electric furnace at 600°C for 3 hours to complete the TiO2 molded carrier.

[0088] Next, the TiO2 molded support was impregnated with a precursor solution prepared by co-dissolving 1.3 g of cerium nitrate hydrate (Kanto Co.) and 1.3 g of zirconium chloride hydrate (Kanto Co.) in 6.0 g of DIW, and then 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 with a ceria content of 2.5% and a zirconia content of 2.5%.

[0089] Next, 20 g of the obtained molded support was impregnated with a precursor solution prepared by dissolving 0.8 g of ruthenium chloride hydrate (KOJIMA) in 6.0 g of DIW, and then dried in an oven at 100° C. for 4 hours.

[0090] Finally, the dried shaped support was calcined in an electric furnace at 350° C. for 3 hours to obtain a shaped catalyst having a ruthenium oxide content of 2.6%, a ceria content of 2.5%, and a zirconia content of 2.5%.

[0091] Example 1. Production of chlorine by hydrogen chloride oxidation reaction (1 wt% CO / 99 wt% O2) 1.35 g of the molded catalyst obtained in the above Preparation Example was packed into a nickel reaction tube (1-inch outer diameter tube). The catalyst layer was heated to 300°C, and 50 wt% hydrogen chloride and 50 wt% mixed gas (1 wt% CO / 99 wt% O) were supplied at a rate of 100 mL / min under atmospheric pressure to produce chlorine for 50 hours.

[0092] Example 2. Chlorine production by hydrogen chloride oxidation reaction (2 wt% CO / 98 wt% O2) Chlorine was produced using the same method as in Example 1, except that the mixed gas was 2 wt% CO / 98 wt% O2.

[0093] Example 3. Production of chlorine by hydrogen chloride oxidation reaction (0.4wt%CO / 2.6wt%CO2 / 97wt%O2)

[0094] Chlorine was produced using the same method as in Example 1, except that the mixed gas was 0.4 wt% CO / 2.6 wt% CO2 / 97 wt% O2.

[0095] Comparative example: Chlorine production by hydrogen chloride oxidation reaction (100 wt% O2) Chlorine was produced using the same method as in Example 1, except that the mixed gas was 100 wt% O2.

[0096] Experimental example: Chlorine yield measurement To measure the yield of chlorine produced in the examples and comparative examples, 50 hours after the start of the reaction, sampling was performed for 10 minutes by passing the gas from the outlet of the reaction tube through a 15% potassium iodide aqueous solution. The amount of chlorine produced was then measured using the iodine titration method, and the yield of hydrogen chloride was calculated using the following mathematical formula 1. The results are shown in Table 1 below.

[0097]

number

[0098] [Table 1]

[0099] As shown in Table 1, it was confirmed that when carbon oxides were used as a mixed gas according to the embodiment of the present invention, the chlorine yield was higher than that of the comparative example in which oxygen alone was used.

[0100] Therefore, it was confirmed that when CO and / or CO2 is used as an additive to the mixed gas according to the present invention, an improved chlorine yield is observed at the same reaction temperature and space velocity.

[0101] Although the present invention has been described in detail above with reference to the drawings and preferred embodiments, the scope of the technical concept of the present invention is not limited to these drawings and embodiments. Therefore, various modifications or equivalent embodiments may exist within the scope of the technical concept of the present invention. Therefore, the scope of the technical concept of the present invention should be interpreted by the claims, and any technical concept equivalent to or within the scope of the claims should be interpreted as belonging to the scope of the present invention. [Industrial Applicability]

[0102] In the method for producing chlorine by oxidation of hydrogen chloride according to the present invention, the oxidation reaction of hydrogen chloride is carried out in a mixed gas containing carbon oxides, and thereby the oxidation reaction activity of hydrogen chloride is improved compared to when the oxidation reaction is carried out in oxygen alone, and chlorine can be produced in a high yield.

[0103] In addition, the catalyst used in the oxidation reaction overcomes the sintering phenomenon of ruthenium oxide that occurs in the commercial production process of chlorine through the oxidation reaction of hydrogen chloride, and can maintain its initial catalytic activity even during long-term catalyst operation.

[0104] Furthermore, the catalyst is provided in the form of pellets in the commercial production process of chlorine by oxidation of hydrogen chloride, and can provide high mechanical strength so that they do not break during the process.

[0105] Finally, the catalyst provides high catalytic activity and durability, is not affected by the reactor configuration, operating conditions, etc., has no restrictions on use, and is easy to handle.

Claims

1. Packing the shaped catalyst for the hydrogen chloride oxidation reaction step into a reactor; and introducing hydrogen chloride and a mixed gas into the reactor and reacting them; Including, the mixed gas contains oxygen and carbon oxides; the content of the carbon oxides is 1 part by weight to 4 parts by weight per 100 parts by weight of the total mixed gas; The carbon oxides include at least one selected from carbon monoxide (CO) and carbon dioxide (CO 2 ); The shaped catalyst for the hydrogen chloride oxidation reaction step is a carrier; and The carrier contains ruthenium oxide, The shaped catalyst further comprises a metal oxide supported on the support, The metal oxide includes a metal oxide represented by the following chemical formula 1: [Chemical formula 1] MO ２ In Formula 1, M is Ce or Zr.

2. 2. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 1, wherein the content of the mixed gas relative to 100 parts by weight of the hydrogen chloride is 50 parts by weight to 150 parts by weight.

3. The carbon monoxide (CO) and carbon dioxide (CO ２ 2. The method for producing chlorine by oxidation of hydrogen chloride according to claim 1, wherein the weight ratio of

4. 2. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 1, wherein the support comprises a support selected from the group consisting of alumina, titania, and combinations thereof.

5. For 100 parts by weight of the carrier, the content of the ruthenium oxide is 1 part by weight to 10 parts by weight, 2. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 1, wherein the content of the metal oxide is 0.5 to 10 parts by weight.

6. 2. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 1, wherein the shaped catalyst is in a form selected from the group consisting of powder, particles, pellets, and combinations thereof.

7. 7. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 6, wherein when the shaped catalyst is in the form of pellets, the pellets have a diameter of 1 mm to 10 mm.

8. 2. The method for producing chlorine by oxidation reaction of hydrogen chloride according to claim 1, wherein the reaction of hydrogen chloride and the mixed gas is carried out at a temperature of 280°C to 380°C.

9. A method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step according to claim 1, comprising the steps of: Supporting the metal oxide on a support; and a step of supporting a ruthenium precursor on the metal oxide-supported support; A method for producing a shaped catalyst for a hydrogen chloride oxidation reaction step, comprising:

10. The method for producing the shaped catalyst for the hydrogen chloride oxidation reaction step includes: supporting the ruthenium precursor; then 10. The method for preparing a shaped catalyst for the hydrogen chloride oxidation reaction step according to claim 9, further comprising the steps of drying and calcining the support.

11. The drying is carried out at a temperature of 50°C to 150°C for 3 hours; The method for producing a shaped catalyst for use in a hydrogen chloride oxidation reaction step according to claim 10, wherein the calcination is carried out at a temperature of 300°C to 700°C for 2 hours to 6 hours.

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