JP5563937B2 - Chlorine production method - Google Patents

Description

  In the fixed bed reactor, when chlorine is produced by oxidizing hydrogen chloride with oxygen, the reduction in chlorine productivity due to carbon monoxide contained in the raw material gas is suppressed for a long time. The present invention relates to a method capable of producing chlorine efficiently, economically and stably with high productivity.

It is well known that chlorine is useful as a raw material for vinyl chloride, phosgene and the like, and can be produced industrially by electrolysis of sodium chloride or catalytic oxidation of hydrogen chloride.
However, the salt electrolysis method is disadvantageous in terms of energy because it uses a large amount of electric power, and since it produces caustic soda as a by-product, the supply-demand balance between chlorine and caustic soda always becomes a problem.

  On the other hand, production by catalytic oxidation of hydrogen chloride has been devised as one of the methods for recovering hydrogen chloride by-produced when producing vinyl chloride monomers and isocyanates. Since hydrogen chloride produced as a by-product is used as a raw material, it can be said that this is a very effective process from the viewpoint of environmental impact. In addition, as a catalyst, for example, a copper catalyst conventionally called a Deacon catalyst is said to have excellent activity, and a catalyst in which various compounds are added as a third component to copper chloride and potassium chloride, and chromium oxide is used. A catalyst containing the catalyst or a catalyst containing ruthenium oxide has been proposed.

  However, the hydrogen chloride gas used as a raw material usually contains carbon monoxide at a high concentration. For this reason, the volatilization amount of the catalyst component increases due to the high concentration of carbon monoxide, and the generation of carbon dioxide due to the oxidation of carbon monoxide is accompanied by a significant exotherm. Causes possible local temperature rise (hot spot), resulting in decreased or deactivated catalyst activity, and carbon monoxide adsorption due to adsorption of carbon monoxide on the catalyst surface, suppressing the chlorine generation reaction Is a problem. These phenomena are particularly noticeable in the fixed bed process, and an expensive carbon monoxide separation step may be required. (Patent Documents 1 and 2).

  The fixed bed process has a high reaction yield because it has little axial fluid mixing and can approximate an extruded flow. Moreover, it is easy to change the contact time between the reaction fluid and the catalyst, and it can be applied from a fast reaction to a slow reaction. Therefore, it is used in a wide range of fields and can be said to be the most preferable process industrially.

  However, when chlorine is produced in a fixed bed reactor, the influence of the hot spots described above becomes very large. Therefore, unless hydrogen chloride and carbon monoxide are separated, chlorine is produced stably industrially. It is difficult to do.

  Therefore, when chlorine is produced by catalytic oxidation of hydrogen chloride using a fixed bed reactor, the chlorine is increased efficiently, economically and stably over the long term without being affected by carbon monoxide. A method that can be manufactured with productivity has been desired.

  Patent Document 3 discloses a production model that is a method for producing chlorine using a fixed bed reactor and assumes that the raw material gas contains carbon monoxide as an impurity. However, since Patent Document 3 is an ideal model based on computational chemistry to the last, it cannot be immediately applied to the actual production of chlorine, and there is room for further study and improvement in order to obtain an industrially suitable production method. is there.

JP-A-62-270404 Special table 2009-537450 gazette JP 2010-189206 A

  The present invention uses a fixed bed reactor to oxidize hydrogen chloride with oxygen to produce chlorine. Even if a raw material gas containing carbon monoxide is used, the productivity of chlorine can be reduced efficiently. An object of the present invention is to provide a method for producing chlorine that is economical and stable and that can maintain high productivity over a long period of time.

  The method for producing chlorine of the present invention uses a fixed bed reactor having a reaction zone composed of a catalyst packed bed, and converts hydrogen chloride in a raw material gas containing hydrogen chloride, oxygen and carbon monoxide under a catalyst for producing chlorine. The method of producing chlorine by oxidizing with oxygen, wherein carbon monoxide contained in the raw material gas is 0.1 vol% or more and 8 vol% or less with respect to 100 vol% of the raw material gas, The catalyst for use is a catalyst in which an active component containing a copper element, an alkali metal element and a lanthanoid metal element satisfying a bond dissociation energy with oxygen at 298 K of 100 to 185 kcal / mol is supported on a porous carrier. To do.

The gas superficial velocity in the reaction zone is preferably 0.002 m / s or more and 10.0 m / s or less in a standard state (0 ° C., 0.1 MPa).
It is preferable that the copper element is 1.5 wt% or more and 15 wt% or less per 100 wt% of the catalyst for chlorine production.

The reaction temperature in the reaction zone is preferably 300 ° C. or higher and 420 ° C. or lower.
The gas space velocity of hydrogen chloride in the reaction zone is preferably 250 h ⁻¹ or more and 2000 h ⁻¹ or less in a standard state (0 ° C., 0.1 MPa).

  It is preferable that the porous carrier is a porous carrier made of silica.

  According to the present invention, in a reaction in which hydrogen chloride is oxidized with oxygen using a fixed bed reactor to generate chlorine, carbon monoxide, which causes a reduction in chlorine productivity, is contained in the raw material gas. Even so, chlorine can be produced efficiently, economically and stably over a long period of time with high productivity. Moreover, since the amount of catalyst to be used can be reduced by using the catalyst for chlorine production suitable for the manufacturing method of the present invention, it is possible to minimize the burden on the environment.

FIG. 1 shows a schematic diagram of Hastelloy reaction tubes used in the catalytic reaction test method in Examples and Comparative Examples.

  The method for producing chlorine according to the present invention uses a fixed bed reactor having a reaction zone composed of a catalyst packed bed to convert hydrogen chloride contained in a raw material gas into oxygen contained in the raw material gas under a chlorine production catalyst. This is a method for producing chlorine by oxidation with the use of carbon monoxide in the raw material gas. Carbon monoxide contained in the raw material gas is 0.1 vol% or more and 8 vol% or less with respect to 100 vol% of the raw material gas, and the catalyst for producing chlorine includes copper element, alkali metal element and oxygen at 298K. An active component containing a lanthanoid metal element satisfying a bond dissociation energy of 100 to 185 kcal / mol is a catalyst supported on a porous carrier.

  The chlorine production method of the present invention is carried out by forming a reaction zone by filling a catalyst for chlorine production in a fixed bed reactor. The fixed bed reactor is not particularly limited. For example, see page 189 of Chemical Engineering Handbook (6th revised edition, date of publication: February 25, 1999, editor: Society of Chemical Engineering, publisher: Maruzen Co., Ltd.). Although the known fixed bed reactors described can be used arbitrarily, a multitubular heat exchanger type is preferred because the oxidation reaction of hydrogen chloride is an exothermic reaction.

  Moreover, in this invention, you may have the reaction zone which consists of two or more catalyst packed layers in a fixed bed reaction tube. As a method of forming a reaction zone composed of two or more catalyst packed beds, the catalyst packed bed in the reaction tube is divided into two or more reaction zones in the tube axis direction, and the same or active component composition or catalyst is divided. Examples include a method of filling a catalyst having a different shape and the like, a method of filling a mixed catalyst obtained by diluting the catalyst with an inert substance such as a carrier only, and changing the dilution rate. Can be used in combination.

  Usually, continuous reaction zones are in direct contact with each other, but a layer composed of only an inert substance or a carrier may be provided between the reaction zones. However, a packed bed consisting only of a packing formed only with an inert substance or a carrier is not regarded as a catalyst packed bed.

  In the chlorine production method of the present invention, the temperature control of the reaction zone comprising the catalyst packed bed may be controlled by two or more independent temperature control methods. As a method of performing temperature control by two or more independent temperature controls, for example, a catalyst packed bed composed of at least two or more different catalysts in the tube axis direction is installed in the reaction tube, and the reaction is divided into reaction zones. A method of controlling the temperature of the catalyst packed bed by controlling the amount of heat generated, a method of installing independent heat exchangers in each of the reaction zones divided into at least two, and performing temperature control independently of each other, Examples include a method in which at least two fixed bed reactors are connected in series and temperature control is independently performed, and these methods can be used alone or in combination. By these methods, it is possible to easily control the temperature of the reaction zone composed of the catalyst packed bed.

  In the present invention, the inner diameter of the fixed bed reaction tube is usually 10 to 80 mm, preferably 10 to 60 mm, and more preferably 10 to 50 mm. If the inner diameter of the reaction tube is less than 10 mm, an excessive number of reaction tubes are required to secure a certain amount of chlorine production, which is not preferable because the production efficiency is poor and the construction cost of the apparatus increases. . On the other hand, if the inner diameter of the reaction tube is larger than 80 mm, it is difficult to control the temperature of the reaction zone composed of the catalyst packed layer, and an excessive hot spot may be generated, which is not preferable.

  The hydrogen chloride used in the present invention is not particularly limited, and a gas containing hydrogen chloride that is normally supplied in a gaseous form from a hydrogen chloride generation source is supplied to the reactor as it is. When hydrogen chloride is obtained industrially, since hydrogen chloride is obtained as a by-product such as a substitution reaction or condensation reaction of an organic compound, it is not necessarily highly pure, and impurities such as organic compounds such as benzene and chlorobenzene, nitrogen Inorganic gas such as argon, carbon monoxide, carbon dioxide and hydrogen may be contained. Of these, organic compounds are chlorinated to become high-boiling compounds, which can cause plant troubles such as gas line blockage and are usually removed before the reaction. Also in the present invention, it is preferable to remove organic compounds in hydrogen chloride as much as possible. A method for removing the organic compound is not particularly limited, but a method for removing the organic compound by contacting with an adsorbent such as activated carbon, or a method for condensing and removing the organic compound by pressurizing and cooling a gas containing the organic compound. Etc. Moreover, you may use these methods together.

  Moreover, when manufacturing chlorine industrially, it is common to recycle the gas which isolate | separated the product chlorine from the reaction gas to a fixed bed reactor again. This recycle gas contains hydrogen chloride, oxygen, chlorine, carbon monoxide, carbon dioxide, nitrogen, etc., depending on the method for separating chlorine.

  Therefore, the source gas according to the present invention contains organic compounds such as benzene and chlorobenzene, nitrogen, argon, carbon monoxide, carbon dioxide, hydrogen, chlorine, etc., in addition to hydrogen chloride and oxygen which are chlorine raw materials. There is.

  Inorganic gas other than carbon monoxide contained in the raw material gas can be mixed into the reactor as it is, but there is no problem, but as the concentration of the inorganic gas increases, the concentration of hydrogen chloride and oxygen decreases relatively. As a result, the productivity of chlorine may decrease, which is not preferable. In the present invention, the total concentration of inorganic gases other than carbon monoxide is 50 vol% or less, preferably 40 vol% or less, more preferably 30 vol% or less, based on the total amount of gas supplied.

  In the present invention, the concentration of hydrogen chloride contained in the raw material gas during steady operation is not particularly limited, but is usually 20 vol% or more and 80 vol% or less, preferably 30 vol% or more with respect to 100 vol% of the raw material gas. 70 vol% or less, more preferably 40 vol% or more and 60 vol% or less. If it is less than 20 vol%, the concentration of hydrogen chloride as a raw material is low, which may reduce the productivity of chlorine, which is not preferable. On the other hand, if it is larger than 80 vol%, oxygen is insufficient with respect to hydrogen chloride, so the conversion rate of hydrogen chloride to chlorine is lowered, and there is a possibility that chlorine cannot be produced stably, which is not preferable.

  In addition, the raw material gas contains carbon monoxide in an amount of 0.1 vol% or more and 8 vol% or less with respect to 100 vol% of the raw material gas. If the concentration of carbon monoxide exceeds 8 vol%, the concentration of hydrogen chloride decreases, and the productivity of chlorine is significantly reduced. In the production of chlorine, since it is desirable that carbon monoxide is not completely contained in the raw material gas, the lower limit value is ideally 0 vol%. In the present invention, the lower limit of 0.1 vol%, which is estimated to have an adverse effect in the conventional production method, is described as the lower limit. However, even if less than this value, the purpose of the present invention is not impaired. Can be used.

  In the present invention, the concentration of oxygen contained in the raw material gas during steady operation is not particularly limited, but is usually 10 vol% or more and 50 vol% or less, preferably 15 vol% or more, relative to 100 vol% of the raw material gas. It is 45 vol% or less, More preferably, it is 20 vol% or more and 40 vol% or less. If it is less than 10 vol%, the concentration of oxygen as a raw material is low, which may reduce the productivity of chlorine, which is not preferable. On the other hand, if it is higher than 50 vol%, the concentration of hydrogen chloride is lowered, the productivity of chlorine is lowered, and there is a possibility that chlorine cannot be produced stably. The oxygen used in the present invention is oxygen or air. Although air may be used as it is, the oxidation reaction of hydrogen chloride is an equilibrium reaction, and the higher the oxygen partial pressure in the gas, the more the equilibrium acts on chlorine generation, so use oxygen gas with less impurity gas It is preferable to use high-purity oxygen.

  In the chlorine production method of the present invention, the theoretical molar amount of oxygen with respect to 1 mol of hydrogen chloride is 0.25 mol. However, from the viewpoint of improving the productivity of chlorine, it is possible to supply oxygen in excess of the theoretical molar amount. Preferably, the molar ratio of oxygen to hydrogen chloride in the raw material gas is preferably 0.25 or more and 2.0 or less, more preferably 0.30 or more and 1.5 or less, and 0.40 or more and 1.0 or less. Most preferred. If the molar ratio of oxygen to hydrogen chloride is less than 0.25, oxidation of hydrogen chloride may not proceed sufficiently, such being undesirable. If it is larger than 2.0, the concentration of hydrogen chloride contained in the raw material gas is lowered, and as a result, the productivity of chlorine may be deteriorated, which is not preferable.

The amount of hydrogen chloride relative to the amount of catalyst for chlorine production in the present invention, that is, the gas space velocity (GHSV) of hydrogen chloride, the supply rate of hydrogen chloride (L / hr) in the standard state (0 ° C., 0.1 MPa), and the catalyst filling can be expressed by the ratio of the volume (L) of the layer, usually, 250h ^-1 or more, 2000h ^-1 or less, preferably 300h ^-1 or more and 1500h ^-1 or less. If it is less than 250 h ⁻¹ , the amount of catalyst used is excessive with respect to the amount of hydrogen chloride, and the catalyst cost increases, which is not efficient. If it is larger than 2000 h ⁻¹ , the hydrogen chloride oxidation reaction does not proceed sufficiently and the productivity of chlorine may be deteriorated, which is not preferable.

  In the present invention, the gas superficial velocity in the reaction zone composed of the catalyst packed bed is preferably 0.002 m / s or more and less than 10.0 m / s, 0.005 m / s or more, 5.0 m / s. Is more preferably 0.01 m / s or more and less than 3.0 m / s. Note that the gas superficial velocity in the present invention refers to the supply rate in the standard state (0 ° C., 0.1 MPa) of all gases supplied to the catalyst packed bed, that is, the inner sectional area of the fixed bed reaction tube. Means the ratio of Note that the gas superficial velocity generally decreases as the latter half of the reaction zone is reached. In the present invention, the gas superficial velocity at the initial stage of the reaction zone, that is, the gas superficial velocity at the first reaction zone inlet is shown. The first reaction zone means the most upstream reaction zone in the raw material gas flow.

  In the present invention, the maximum temperature of the reaction zone composed of the catalyst layer is preferably 300 ° C. or higher and 420 ° C. or lower, more preferably 320 ° C. or higher and 410 ° C. or lower, from the viewpoint of being able to produce chlorine with high efficiency and high productivity. It is preferably 340 ° C. or higher and 400 ° C. or lower. When the maximum temperature is less than 300 ° C., the hydrogen chloride oxidation reaction does not proceed sufficiently, which is not preferable. On the other hand, if it is higher than 420 ° C., the volatilization rate of copper, which is the main component of the catalyst, increases, which may lead to deterioration of catalytic activity and cause hot spots, which is not preferable.

  In the present invention, the pressure in the fixed bed reactor is not particularly limited, but usually normal pressure to 5 MPaG is preferable. When the reaction is carried out under pressurized conditions, the gas charged into the reactor is pressurized using a known compressor. Examples of the compressor include a turbo type axial flow compressor, a centrifugal compressor, a positive displacement reciprocating compressor, a screw type (screw) compressor, and the like, and are appropriately selected in consideration of the required pressure and air volume. Is done. From the viewpoint of corrosion of the compressor, it is preferable to dry the gas charged into the reactor, particularly hydrogen chloride.

In the method for producing chlorine in the present invention, the production process is not particularly limited, but preferably includes the following steps.
(1) A step of preheating a source gas containing hydrogen chloride, oxygen, and carbon monoxide (2) A step of performing an oxidation reaction of hydrogen chloride (3) Hydrogen chloride, oxygen, chlorine, water, carbon monoxide, carbon dioxide (4) Steps for recovering and removing hydrogen chloride from the product gas (5) Steps for dehydrating the product gas (6) Compressing and cooling the product gas to separate chlorine as liquefied chlorine Process

  In the step of preheating the raw material gas containing hydrogen chloride, oxygen, and carbon monoxide, it is preferably heated to 100 ° C. or more and less than 400 ° C. before the gas is introduced into the fixed bed reactor, 150 ° C. or more, More desirably, the temperature is less than 350 ° C. If the temperature to be heated in advance is less than 100 ° C., hydrogen chloride gas condenses in the system, and there is a possibility that device corrosion proceeds, which is not preferable.

  In the process of cooling the product gas containing hydrogen chloride, oxygen and carbon monoxide and the products chlorine, water and carbon dioxide, chlorine, water and carbon dioxide produced in the fixed bed reactor The product gas containing hydrogen chloride, oxygen and carbon monoxide in the reaction is cooled by a refrigerant. The refrigerant is not particularly limited, but water is preferable.

  The step of recovering / removing hydrogen chloride from the product gas aims at recovering / removing unreacted hydrogen chloride from the product gas containing hydrogen chloride, oxygen, chlorine, water, carbon monoxide, and carbon dioxide. The method for recovering and removing hydrogen chloride is not particularly limited, but a method in which hydrogen chloride is absorbed by the recovery medium is preferable. The recovery medium is not particularly limited, but water is preferable because of easy handling. In addition, the step of cooling the product gas and the step of absorbing hydrogen chloride may be performed using separate apparatuses or may be performed using the same apparatus.

  The step of dehydrating the product gas is intended to remove water from the product gas containing chlorine, oxygen, and water. The dehydration method is not particularly limited, and methods such as a cooling dehydration method, an absorption dehydration method, an adsorption dehydration method, and a compression dehydration method can be suitably used, and a method by an absorption dehydration method is particularly preferable. By using this process, residual moisture contained in the product gas can be removed almost completely.

  In the step of compressing and cooling the product gas and separating chlorine as liquefied chlorine, the product gas from which moisture has been removed in the previous step is compressed and cooled to liquefy the chlorine and separate it from the gas phase. At this time, the gas phase after chlorine is liquefied and separated contains oxygen and unrecovered chlorine. This gas containing oxygen can be used as a raw material gas in the (2) hydrogen chloride oxidation reaction step by reintroducing it into the step of (1) preheating the hydrogen chloride and oxygen-containing raw material gas in advance. it can.

Through these steps, high-purity chlorine can be produced continuously and efficiently.
A catalyst for producing chlorine according to the present invention is a catalyst in which an active component containing a lanthanoid metal element satisfying a bond dissociation energy with oxygen at 298 K of 100 to 185 kcal / mol is supported on a porous carrier. It is. In the present invention, by using such a specific catalyst, chlorine can be produced efficiently, economically and stably over a long period of time even when carbon monoxide is contained in the raw material gas. Can do. Further, since the catalyst has a long life, the amount of catalyst used can be significantly reduced, and the burden on the environment can be minimized.

  In the catalyst, the copper element may be contained in either a monovalent or divalent state. The content of copper element is 1.5% by weight or more and 15.0% by weight or less per 100% by weight of the catalyst, preferably 3.0% by weight or more and 7.5% by weight or less, more preferably 4. 5 wt% or more and 10.0 wt% or less. The higher the copper content is, the higher the activity is. However, when the content is more than 15.0% by weight, it may be difficult to produce the catalyst. This is not preferable, and the copper content is less than 1.5% by weight. It is not preferable because a high chlorine yield may not be obtained.

  Examples of the alkali metal element contained in the catalyst include lithium, sodium, potassium, rubidium, cesium, and francium. These alkali metal elements may be contained alone or in combination of two or more in the catalyst. Among these, sodium and / or potassium are preferable, and potassium is more preferable. The content of the alkali metal element is not particularly limited, but is preferably 1.0% by weight or more and 10.0% by weight or less, more preferably 2.0% by weight or more and 8.0% by weight or less per 100% by weight of the catalyst. Preferably, 3.0% by weight or more and 6.0% by weight or less is more preferable.

  The lanthanoid element contained in the catalyst has a bond dissociation energy with oxygen at 298 K in the range of 100 to 185 kcal / mol among so-called lanthanoid elements having atomic numbers 57 to 71. Here, the bond dissociation energy of lanthanoid and oxygen at 298K is as shown in the following Table 1, and specific examples of lanthanoid elements contained in the catalyst include praseodymium (Pr), neodymium (Nd), and promethium. (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) and lutetium (Lu) One or more lanthanoid elements selected from the group can be mentioned.

なお、上記表１に記載の２９８ＫでのＬｎ−Ｏ（ランタノイド−酸素）結合解離エネルギーＤ₂₉₈の値は、有機金属反応剤ハンドブック（玉尾皓平編著、化学同人、発行年月：２００３年６月）２２３頁表２に記載の値である。

Incidentally, Ln-O at 298K according to Table 1 - the value of (lanthanide oxygen) bond dissociation energy D ₂₉₈ is an organometallic reagent Handbook (Tamao Akirataira eds, Kagaku Dojin, Publication date: June 2003 ) The values described in Table 2 on page 223.

  In the present invention, if the bond dissociation energy of the lanthanoid element exceeds 185 kcal / mol, the bond with oxygen becomes too strong, and if it is less than 100 kcal / mol, the affinity with oxygen becomes too low, so the reaction activity ( (Chlorine yield) may not be sufficiently improved.

  Of these lanthanoid elements, praseodymium, neodymium, samarium, europium, gadolinium, and dysprosium are preferable, and praseodymium, neodymium, samarium, and europium are more preferable. These lanthanoid elements may be used alone or in combination of two or more.

  The content of the lanthanoid element is not particularly limited, but is preferably 1.5% by weight or more and 15.0% by weight or less per 100% by weight of the catalyst for chlorine production, and is 3.0% by weight or more and 12.5% by weight or less. Is more preferably 4.5% by weight or more and 10.0% by weight or less.

  The weight ratio of copper element, alkali metal element, and lanthanoid element in the catalyst is not particularly limited, but the weight ratio of copper element to alkali metal element is in the range of 1: 0.2 to 1: 4.0, And it is preferable that the weight ratio of a copper element and a lanthanoid element is the range of 1: 0.2-1: 6.0. The weight ratio of copper element to alkali metal element is in the range of 1: 0.2 to 1: 2.0, and the weight ratio of copper element to lanthanoid element is 1: 0.2 to 1: 3. More preferably, the weight ratio of copper element to alkali metal element is 1: 0.3 to 1: 1.5, and the weight ratio of copper element to lanthanoid element is 1: 0.3. More preferably, the weight ratio of copper element to alkali metal element is 1: 0.4 to 1: 1.0, and the weight ratio of copper element to lanthanoid element is Most preferably, it is 1: 0.4 to 1: 2.0. The above range is preferable because each element as an active component is easily complexed, a long life is obtained, and the catalyst for producing chlorine is excellent in activity.

  Further, the catalyst may contain one or more of iron element, nickel element, or other rare earth elements such as lanthanum, cerium, ytterbium, scandium, yttrium and the like within a range not impairing the object of the present invention. Good. These elements can be appropriately used as long as the object of the present invention is not impaired, but preferably 0.001% by weight or more and 10% by weight or less per 100% by weight of the catalyst for chlorine production.

  The catalyst has a total content of noble metal elements composed of gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and osmium, and chromium element of 1.0% by weight or less per 100% by weight of the catalyst. Preferably, it is 0.5 wt% or less, and most preferably 0.1 wt% or less. If the content of the noble metal element and chromium element is greater than 1.0% by weight, the oxidation reaction of carbon monoxide contained in the raw material gas may proceed rapidly, making it difficult to control the reaction temperature in the reaction zone. Because it is not desirable.

  The catalyst is not particularly limited, but for example, the average pore diameter is preferably 3 nm or more and 50 nm or less, and more preferably 6 nm or more and 30 nm or less. If the average pore diameter is less than 3 nm, it is difficult to introduce an active ingredient such as copper into the pores, which leads to aggregation on the surface and blockage of the pores. On the other hand, if the average pore diameter is larger than 50 nm, the surface area of the catalyst is decreased, and the reaction efficiency may be decreased, which is not preferable.

The catalyst is not particularly limited, but for example, the specific surface area is preferably 30 m ² / g or more and 1000 m ² / g or less, and preferably 50 m ² / g or more and 500 m ² / g or less. more preferably, 100 m ² / g or more, more preferably 300 meters ² / g or less. In addition, in this invention, the specific surface area was measured using the BET method specific surface area measuring apparatus (BELSORP-max, Nippon Bell Co., Ltd. product).

  The catalyst is not particularly limited, but preferably has a bulk density of 0.20 g / ml or more and 1.00 g / ml or less, and 0.30 g / ml or more and 0.80 g / ml or less. More preferably.

  The catalyst is not particularly limited, but preferably has a pore volume of 0.3 ml / g or more and 3.0 ml / g or less, 0.5 ml / g or more and 2.0 ml / g or less. It is more preferable that it is 0.6 ml / g or more and 1.5 ml / g or less. If it is less than 0.3 ml / g, the space in the pores is insufficient and the diffusion of the substrate becomes insufficient, the specific surface area is lowered, and the reaction efficiency is lowered. On the other hand, if it is larger than 3.0 ml / g, the strength as a catalyst is lowered, and the catalyst itself may be destroyed during the reaction, which is not preferable.

  The shape of the catalyst is preferably a molded body from the viewpoint of controlling the reaction pressure. The shape of the molded body is not particularly limited, and any shape such as a tablet shape, a ring shape, a cylindrical shape, a spherical shape, a granular shape, a lump shape, or a flake shape can be suitably used. The size of the catalyst is not particularly limited as long as it can be charged into the reactor, but the major axis of the catalyst is preferably in the range of 0.5 to 10 mm, particularly preferably 1 to 8 mm. If the size of the catalyst is too small, the pressure loss increases and it is necessary to pressurize. Although depending on the reaction tube size, when the reaction tube diameter is small, if the catalyst size is too large, gas may escape and the reaction rate may decrease. The major axis of the catalyst here means, for example, the diameter of a sphere in the case of a spherical shape, the diameter of the longer cross section in the case of a cylindrical pellet, and the maximum diameter in other shapes.

  Examples of the material for the porous carrier in the catalyst include silica, alumina, titania, zirconia, silica alumina, and the like. Among them, silica is preferable because of its high strength and long life of the catalyst.

  The average value of pore diameter (hereinafter also referred to as average pore diameter) of the porous carrier is preferably 3 nm or more and 50 nm or less, and more preferably 6 nm or more and 30 nm or less. If the average pore diameter is less than 3 nm, it is difficult to introduce active ingredients such as copper into the pores, which may cause aggregation on the surface, blockage of pores, and the like, which is not preferable. On the other hand, when the average pore diameter is larger than 50 nm, the surface area of the carrier is reduced, and the reaction efficiency may be lowered.

The specific surface area of the porous carrier is preferably 30 m ² / g or more and 1000 m ² / g or less, more preferably 50 m ² / g or more and 500 m ² / g or less, 100 m ² / g or more, More preferably, it is 300 m ² / g or less. If the specific surface area is less than 30 m ² / g, the reaction point may be decreased, which is not preferable. If it is larger than 1000 m ² / g, a special method is required for production of the carrier, which is not efficient and is not preferable from the viewpoint of production cost. In addition, in this invention, the specific surface area was measured using the BET method specific surface area measuring apparatus (BELSORP-max, Nippon Bell Co., Ltd. product).

The bulk density of the porous carrier is preferably 0.20 g / ml or more and 1.00 g / ml or less, more preferably 0.30 g / ml or more and 0.80 g / ml or less.
Further, the pore volume of the porous carrier is preferably 0.3 ml / g or more and 3.0 ml / g or less, more preferably 0.5 ml / g or more and 2.0 ml / g or less. More preferably, it is 6 ml / g or more and 1.5 ml / g or less. If it is less than 0.3 ml / g, the space in the pores is not sufficient, and the reaction efficiency may be lowered. On the other hand, when it is larger than 3.0 ml / g, the strength as a support is lowered, and the catalyst itself may be destroyed during the reaction, which is not preferable.

Although the catalyst for chlorine manufacture concerning this invention is not specifically limited, For example, it can manufacture by the following methods.
The catalyst has a structure in which an active component containing a copper element, an alkali metal element and a specific lanthanoid metal element is supported on a porous carrier. The method of supporting an active ingredient includes a step of dispersing a copper compound, an alkali metal compound, and a lanthanoid compound in a porous carrier, and a step of drying or firing the carrier in which the copper compound, the alkali metal compound, and the lanthanoid compound are dispersed. And have. The active element copper element, alkali metal element, and specific lanthanoid element are dispersed in the porous carrier as a copper compound, an alkali metal compound, and a lanthanoid compound, respectively. As the porous carrier, those described above can be preferably used.

  The method for dispersing and supporting the active ingredient on the porous carrier is not particularly limited, and any of the above-described element deposition in a vacuum chamber, vapor phase loading, and liquid phase loading (liquid phase preparation method) can be used. However, in consideration of operability and uniform dispersibility, liquid phase support is desirable. In the case of liquid phase support, a compound containing each active ingredient may be added to a solvent to obtain a raw material solution or a raw material dispersion in which the raw material is dispersed in the solvent, and then sprayed onto the porous carrier, or the porous carrier May be evaporated and dried while stirring the raw material solution or the raw material dispersion as it is, and a porous carrier may be used as the raw material containing the active ingredient. It is also possible to employ a method in which the porous carrier is lifted from the raw material solution or the raw material dispersion and dried after being immersed in the solution or the raw material dispersion.

  In the case where the porous carrier is dispersed and supported in a raw material solution or raw material dispersion containing the active ingredient, if the supported amount is small, the porous carrier is again immersed in the raw material solution or raw material dispersion. The content of the active ingredient can be increased. The active ingredient in the raw material solution or the raw material dispersion liquid may be in a solid state not dissolved in the solvent as long as the active ingredient has a size that can enter the pores of the carrier. In order to disperse in the inside, it is preferable that each active ingredient is dissolved in a solvent, that is, a raw material solution.

  When the raw material solution or the raw material dispersion in which the raw material is dispersed in the solvent is sprayed on the porous carrier, the volume of the raw material dispersion is preferably equal to or less than the pore volume of the porous carrier. When the volume of the raw material dispersion is larger than the pore volume of the porous carrier, the raw material dispersion cannot be completely filled in the pores of the porous carrier and is present on the surface of the porous carrier, which is not preferable.

  The solvent for each active ingredient when supported in the liquid phase is not particularly limited as long as it can dissolve or disperse the compound containing the active ingredient, but water is preferable from the viewpoint of ease of handling. The concentration when the active ingredient is dissolved and dispersed in the solvent is not particularly limited as long as the compound of the active ingredient can be uniformly dissolved or dispersed. However, if the concentration is too low, it takes time to carry the active ingredient and the total amount of the active ingredient and the solvent. The amount of the active ingredient per 100% by weight is preferably 1 to 50% by weight, more preferably 2 to 40% by weight.

  When the catalyst is produced, if a solvent having an amount larger than the pore volume remains in the catalyst after the dispersion, it is necessary to remove the solvent after the dispersion and before filling the reactor. As long as the amount of the solvent is not more than the pore volume, it may be used in the reaction as it is, or the solvent may be removed. When removing the solvent, only drying may be performed, but further baking may be performed. Although it does not specifically limit as drying conditions, Usually, it implements on the conditions of 0-200 degreeC and 10min-24hr in air | atmosphere or under pressure reduction. Moreover, it is although it does not specifically limit as baking conditions, Usually, it can implement on the conditions of 200 to 600 degreeC and 10 min to 24 hr under air | atmosphere.

  The copper compound, alkali metal compound, and specific lanthanoid compound dispersed in the porous carrier may be any compound, salt or complex salt, but independently of each other, halide, nitrate, sulfate, acetate, carbonate An oxalate, an alkoxide, or a complex salt is preferable. Of these, chlorides, nitrates and acetates are preferred from the viewpoint that complex salts are easily formed.

A commercially available porous carrier can be used as it is, but it can also be used after drying or baking at a temperature of 30 to 700 ° C. before supporting the active ingredient.
As a method for producing a molded body of the catalyst, an active component may be supported on a preformed porous carrier, a porous carrier supporting an active component may be molded, or one of the active components may be molded. Alternatively, a method may be used in which the remaining active ingredient is supported after the porous carrier supporting the part is formed. It does not specifically limit as a shaping | molding method, A well-known method can be utilized. For example, a compression molding method, an extrusion molding method, a spray drying granulation method, a rolling granulation method, a bead granulation method, a tableting molding method, and the like can be suitably used. Moreover, it is also possible to use a known binder or additive for imparting or improving processability, shape retention, homogeneity, etc. during each molding.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In addition, the measurement of the chlorine yield in the catalyst activity evaluation of the catalyst obtained by the following example or the comparative example was performed with the following method.

[Chlorine yield]
Potassium iodide (Kanto Chemical Co., Inc., for oxidant measurement) is dissolved in water to prepare a 0.2 mol / L solution. The generated gas was absorbed into the 300 ml of the solution from the reaction tube for 8 minutes. This solution was titrated with a 0.1 mol / L sodium thiosulfate solution (Kanto Chemical Co., Inc.), and the amount of generated chlorine was measured to determine the chlorine yield.

[Concentration of each element in the catalyst]
The content of each element in the catalyst was measured using a fluorescent X-ray analysis method (LAB CENTER XRE-1700, manufactured by Shimadzu Corporation).

[Bulk density of catalyst]
The bulk density was calculated from the weight: m (g) according to the following formula by filling catalyst particles in a 100 ml graduated cylinder so that the volume was 100 ml.
Bulk density (g / ml) = m (g) / 100

[Catalyst Preparation Example 1]
In a 200 ml glass beaker, cupric nitrate trihydrate (Wako Pure Chemical Industries, Ltd., purity: 99.9%): 12.12 g, potassium nitrate (Wako Pure Chemical Industries, purity: 99%) ): 4.9 g, samarium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.9%): 9.42 g is weighed. Water is added so that the volume becomes 50 ml, and the mixture is stirred at room temperature and completely dissolved to prepare the impregnating solution 1. 20.00 g of silica (SS62138, manufactured by Saint-Gobain Co., Ltd., particle size: φ4 mm, total pore volume: 0.96 ml / g) is added to the impregnating liquid 1. After standing at room temperature for 1 hour, the impregnating liquid 1 and silica are separated using a polyethylene mesh sheet. After the impregnating liquid 1 adhering to the silica surface was wiped off with a commercially available paper, it was dried at 120 ° C. for 3 hours using an electric furnace and then subjected to a calcination treatment at 500 ° C. for 5 hours to obtain a supported catalyst 1.

  The copper concentration contained in the supported catalyst 1 was 5.0 wt%, the potassium concentration was 3.0 wt%, the samarium concentration was 5.0 wt%, and the bulk density was 0.47 g / ml.

[Catalyst Preparation Example 2]
Same as Catalyst Preparation Example 1 except that the amount of cupric nitrate trihydrate used was 16.96 g, the amount of potassium nitrate used was 6.99 g, and the amount of samarium nitrate hexahydrate used was 13.19 g. The supported catalyst 2 was prepared by the method described above.

  The copper concentration contained in the supported catalyst 2 was 7.0 wt%, the potassium concentration was 4.2 wt%, the samarium concentration was 7.0 wt%, and the bulk density was 0.49 g / ml.

[Catalyst Preparation Example 3]
Samarium nitrate hexahydrate: The same method as in Catalyst Preparation Example 1, except that instead of 9.42 g, praseodymium nitrate hexahydrate (Aldrich, purity: 99.9%): 9.22 g was used. Thus, supported catalyst 3 was prepared.

  The copper concentration contained in the supported catalyst 3 was 5.0 wt%, the potassium concentration was 3.0 wt%, the praseodymium concentration was 5.0 wt%, and the bulk density was 0.47 g / ml.

[Catalyst Preparation Example 4]
Catalyst Preparation Example 1 except that neodymium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.5%): 9.33 g was used instead of 9.42 g of samarium nitrate hexahydrate A supported catalyst 4 was prepared in the same manner as described above.

  The copper concentration contained in the supported catalyst 4 was 5.0% by weight, the potassium concentration was 3.0% by weight, the neodymium concentration was 5.0% by weight, and the bulk density was 0.47 g / ml.

[Catalyst Preparation Example 5]
Samarium nitrate hexahydrate: The same method as in Catalyst Preparation Example 1, except that instead of 9.42 g, europium nitrate pentahydrate (Aldrich, purity: 99.9%): 9.07 g is used. Thus, supported catalyst 5 was prepared.

  The copper concentration contained in the supported catalyst 5 was 5.0% by weight, the potassium concentration was 3.0% by weight, the europium concentration was 5.0% by weight, and the bulk density was 0.47 g / ml.

[Catalyst Preparation Example 6]
CuCl ₂ · 2H ₂ O 6.71 g, KCl 2.85 g, La (NO ₃ ) ₃ · 6H ₂ O 7.79 g were dissolved in 50 g of a fine chromium oxide catalyst composed of 75% by weight of chromia and 25% by weight of silicon oxide. After impregnation in 25 ml of an aqueous solution, it was fired at 510 ° C. for 5 hours to obtain a supported catalyst 6 composed of silicon oxide and chromium oxide. The bulk density of the supported catalyst 6 was 1.01 g / ml.

  This catalyst was prepared with reference to the methods described in Japanese Patent Application Laid-Open No. Sho 61-275104 and Japanese Patent No. 3270670.

[Catalyst Preparation Example 7]
Catalyst preparation example 1 except that samarium nitrate hexahydrate: 9.18 g was used instead of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.9%): 9.18 g A supported catalyst 7 was prepared in the same manner as described above.

  The copper concentration contained in the supported catalyst 7 was 5.0% by weight, the potassium concentration was 3.0% by weight, the lanthanum concentration was 5.0% by weight, and the bulk density was 0.48 g / ml.

[Example 1] (Reference Example)
The supported catalyst 1 was crushed in an alumina mortar and then adjusted to a particle size of 10 to 20 mesh. Then, 2.0 g of the catalyst was charged into a Hastelloy reaction tube having an inner diameter of 1/2 inch as shown in FIG. While circulating oxygen: 24 ml / min and nitrogen: 14 ml / min, the temperature of the catalyst layer was raised with a heater until the temperature reached 350 ° C. After the temperature of the catalyst layer reached 350 ° C., hydrogen chloride: 40 ml / min and carbon monoxide: 2 ml / min were additionally supplied to start the hydrogen chloride oxidation reaction. During the reaction, the reaction temperature of the catalyst layer was controlled to be 350 ° C. At this time, the gas space velocity of hydrogen chloride in the standard state (0 ° C., 0.1 MPa) was 564 h ⁻¹ and the gas superficial velocity in the standard state (0 ° C., 0.1 MPa) was 0.011 m / s.
The chlorine yield after 5 hours from the start of the reaction was 50.1%, and the chlorine yield after 100 hours from the start of the reaction was 49.3%.

[Example 2] (Reference Example)
A hydrogen chloride oxidation reaction was performed in the same manner as in Example 1 except that the supported catalyst 2 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield when 5 hours passed after the start of the reaction was 54.2%, and the chlorine yield when 100 hours passed after the start of the reaction was 53.4%.

[Example 3] (Reference Example)
A hydrogen chloride oxidation reaction was performed in the same manner as in Example 1 except that the supported catalyst 3 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield when 4 hours passed after the start of the reaction was 49.8%, and the chlorine yield when 100 hours passed after the start of the reaction was 49.4%.

[Example 4] (Reference Example)
A hydrogen chloride oxidation reaction was performed in the same manner as in Example 1 except that the supported catalyst 4 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield after 5 hours from the start of the reaction was 50.3%, and the chlorine yield after 100 hours from the start of the reaction was 49.9%.

[Example 5] (Reference Example)
A hydrogen chloride oxidation reaction was carried out in the same manner as in Example 1 except that the supported catalyst 5 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield after 5 hours from the start of the reaction was 49.2%, and the chlorine yield after 100 hours from the start of the reaction was 49.1%.

[Reference Example 1]
The supported catalyst 1 was crushed in an alumina mortar and then adjusted to a particle size of 10 to 20 mesh. Then, 2.0 g of the catalyst was charged into a Hastelloy reaction tube having an inner diameter of 1/2 inch as shown in FIG. While circulating oxygen: 24 ml / min and nitrogen: 14 ml / min, the temperature of the catalyst layer was raised with a heater until the temperature reached 350 ° C. After the temperature of the catalyst layer reached 350 ° C., hydrogen chloride: 40 ml / min and nitrogen: 2 ml / min were additionally supplied to start the hydrogen chloride oxidation reaction. During the reaction, the reaction temperature of the catalyst layer was controlled to be 350 ° C. At this time, the gas space velocity of hydrogen chloride in the standard state was 564 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield when 5 hours passed after the start of the reaction was 50.8%, and the chlorine yield when 100 hours passed after the start of the reaction was 49.9%.

[Reference Example 2]
A hydrogen chloride oxidation reaction was carried out in the same manner as in Reference Example 1 except that the supported catalyst 2 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield after 5 hours from the start of the reaction was 54.7%, and the chlorine yield after 100 hours from the start of the reaction was 54.1%.

[Comparative Example 1]
The supported catalyst 1 was crushed in an agate mortar and then adjusted to a particle size of 10 to 20 mesh. Then, 2.0 g of the catalyst was charged into a Hastelloy reaction tube having an inner diameter of 1/2 inch as shown in FIG. While circulating oxygen: 24 ml / min and nitrogen: 8 ml / min, the temperature was raised with a heater until the temperature of the catalyst layer reached 350 ° C. After the temperature of the catalyst layer reached 350 ° C., hydrogen chloride: 40 ml / min and carbon monoxide: 8 ml / min were additionally supplied to start the hydrogen chloride oxidation reaction. During the reaction, the reaction temperature of the catalyst layer was controlled to be 350 ° C. At this time, the gas space velocity of hydrogen chloride in the standard state was 564 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield after 4 hours from the start of the reaction was 44.2%, and the chlorine yield after 100 hours from the start of the reaction was 39.8%.

[Comparative Example 2]
A hydrogen chloride oxidation reaction was carried out in the same manner as in Comparative Example 1 except that the supported catalyst 2 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 588 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield when 4 hours passed after the start of the reaction was 48.7%, and the chlorine yield when 100 hours passed after the start of the reaction was 42.1%.

[Comparative Example 3]
A hydrogen chloride oxidation reaction was carried out in the same manner as in Example 1 except that the supported catalyst 6 was used in place of the supported catalyst 1 and the amount of the catalyst was 4.0 g. At this time, the gas space velocity of hydrogen chloride in the standard state was 606 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield when 2 hours passed after the start of the reaction was 28.1%, and the chlorine yield when 2 hours passed after the start of the reaction was 20.4%.

[Comparative Example 4]
A hydrogen chloride oxidation reaction was carried out in the same manner as in Example 1 except that the supported catalyst 7 was used instead of the supported catalyst 1. At this time, the gas space velocity of hydrogen chloride in the standard state was 576 h ⁻¹ , and the gas superficial velocity in the standard state was 0.011 m / s.
The chlorine yield after 3 hours from the start of the reaction was 37.1%, and the chlorine yield after 100 hours from the start of the reaction was 35.3%.

According to the present invention, chlorine can be produced efficiently, economically and stably over a long period of time with high productivity.
In addition, since the amount of catalyst used can be greatly reduced, the burden on the environment can be minimized.

DESCRIPTION OF SYMBOLS 1 Source gas 2 Generated gas 3 Hastelloy reaction tube 4 Heater 5 Quartz sand 6 Catalyst layer 7 Glass wool

Claims (6)

Using a fixed bed reactor with a reaction zone consisting of a catalyst packed bed, hydrogen chloride in the raw material gas containing hydrogen chloride, oxygen and carbon monoxide is oxidized with oxygen under a catalyst for chlorine production to produce chlorine. And how to
Carbon monoxide contained in the raw material gas is 0.1 vol% or more and 8 vol% or less with respect to 100 vol% of the raw material gas , and the molar ratio of oxygen to hydrogen chloride in the raw material gas is 0.25. Above and below 2.0,
The chlorine production catalyst is elemental copper, the active ingredient bond dissociation energy comprises a lanthanoid metal element satisfying 100~185kcal / mol with oxygen in an alkaline metal element and 298K is, Ri catalyst der supported on a porous carrier The copper element is 1.5% by weight or more and 15% by weight or less per 100% by weight of the catalyst for chlorine production, and the lanthanoid metal element is at least one selected from praseodymium, neodymium, samarium and europium. The weight ratio of copper element to alkali metal element is in the range of 1: 0.2 to 1: 4.0, and the weight ratio of copper element to lanthanoid element is 1: 0.2 to 1 : In the range of 6.0,
The gas superficial velocity in the reaction zone is 0.01 m / s or more and 10.0 m / s or less in a standard state (0 ° C., 0.1 MPa),
The gas space velocity (GHSV) of hydrogen chloride in the reaction zone is 250 h ⁻¹ or more and 1500 h ⁻¹ or less in a standard state (0 ° C., 0.1 MPa) ,
Maximum temperature in the reaction zone, 300 ° C. or higher, the production method of chlorine, wherein 420 ° C. der Rukoto less
(However, it is a method of oxidizing hydrogen chloride in a gas containing hydrogen chloride using a gas containing oxygen in a fixed bed reaction system having a reaction zone composed of a catalyst packed bed, and a superficial velocity in the reaction zone. Is less than 0.70 m / s, and the bulk density of the catalyst packed in the catalyst packed bed is less than 700 kg / m ³ ). The method for producing chlorine according to claim 1, wherein the alkali metal element is sodium and / or potassium. The alkali metal element is 1.0 wt% or more and 10 wt% or less per 100 wt% of the catalyst for chlorine production,
The lanthanoid metal element is not less than 1.5% by weight and not more than 15% by weight per 100% by weight of the catalyst for chlorine production.
The method for producing chlorine according to claim 1 or 2, wherein: A method for producing the chlorine,
(1) A step of previously heating a source gas containing hydrogen chloride, oxygen, and carbon monoxide
(2) Step of performing oxidation reaction of hydrogen chloride
(3) Step of cooling the product gas containing hydrogen chloride, oxygen, chlorine, water, carbon monoxide, carbon dioxide
(4) Process for recovering and removing hydrogen chloride from the product gas
(5) Dehydrating the generated gas
(6) The process of compressing and cooling the product gas and separating chlorine as liquefied chlorine
The method for producing chlorine according to any one of claims 1 to 3, comprising: The chlorine according to any one of claims 1 to 4, wherein the heating performed before introducing the raw material gas into the fixed bed reactor in the step (1) is 100 ° C or higher and lower than 400 ° C. Manufacturing method. The said porous support | carrier is a porous support | carrier which consists of silicas, The manufacturing method of the chlorine as described in any one of Claims 1-5 characterized by the above-mentioned.

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