Chlorinated organic compound selective hydrodechlorination catalyst and preparation method thereof

Abstract

The invention relates to a chlorinated organic compound selective hydrodechlorination catalyst and a preparation method thereof. The invention provides a catalyst for selective hydrodechlorination of chlorinated organic compounds, the catalyst comprises a first metal component and a second metal component which are loaded on a carrier, the carrier is treated by organic acid, the first metal component is selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal component is selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

Description

Technical Field

[0001] The present application relates to the technical field of catalysts, and in particular to a catalyst for selective hydrodechlorination of chlorinated organic matter, a preparation method thereof, and application of the catalyst in hydrodechlorination reactions of chlorinated organic matter. Background Art

[0002] Polychlorinated organic compounds are extremely harmful to the environment due to their inherent difficulty in degradation and harmfulness. In addition, the value and market demand of polychlorinated organic compounds are often low, and most industrial methods of treating these polychlorinated organic compounds are to treat them as waste. If polychlorinated organic compounds can be treated by appropriate means to remove one or more chlorines from them, thus turning polychlorinated compounds with no industrial use into useful low-chlorine compounds, it will help waste treatment, save corporate costs, and achieve the concept of green production.

[0003] At present, the common hydrodechlorination catalysts are mainly Pd, Pt, Rh and Ni catalysts. Compared with Ni-based catalysts, precious metal catalysts have higher activity and stability under mild conditions and have stronger resistance to chlorine poisoning. Among them, Pd catalyst has better hydrodechlorination performance.

[0004] CN110407664B discloses a method for hydrodechlorination of polychlorobenzenes to dichlorobenzenes. However, the autoclave technology used requires the use of a large amount of alkali, which is not conducive to safe production and the reduction of equipment costs. US4827057A uses Pt / spinel catalyst to successfully selectively hydrodechlorinate polychlorobenzenes, but its dechlorination product components are relatively complex, which is not conducive to the further application of recyclates. CN111233621B discloses a method for treating dichlorobenzene distillation residues, and its Pd catalyst can selectively hydrodechlorinate polychlorobenzenes to benzene through a fixed bed reactor, but the added value of benzene is relatively low, and there is still room for further selective regulation.

[0005] On the other hand, in the hydrodechlorination process of the tubular reactor, due to the lack of alkali absorption, the generated HCl causes problems with the stability of the catalyst. In addition, different catalysts also have problems of metal loss and sintering due to their own structures. The Pt / spinel catalyst used in US4827057A has a stable operating time of 2000h for the hydrogenation of polychlorinated benzenes. US5426252A discloses a catalyst for the hydrodechlorination of carbon tetrachloride, whose selectivity for chloroform can reach 99%, but it will quickly deactivate within 20 hours. Patent USP5105032 uses HCl to pretreat the catalyst, and its selectivity reaches 70-80%, and its stability is improved to 2000h.

[0006] As can be seen from the above, the catalysts currently described still have the problem of low selectivity and stable operation time for the selective hydrogenation of chlorinated organic compounds. Therefore, it is necessary to develop a catalyst with high selectivity and long-term stable operation (e.g., more than 2000 hours, such as 3000, 4000 or 5000 hours), so as to reduce costs for enterprises and achieve green production. Summary of the invention

[0007] The main purpose of the present application is to provide a highly selective and highly stable hydrodechlorination catalyst for chlorinated organic matter and a preparation method thereof in view of the problems existing in the prior art.

[0008] After extensive research, the inventors of the present application have discovered that by modifying the surface of the carrier through treatment with an organic acid, the active metal and the second metal component can be highly dispersed on the surface of the carrier through the anchoring effect of the carrier surface, and then the spatial and electronic structure of the active metal can be regulated through metal-carrier interaction and metal-metal interaction, thereby inhibiting excessive hydrogenation of chlorinated organics and improving the stability of the catalyst.

[0009] On the one hand, the present application provides a catalyst for selective hydrodechlorination of chlorinated organic matter, the catalyst comprising a first metal component and a second metal component supported on a carrier, the carrier being treated with an organic acid, the first metal component being selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal component being selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

[0010] On the other hand, the present application provides a method for preparing a catalyst for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps:

[0011] Step S1: treating the carrier with an organic acid;

[0012] Step S2: adding the treated support obtained in S1 to a metal salt solution containing a first metal component and a metal salt solution containing a second metal component for treatment;

[0013] Step S3: reducing the solid obtained in S2 to obtain the catalyst,

[0014] The first metal is selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal is selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

[0015] In another aspect, the present application provides a method for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps:

[0016] (1) providing a catalyst for selective hydrodechlorination of chlorinated organic compounds as described in the present application; and

[0017] (2) Using the catalyst to selectively hydrodechlorinate chlorinated organic matter. DETAILED DESCRIPTION

[0018] "Scope" disclosed herein is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0019] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0020] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0021] In the present application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0022] In this application, unless otherwise specified, the terms "include" and "comprising" mentioned herein may be open-ended or closed-ended. For example, the terms "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0023] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number itself, and "several" in "one or several" means two or more.

[0024] In the description herein, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0025] Herein, unless otherwise specified, percentage (%) or part refers to percentage by weight or part by weight relative to the composition.

[0026] Herein, if there is no contrary description, the sum of the contents of the various components in the composition is 100%.

[0027] Herein, if there is no contrary description, the sum of the parts of each component in the composition may be 100 parts by weight.

[0028] In this document, unless otherwise specified, "a combination thereof" means a multi-component mixture of the elements described, for example a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0029] If not specifically stated, the terms "a" or "an" used in the present specification means "at least one".

[0030] Herein, unless otherwise stated, all reactions are carried out at normal temperature and pressure.

[0031] On the one hand, the present application provides a catalyst for selective hydrodechlorination of chlorinated organic matter, the catalyst comprising a first metal component and a second metal component supported on a carrier, the carrier being treated with an organic acid, the first metal component being selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal component being selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

[0032] In one example of the present application, the carrier may be a carrier commonly used in the art for catalysts, such as a porous carrier and a non-porous carrier. In one example of the present application, the carrier is selected from one or more of activated carbon, zeolite, Al2O3, CeO2, SiO2, ZrO2, and TiO2.

[0033] In one example of the present application, the organic acid can be an organic acid commonly used in the art, such as carboxylic acid (fatty acid), sulfonic acid, sulfinic acid, etc. In one example of the present application, the organic acid can be a monoprotic acid, a diprotic acid or a triprotic acid. For example, the organic acid can be selected from one or more of oxalic acid, acetic acid, tartaric acid, succinic acid, salicylic acid, succinic acid, malic acid, ascorbic acid, and citric acid.

[0034] In one example of the present application, the mass ratio of the organic acid to the carrier may be 0.05-5, such as 0.1-3, 0.2-2, 0.2-1.

[0035] In one example of the present application, the carrier treated with an organic acid can be carried out in a solvent (e.g., water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), and the treatment temperature can be 20-100°C, such as 25-80°C; the treatment time can be, for example, 1-24h (e.g., 2-12 hours, 3-8 hours). In another example of the present application, the carrier treated with an organic acid can be further dried, for example, the drying temperature is 40-150°C (generally 60-120°C), and the drying time can be 1-48h (generally 2-24h).

[0036] In one example of the present application, based on the total weight of the catalyst, the content of the first metal component is 0.01-5 wt%, for example, 0.01-0.5 wt% (for example, 0.02-0.2 wt%, 0.03-0.1 wt%), 0.1-3 wt% (for example, 0.2-2 wt%, 0.5-1.5 wt%); the content of the second metal component is 0.01-10 wt%, for example, 0.05-1 wt% (for example, 0.05-0.5 wt%, 0.06-0.2 wt%), 0.1-8 wt% (for example, 1-6 wt%, 1.5-5 wt%).

[0037] On the other hand, the present application provides a method for preparing a catalyst for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps:

[0038] Step S1: treating the carrier with an organic acid;

[0039] Step S2: adding the treated support obtained in S1 to a metal salt solution containing a first metal component and a metal salt solution containing a second metal component for treatment;

[0040] Step S3: reducing the solid obtained in S2 to obtain the catalyst,

[0041] The first metal is selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal is selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

[0042] In one example of the present application, the carrier may be a carrier commonly used in the art for catalysts, such as a porous carrier and a non-porous carrier. In one example of the present application, the carrier is selected from one or more of activated carbon, zeolite, Al2O3, CeO2, SiO2, ZrO2, and TiO2.

[0043] In one example of the present application, the organic acid can be an organic acid commonly used in the art, such as carboxylic acid (fatty acid), sulfonic acid, sulfinic acid, etc. In one example of the present application, the organic acid can be a monoprotic acid, a diprotic acid or a triprotic acid. For example, the organic acid can be selected from one or more of oxalic acid, acetic acid, tartaric acid, succinic acid, salicylic acid, succinic acid, malic acid, ascorbic acid, and citric acid.

[0044] In one example of the present application, the mass ratio of the organic acid to the carrier may be 0.05-5, such as 0.1-3, 0.2-2, 0.2-1.

[0045] In one example of the present application, the carrier treated with an organic acid can be carried out in a solvent (such as water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), and the treatment temperature can be 20-100°C, such as 25-80°C; the treatment time can be, for example, 1-24h (e.g., 2-12 hours, 3-8 hours).

[0046] In the above step S1, the carrier treated with organic acid can be subjected to solid-liquid separation and dried. The solid-liquid separation can be carried out by methods commonly used in the art, including but not limited to filtration, centrifugation, standing, etc. In another example of the present application, the carrier treated with organic acid can be further dried, for example, the drying temperature is 40-150°C (generally 60-120°C), and the drying time can be 1-48h (generally 2-24h).

[0047] In the above step S2, the metal salts of the first metal component and the second metal component can be salts commonly used in the art, such as nitrates, sulfates, halides (such as chlorides, bromides, etc.), complexes (such as acids of the first metal or the second metal and salts thereof (such as ammonium salts, sodium salts, potassium salts)) or combinations thereof. In one example of the present application, the complex can be, for example, palladium acid, bromopalladic acid, chloropalladic acid, platinic acid, bromoplatinic acid, chloroplatinic acid, rhodic acid, bromorhodic acid, chlororhodic acid and salts thereof (such as ammonium salts, sodium salts, potassium salts). The metal salt of the first metal component can be the same as or different from the metal salt of the second metal component. The metal salt of the first metal component and the metal salt of the second metal component are usually provided in the form of a solution, wherein the solvent can be water or an organic solvent, including but not limited to water, alcohols (such as methanol, ethanol, etc.), ethers (such as ether), etc. In one example of the present application, the metal salts of the first metal component and the second metal component can be, for example, sodium chloropalladate, chloroplatinic acid, rhodium chloride, manganese chloride, copper nitrate, cobalt nitrate, nickel nitrate, iron nitrate, iron chloride or a combination thereof.

[0048] In the above step S2, the amount of the metal salt of the first metal component and the metal salt of the second metal component is such that in the final catalyst, based on the total weight of the catalyst, the content of the first metal component is 0.01-5% by weight, for example, 0.01-0.5% by weight (for example, 0.02-0.2% by weight, 0.03-0.1% by weight), 0.1-3% by weight (for example, 0.2-2% by weight, 0.5-1.5% by weight); the content of the second metal component is 0.01-10% by weight, for example, 0.05-1% by weight (for example, 0.05-0.5% by weight, 0.06-0.2% by weight), 0.1-8% by weight (for example, 1-6% by weight, 1.5-5% by weight).

[0049] In one example of the present application, the treatment in step S2 can be carried out in a solvent (such as water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), and the treatment temperature can be 100-200°C, such as 120-160°C; the treatment time can be, for example, 1-72 hours, such as 2-48 hours.

[0050] In one example of the present application, the treatment in step S2 can be carried out in steps, that is, the treated carrier obtained in S1 is treated with a metal salt solution containing a first metal component and a metal salt solution containing a second metal component, respectively. The treatment conditions of each step may be the same or different. For example, the treatment can be carried out in a solvent (such as water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), the treatment temperature can be 100-200°C, for example, 120-160°C; the treatment time can be, for example, 1-72 hours, for example, 2-48 hours; the pH is 7-14 (for example, 7-10, 7-8).

[0051] In one example of the present application, a precipitant may be added in step S2, and the precipitant is selected from one or more of ammonia water, urea, ammonium bicarbonate, sodium carbonate, and sodium bicarbonate. In one example of the present application, the treated carrier obtained in S1 may be added to a metal salt solution containing a first metal component and a metal salt solution containing a second metal component for treatment before adding the precipitant.

[0052] In the above step S3, the reduction can be carried out by treating the solid obtained in step S2 with a reducing gas or a gas stream containing a reducing gas. Before the reduction treatment, the solid obtained in step S2 can be subjected to solid-liquid separation and dried. The solid-liquid separation can be carried out by methods commonly used in the art, including but not limited to filtration, centrifugation, standing, etc.

[0053] In one example of the present application, the reducing gas is selected from H2, CO, CH4 or a combination thereof. In one example of the present application, the inert gas includes a rare gas (helium, neon, argon, krypton or xenon), nitrogen, carbon dioxide or a combination thereof. The volume ratio of the reducing gas to the inert gas can be 1:1-50, for example, 1:2-40, 1:5-30, 1:8-25.

[0054] In one example of the present application, the reduction treatment conditions are: pressure, 0.05-10 MPa (e.g., 0.1-5 MPa, 0.1-2 MPa); space velocity, 0.01-10 h -1 (e.g. 0.05-8h -1 , 0.1-5h -1 ); temperature, 150-800°C (e.g., 200-700°C, 200-600°C); time, 0.1-20 hours (e.g., 0.5-16 hours, 1-12 hours).

[0055] In another aspect, the present application provides a method for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps:

[0056] (1) providing a catalyst for selective hydrodechlorination of chlorinated organic compounds as described in the present application; and

[0057] (2) Using the catalyst to selectively hydrodechlorinate chlorinated organic matter.

[0058] The catalyst described in the present application can be used for selective hydrodechlorination of chlorinated organic matter. In one example of the present application, the chlorinated organic matter includes but is not limited to chlorinated alkanes (e.g., chlorinated C1-C20 alkanes, chlorinated C1-C10 alkanes, chlorinated C1-C6 alkanes), chlorinated aromatic hydrocarbons (e.g., chlorinated C6-C20 aromatic hydrocarbons, chlorinated C6-C12 aromatic hydrocarbons), etc., such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, and one or more of chlorinated naphthalene, chlorinated anthracene, chlorinated phenanthrene, chlorinated biphenyl, and chlorinated fluorene. In a preferred embodiment of the present application, the catalyst selectively dechlorinates and hydrogenates polychlorinated organic matter (e.g., polychlorinated C1-C20 alkanes, polychlorinated C1-C10 alkanes, polychlorinated C1-C6 alkanes; polychlorinated C6-C20 aromatics, polychlorinated C6-C12 aromatics, preferably trichlorobenzene (e.g., 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene or 1,3,5-trichlorobenzene)). Preferably, the catalyst of the present application can selectively dechlorinate and hydrogenate trichlorobenzene to form dichlorobenzene.

[0059] In one example of the present application, the catalyst of the present application selectively dechlorinates and hydrogenates trichlorobenzene (e.g., 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, or 1,3,5-trichlorobenzene) to obtain a dichlorobenzene product. Preferably, the selectivity of dichlorobenzene in the product is greater than or equal to 80%, such as 80-99%, 85-99%, 90-99%.

[0060] In the present application, the conditions for selectively hydrodechlorinating chlorinated organic matter using the catalyst may be the hydrodechlorinating conditions commonly used in the art.

[0061] The advantages of this applicant are:

[0062] 1. The catalyst of the applicant is synthesized by a simple process, which is a simple and environmentally friendly process and is conducive to large-scale production.

[0063] 2. The applicant modified the carrier by treating it with an organic acid, thereby greatly improving the dispersion of the metal when loaded, enhancing the interaction between the metal and the carrier, regulating the electronic structure of the first metal (precious metal), and enhancing the stability of the metal.

[0064] 3. The present application further regulates the electronic structure of the noble metal active center by combining the first metal (noble metal) and the second metal, thereby solving the problem of the catalyst being prone to over-hydrogenation and the loss of noble metal.

[0065] 4. The applicant shows excellent stability and selectivity in the process of hydrodechlorination of chlorine-containing organic compounds, has strong stability for various hydrodechlorination reactions, and can effectively prevent excessive hydrogenation of substrates through the regulation of reaction processes. In particular, in the process of selective hydrogenation of polychlorinated benzenes to dichlorobenzenes, the selectivity of dichlorobenzenes can reach greater than or equal to 80% (e.g., 80-99%, 85-99%, 90-99%), and the service life of the catalyst can reach more than 3000 hours, such as more than 4000 hours, more than 5000 hours, 3000-8000 hours, 4000-8000 hours, 5000-7000 hours.

[0066] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0067] Main reagents for the experiment

[0068]

[0069]

[0070] Main experimental instruments

[0071] Instrument Name model Manufacturer Fixed bed HF-V1 Shanghai Baikal Technology Reactor BKLS-5L Shanghai Baikal Technology Gas chromatography 7890 Agilent Blast drying oven DHG-900A Shenzhen Kejing Zhida Technology

[0072] Specific test methods used in the examples

[0073] The liquid after the reaction was collected and analyzed by Agilent 7890 gas chromatograph. The concentration of each component was calculated by external standard method using hydrogen flame detector (FID).

[0074] Catalyst life (h) refers to the operating time during which the reaction conversion rate and reaction selectivity decay to less than or equal to 80%.

[0075] Example 1

[0076] Disperse 50g of activated carbon carrier and 25g of oxalic acid in 1000g of water. After stirring at 40°C for 12h, filter, wash with clean water and dry at 60°C for 24h to obtain the treated activated carbon carrier. Mix the treated activated carbon carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (the metal accounts for about 1% of the final catalyst mass) and heat to 150°C for hydrothermal treatment for 12h. After the hydrothermal treatment, add 50mgFe / ml ferric chloride solution (the metal accounts for about 3% of the final catalyst mass) and stir for 12h, then add ammonia solution to control the pH to 7-8, heat to 150°C for hydrothermal treatment for 12h. After hydrothermal treatment, filter and wash the obtained solid, and dry it at 60°C for 24h. The catalyst is then loaded into a fixed bed for reduction, and the H2 / N2 flow rate ratio is controlled to be 1:10 and the air velocity is 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0077] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0078] Comparative Example 1 (without second metal component)

[0079] The catalyst was prepared and tested in substantially the same manner as in Example 1, except that no ferric chloride solution was used in the preparation process.

[0080] Comparative Example 2 (Commercial Pd / C)

[0081] The same method as in Example 1 was used to test commercial Pd / C.

[0082] Comparative Example 3 (impregnated bimetallic catalyst without organic acid treatment)

[0083] 50g of activated carbon carrier was dispersed and impregnated in a mixed solution of 10mgPd / ml sodium chloropalladate aqueous solution (metal accounted for about 1% of the final catalyst mass) and 50mgFe / ml ferric chloride aqueous solution (metal accounted for about 3% of the final catalyst mass). After the impregnation, the obtained solid was filtered and washed, and dried at 60°C for 24h. The catalyst was then loaded into a fixed bed for reduction, and the H2 / N2 flow rate ratio was controlled to be 1:10 and the air velocity was 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0084] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1, the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0085] Comparative Example 4 (a bimetallic catalyst in which the second metal is selected to be other than Fe, Co, Ni, or Cu)

[0086] The catalyst was prepared and tested in substantially the same manner as in Example 1, except that a 50 mg Mn / ml manganese chloride aqueous solution was used instead of a ferric chloride solution during the preparation process, wherein manganese accounted for about 3% of the weight of the final catalyst.

[0087] Example 2

[0088] Disperse 50g of alumina carrier and 5g of salicylic acid in 250g of water. After stirring at room temperature for 24h, filter, wash with clean water and dry at 80℃ for 12h to obtain the treated alumina carrier. Mix the treated alumina carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (the metal accounts for about 1% of the final catalyst mass) and heat to 100℃ for hydrothermal treatment for 72h. After the hydrothermal treatment, add 50mgFe / ml ferric chloride solution (the metal accounts for about 3% of the final catalyst mass) and stir for 1h, then add urea solution to control the pH to 7-8, heat to 200℃ and hydrothermally treat for 1h. After hydrothermal treatment, filter and wash the obtained solid, and dry it at 80℃ for 12h. Then load the catalyst into a fixed bed for reduction, control the H2 / N2 flow rate ratio to 1:10, and the air velocity to 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0089] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0090] Example 3

[0091] Disperse 50g of titanium dioxide carrier and 10g of tartaric acid in 500g of water. Stir at room temperature for 24h, filter, wash with clean water and dry at 80℃ for 12h to obtain the treated titanium dioxide carrier. Mix the treated titanium dioxide carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (metal accounts for about 1% of the final catalyst mass) and heat to 120℃ for hydrothermal treatment for 36h. After the hydrothermal treatment, add 50mgFe / ml ferric chloride aqueous solution (metal accounts for about 3% of the final catalyst mass) and stir for 2h, then add ammonium bicarbonate solution to control the pH to 7-8, heat to 180℃ for hydrothermal treatment for 2h. After hydrothermal treatment, filter and wash the obtained solid, and dry it at 80℃ for 12h. Then load the catalyst into a fixed bed for reduction, control the H2 / N2 flow rate ratio to 1:10, and the air velocity to 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0092] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0093] Example 4

[0094] Disperse 50g of silica carrier and 50g of citric acid in 1000g of water. After stirring at 80℃ for 2h, let it stand, filter, wash it with clean water and dry it at 120℃ for 1h to obtain the treated silica carrier. Mix the treated silica carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (the metal accounts for about 1% of the final catalyst mass) and heat it to 160℃ for hydrothermal treatment for 8h. After the hydrothermal treatment, add 50mgFe / ml ferric chloride aqueous solution (the metal accounts for about 3% of the final catalyst mass) and stir for 4h, then add sodium bicarbonate and sodium carbonate solution to control the pH to 7-8, and heat it to 160℃ for hydrothermal treatment for 8h. After hydrothermal treatment, let the obtained solid stand, filter, wash, and dry it at 120℃ for 1h. Then load the catalyst into a fixed bed for reduction, control the H2 / N2 flow rate ratio to 1:10, and the air velocity to 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0095] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1, the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0096] Example 5

[0097] Disperse 50g of cerium dioxide carrier and 25g of ascorbic acid in 2500g of water. Stir at room temperature for 12h and then centrifuge, wash with clean water and dry at 60°C for 24h to obtain the treated cerium dioxide carrier. Mix the treated cerium dioxide carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (metal accounts for about 1% of the final catalyst mass) and 50mgFe / ml ferric chloride aqueous solution (metal accounts for about 3% of the final catalyst mass) and heat to 160°C for hydrothermal treatment for 8h. After hydrothermal treatment, the obtained solid is centrifuged and washed, and dried at 60°C for 24h. The catalyst is then loaded into a fixed bed for reduction, and the H2 / N2 flow rate ratio is controlled to be 1:10 and the air velocity is 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0098] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0099] Example 6

[0100] Disperse 50g of zirconium dioxide carrier, 10g of malic acid and 10g of succinic acid in 1500g of water. Stir at room temperature for 12h and then centrifuge. Wash with clean water and dry at 60°C for 24h to obtain the treated zirconium dioxide carrier. Mix the treated zirconium dioxide carrier with 500g of water and add it to the reactor. Then add 10mgPd / ml sodium chloropalladate aqueous solution (the metal accounts for about 1% of the final catalyst mass) and 50mgFe / ml ferric chloride solution (the metal accounts for about 3% of the final catalyst mass) and heat to 170°C for hydrothermal treatment for 6h. After hydrothermal treatment, the obtained solid is centrifuged and washed, and dried at 60°C for 24h. The catalyst is then loaded into a fixed bed to control the H2 / N2 flow rate ratio to 1:10 and the air velocity to 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0101] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1, the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0102] Example 7

[0103] Disperse 25g of zirconium dioxide, 25g of cerium dioxide carrier and 10g of acetic acid, 10g of succinic acid and 10g of ascorbic acid in 2000g of water. Stir at room temperature for 12h and then centrifuge, wash with clean water and dry at 60°C for 24h to obtain the treated mixed carrier. Mix the treated mixed carrier with 500g of water and add it to the reactor, then add 10mgPd / ml sodium chloropalladate aqueous solution (metal accounts for about 1% of the final catalyst mass) and 50mgFe / ml ferric chloride aqueous solution (metal accounts for about 3% of the final catalyst mass) and heat to 150°C for hydrothermal treatment for 12h. After hydrothermal treatment, the obtained solid is centrifuged and washed, and dried at 60°C for 24h. The catalyst is then loaded into a fixed bed for reduction, and the H2 / N2 flow rate ratio is controlled to be 1:10 and the air velocity is 2h -1 , pressure of 0.5MPa, temperature of 350℃, treatment time of 2h, and the target catalyst was obtained.

[0104] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0105] Test results of examples 1-7

[0106] The metal loading of Examples 1-7 was measured by ICP (inductively coupled plasma), and the results and the reaction results of catalytic 1,2,4-trichlorobenzene hydrodechlorination are listed in the following table:

[0107] Table 1 Comparison of the reaction results of 1,2,4-trichlorobenzene hydrodechlorination catalyzed by different embodiments

[0108]

[0109] Example 8

[0110] On the basis of Example 1, the other catalyst preparation conditions were kept unchanged, and the first and second components added were changed to a mixture of 10 mg Pd / ml sodium chloropalladate aqueous solution (the metal accounted for about 1% of the final catalyst mass), 50 mg Fe / ml ferric nitrate aqueous solution (the metal accounted for about 3% of the final catalyst mass), and 50 mg Ni / ml nickel nitrate aqueous solution (the metal accounted for about 3% of the final catalyst mass).

[0111] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:5, and the dechlorination product is obtained after passing through a fixed bed layer.

[0112] Example 9

[0113] On the basis of Example 1, while ensuring that the other catalyst preparation conditions remain unchanged, the first and second components added are changed to 10 mg Pd / ml sodium chloropalladate aqueous solution (the metal accounts for about 0.05% of the final catalyst mass) and 50 mg Fe / ml ferric chloride aqueous solution (the metal accounts for about 0.1% of the final catalyst mass).

[0114] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 0.05h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the 1,2,4-trichlorobenzene / H2 molar ratio is 1:40, and the dechlorination product is obtained after passing through a fixed bed layer.

[0115] Example 10

[0116] On the basis of Example 1, while ensuring that the other catalyst preparation conditions remain unchanged, the first and second components added are changed to 10 mg Pd / ml sodium chloropalladate aqueous solution (the metal accounts for about 3% of the final catalyst mass) and 50 mg Fe / ml ferric chloride aqueous solution (the metal accounts for about 3% of the final catalyst mass).

[0117] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 2h -1 , the reaction temperature is 120°C, the pressure is 0.1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:20, and the dechlorination product is obtained after passing through a fixed bed layer.

[0118] Embodiment 11

[0119] On the basis of Example 1, the remaining catalyst preparation conditions are guaranteed to remain unchanged, and the first and second components added are changed to 10 mgRh / ml rhodium chloride aqueous solution (the metal accounts for about 1% of the final catalyst mass) and 50 mgCo / ml cobalt nitrate aqueous solution (the metal accounts for about 3% of the final catalyst mass).

[0120] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0121] Example 12

[0122] On the basis of Example 1, while ensuring that the other catalyst preparation conditions remain unchanged, the first and second components added are changed to 10 mg Pt / ml chloroplatinic acid aqueous solution (the metal accounts for about 1% of the final catalyst mass) and 50 mg Cu / ml copper nitrate aqueous solution (the metal accounts for about 3% of the final catalyst mass).

[0123] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0124] Embodiment 13

[0125] On the basis of Example 1, the other catalyst preparation conditions were kept unchanged, and the first and second components added were changed to a mixture of 10 mgPt / ml chloroplatinic acid aqueous solution (the metal accounted for about 0.5% of the final catalyst mass), 10 mgPd / ml sodium chloropalladate aqueous solution (the metal accounted for about 0.5% of the final catalyst mass), and 50 mgFe / ml ferric chloride aqueous solution (the metal accounted for about 3% of the final catalyst mass).

[0126] After the treatment, hydrogen was used as the reaction gas, 1,2,4-trichlorobenzene was used as the substrate, and the space velocity was controlled to be 0.1h -1 , the reaction temperature is 100°C, the pressure is 1MPa, the molar ratio of 1,2,4-trichlorobenzene / H2 is 1:10, and the dechlorination product is obtained after passing through a fixed bed layer.

[0127] Test results of examples 8-13

[0128] On the basis of Example 1, the added first metal and second metal salt solutions and their ratios to the carrier were changed, and element determination was performed by ICP (inductively coupled plasma). The results and the reaction results of catalytic 1,2,4-trichlorobenzene hydrodechlorination are listed in the following table:

[0129] Table 2 Comparison of the results of changing the first and second metal ratios in different embodiments

[0130]

[0131] Examples 14-18

[0132] On the basis of Example 1, the reduction conditions were changed and the results are listed in the following table:

[0133] Table 3 Comparison of results of changing reduction conditions in different embodiments

[0134]

[0135]

[0136] Examples 19-29

[0137] On the basis of Example 1, the hydrodechlorination reaction conditions were changed, and the results are listed in the following table:

[0138] Table 4 Comparison of the results of changing the reaction process in different embodiments

[0139]

[0140] Embodiment 34

[0141] On the basis of Example 1, the other conditions were kept unchanged and the added substrate was changed to 1,2,3-trichlorobenzene.

[0142] Embodiment 35

[0143] On the basis of Example 1, the other conditions were kept unchanged and the added substrate was changed to 1,3,5-trichlorobenzene.

[0144] Embodiment 36

[0145] On the basis of Example 1, the other conditions were kept unchanged, and the added substrate was changed to a mixture of 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, and 1,3,5-trichlorobenzene (1:1:1).

[0146] Test results of Examples 34-36

[0147] Based on Example 1, the substrate was changed, and the corresponding hydrodechlorination reaction results are listed in the following table:

[0148] Table 5 Comparison of the results of changing the substrate in different embodiments

[0149]

[0150] Embodiment 37

[0151] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was chlorobenzene, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 200℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:5, and dechlorination product is obtained after fixed bed. Substrate conversion rate is 98.9%, product composition is: benzene 99.9%, other products <0.1%. Catalyst life can reach 5000h.

[0152] Embodiment 38

[0153] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was a mixture of 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, pentachlorobenzene and hexachlorobenzene, the solvent was mesitylene, the substrate mass fraction was 10%, and the substrate space velocity was 0.5h -1 , reaction temperature is 300℃, pressure is 1MPa, substrate / H2 molar ratio is 1:80, and dechlorination product is obtained after fixed bed. The product composition is: dichlorobenzene 82.5%, chlorobenzene 15.3%, benzene 1.2%, and other substances <1.0%. The catalyst life can reach 3200h.

[0154] Embodiment 39

[0155] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 4-chlorobiphenyl, the solvent was methanol, the substrate mass fraction was 5%, and the space velocity was controlled to be 1h -1 , reaction temperature is 140℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:40, and dechlorination product is obtained after fixed bed. Substrate conversion rate is 99.2%, product composition is: biphenyl>99.9%, other products <0.1%. Catalyst life can reach 4100h.

[0156] Embodiment 40

[0157] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 2,4-dichlorobiphenyl, the solvent was methanol, the substrate mass fraction was 5%, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 160℃, pressure is 0.6MPa, substrate / H2 molar ratio is 1:40, and dechlorination product is obtained after fixed bed. Substrate conversion rate is 98.6%, product composition is: biphenyl>99.5%, other products <0.5%. Catalyst life can reach 4200h.

[0158] Embodiment 41

[0159] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 2,7-dichlorofluorene, the solvent was ethanol, the substrate mass fraction was 10%, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 150℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:40, and dechlorination product is obtained after fixed bed. Substrate conversion rate is 99.0%, product composition is: fluorene>99.8%, other products <0.2%. Catalyst life can reach 4000h.

[0160] Embodiment 42

[0161] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 2-chloronaphthalene, the solvent was benzene, the substrate mass fraction was 10%, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 150℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:20, and dechlorination product is obtained after fixed bed. Substrate conversion rate is 99.3%, product composition is: naphthalene>99.9%, other products <0.1%. Catalyst life can reach 4500h.

[0162] Embodiment 43

[0163] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 2-chloroanthracene, the solvent was benzene, the substrate mass fraction was 10%, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 130℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:15, and dechlorination product is obtained after fixed bed. The substrate conversion rate is 98.7%, and the product composition is: anthracene>99.9%, and other products <0.1%. The catalyst life can reach 4200h.

[0164] Embodiment 44

[0165] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 2-chlorophenanthrene, the solvent was benzene, the substrate mass fraction was 10%, and the space velocity was controlled to be 0.5h -1 , reaction temperature is 140℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:20, and dechlorination product is obtained after fixed bed. The substrate conversion rate is 98.2%, and the product composition is: phenanthrene>99.9%, and other products <0.1%. The catalyst life can reach 3700h.

[0166] Embodiment 45

[0167] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was carbon tetrachloride, and the space velocity was controlled to be 10h -1 , reaction temperature is 90℃, pressure is 0.5MPa, substrate / H2 molar ratio is 1:8, and dechlorination product is obtained after fixed bed. The substrate conversion rate is 90.2%, and the product selectivity is: chloroform>98.9%. The catalyst life can reach 4500h.

[0168] Embodiment 46

[0169] On the basis of Example 1, the other conditions were kept unchanged, and the reaction conditions were changed as follows: the substrate was 1,2-dichloroethane, and the space velocity was controlled to be 10h -1, reaction temperature is 225℃, pressure is 0.1MPa, substrate / H2 molar ratio is 1:7.5, and dechlorination product is obtained after fixed bed. The substrate conversion rate is 98.1%, and the product selectivity is: ethane>98.1%. The catalyst life can reach 4800h.

[0170] The content of the present invention is not limited to the content of the embodiments of the present invention. Specific examples are used in this article to illustrate the structure and implementation of the present invention, and the description of the above embodiments is only used to help understand the core idea of ​​the present invention. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A catalyst for selective hydrodechlorination of chlorinated organic matter, the catalyst comprising a first metal component and a second metal component supported on a carrier, the carrier being treated with an organic acid, the first metal component being selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal component being selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

2. The catalyst according to claim 1, wherein The carrier is a porous carrier or a non-porous carrier; or, the carrier is selected from one or more of activated carbon, zeolite, Al2O3, CeO2, SiO2, ZrO2, TiO2; or, The organic acid is a carboxylic acid (fatty acid), a sulfonic acid, or a sulfinic acid; or, the organic acid is a monobasic acid, a dibasic acid, or a tribasic acid; or, the organic acid can be selected from one or more of oxalic acid, acetic acid, tartaric acid, succinic acid, salicylic acid, succinic acid, malic acid, ascorbic acid, and citric acid; or, The mass ratio of the organic acid to the carrier is 0.05-5, such as 0.1-3, 0.2-2, 0.2-1; or, Based on the total weight of the catalyst, the content of the first metal component is 0.01-5 weight %, for example, 0.01-0.5 weight % (for example, 0.02-0.2 weight %, 0.03-0.1 weight %), 0.1-3 weight % (for example, 0.2-2 weight %, 0.5-1.5 weight %); the content of the second metal component is 0.01-10 weight %, for example, 0.05-1 weight % (for example, 0.05-0.5 weight %, 0.06-0.2 weight %), 0.1-8 weight % (for example, 1-6 weight %, 1.5-5 weight %).

3. A method for preparing a catalyst for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps: Step S1: treating the carrier with an organic acid; Step S2: adding the treated support obtained in S1 to a metal salt solution containing a first metal component and a metal salt solution containing a second metal component for treatment; Step S3: reducing the solid obtained in S2 to obtain the catalyst, The first metal is selected from one or more of Pt, Pd, Rh, Ru, Ir, Au and Ag, and the second metal is selected from one or more of Mn, Ti, V, Fe, Co, Ni, Cu and Zn.

4. The method of claim 3, wherein: The carrier is a porous carrier or a non-porous carrier; or, the carrier is selected from one or more of activated carbon, zeolite, Al2O3, CeO2, SiO2, ZrO2, TiO2; or, The organic acid is a carboxylic acid (fatty acid), a sulfonic acid, or a sulfinic acid; or, the organic acid is a monobasic acid, a dibasic acid, or a tribasic acid; or, the organic acid is selected from one or more of oxalic acid, acetic acid, tartaric acid, succinic acid, salicylic acid, succinic acid, malic acid, ascorbic acid, and citric acid; or, The mass ratio of the organic acid to the carrier is 0.05-5, such as 0.1-3, 0.2-2, 0.2-1; or, Treatment of the carrier with an organic acid can be carried out in a solvent (e.g., water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), and the treatment temperature can be 20-100°C, such as 25-80°C; the treatment time can be, for example, 1-24h (e.g., 2-12 hours, 3-8 hours).

5. The method of claim 3, wherein: In the above step S2, the metal salts of the first metal component and the second metal component are nitrates, sulfates, halides (such as chlorides, bromides, etc.), complexes (such as acids of the first metal or the second metal and salts thereof (such as ammonium salts, sodium salts, potassium salts)) or combinations thereof; Alternatively, the complex is palladium acid, bromopalladium acid, chloropalladium acid, platinic acid, bromoplatinic acid, chloroplatinic acid, rhodium acid, bromorhodium acid, chlororhodium acid and salts thereof (eg, ammonium salt, sodium salt, potassium salt); or, The metal salt of the first metal component is the same as or different from the metal salt of the second metal component; or, The metal salt of the first metal component and the metal salt of the second metal component are provided in the form of a solution; or, The metal salts of the first metal component and the second metal component are sodium chloropalladate, chloroplatinic acid, rhodium chloride, manganese chloride, copper nitrate, cobalt nitrate, nickel nitrate, iron nitrate, iron chloride or a combination thereof; or, The metal salt of the first metal component and the metal salt of the second metal component are used in such an amount that, in the final catalyst, the content of the first metal component is 0.01-5 wt%, such as 0.01-0.5 wt% (e.g. 0.02-0.2 wt%, 0.03-0.1 wt%), 0.1-3 wt% (e.g. 0.2-2 wt%, 0.5-1.5 wt%), based on the total weight of the catalyst; the content of the second metal component is 0.01-10 wt%, such as 0.05-1 wt% (e.g. 0.05-0.5 wt%, 0.06-0.2 wt%), 0.1-8 wt% (e.g. 1-6 wt%, 1.5-5 wt%); or, The treatment in step S2 is carried out in a solvent (e.g., water or an organic solvent, including but not limited to water, methanol, ethanol, acetone, etc.), the treatment temperature may be 100-200° C., such as 120-160° C.; the treatment time may be, for example, 1-72 hours, such as 2-48 hours; or, The treatment in step S2 is performed in steps, that is, the treated support obtained in step S1 is treated with a metal salt solution containing a first metal component and a metal salt solution containing a second metal component respectively; or, In step S2, a precipitant is added, wherein the precipitant is selected from one or more of ammonia water, urea, ammonium bicarbonate, sodium carbonate, and sodium bicarbonate; or, The treated carrier obtained in S1 is added to a metal salt solution containing a first metal component and a metal salt solution containing a second metal component for treatment and then the precipitant is added.

6. The method of claim 3, wherein: In the above step S3, the reduction can be carried out by treating the solid obtained in step S2 with a reducing gas or a gas stream containing a reducing gas; or, The reducing gas is selected from H2, CO, CH4 or a combination thereof; alternatively, the inert gas includes a rare gas (helium, neon, argon, krypton or xenon), nitrogen, carbon dioxide or a combination thereof; alternatively, the volume ratio of the reducing gas to the inert gas can be 1:1-50, for example 1:2-40, 1:5-30, 1:8-25.

7. The method of claim 3, wherein: The reduction treatment conditions are: pressure, 0.05-10MPa (e.g., 0.1-5MPa, 0.1-2MPa); space velocity, 0.01-10h -1 (e.g. 0.05-8h -1 , 0.1-5h -1 ); temperature, 150-800°C (e.g., 200-700°C, 200-600°C); time, 0.1-20 hours (e.g., 0.5-16 hours, 1-12 hours).

8. A method for selective hydrodechlorination of chlorinated organic matter, the method comprising the following steps: (1) providing the catalyst for selective hydrodechlorination of chlorinated organic matter according to claim 1; and (2) Using the catalyst to selectively hydrodechlorinate chlorinated organic matter.

9. The method of claim 8, wherein: The chlorinated organic matter includes chlorinated alkanes (e.g., chlorinated C1-C20 alkanes, chlorinated C1-C10 alkanes, chlorinated C1-C6 alkanes), chlorinated aromatics (e.g., chlorinated C6-C20 aromatics, chlorinated C6-C12 aromatics), and the like, such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, and one or more of chlorinated naphthalene, chlorinated anthracene, chlorinated phenanthrene, chlorinated biphenyl, and chlorinated fluorene; or, The catalyst selectively dechlorinates and hydrogenates polychlorinated organic matter (e.g., polychlorinated C1-C20 alkanes, polychlorinated C1-C10 alkanes, polychlorinated C1-C6 alkanes; polychlorinated C6-C20 aromatics, polychlorinated C6-C12 aromatics, preferably trichlorobenzene (e.g., 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene or 1,3,5-trichlorobenzene)); or, The catalyst selectively dechlorinates and hydrogenates trichlorobenzene to form dichlorobenzene.

10. The method of claim 8, wherein: The catalyst selectively dechlorinates and hydrogenates trichlorobenzene (e.g., 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene or 1,3,5-trichlorobenzene) to obtain a dichlorobenzene product; Preferably, the selectivity of dichlorobenzene in the product is greater than or equal to 80%, such as 80-99%, 85-99%, 90-99%.

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