Post-treatment method of copper-containing catalyst
By adding specific additives after the catalytic hydrogenation reaction to promote the precipitation of copper-containing catalysts, the problem of separation difficulties in traditional methods is solved, achieving efficient catalyst recovery and improved product purity, with significant economic and environmental benefits.
Patent Information
- Application Number
- CN202511248644.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-02
- Publication Date
- 2025-12-12
AI Technical Summary
In existing technologies, the small particle size of copper-containing catalysts makes separation difficult, requiring additional equipment and complex operations, which reduces catalyst recovery rate and increases production costs. At the same time, catalyst residue affects product purity and stability.
After the catalytic hydrogenation reaction, a specific auxiliary agent, such as a divalent or trivalent metal chloride or sulfate, is added. The copper-containing catalyst is then allowed to settle by stirring and settling, followed by filtration and washing to achieve separation. The auxiliary agent exhibits good selectivity and stability.
It improves the separation efficiency and recovery rate of the catalyst, enhances the purity and stability of catalytic hydrogenation products, and reduces the generation of heavy metal waste, thus demonstrating good economic benefits and environmental friendliness.
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of organic synthesis, in particular to a post-treatment method for catalytic hydrogenation reaction using copper-containing catalysts. BACKGROUND
[0002] Catalytic hydrogenation using copper-containing catalysts is a common method in the organic synthesis industry. Due to the needs of the reaction, a powder-like copper-containing catalyst with a particle size of only about 1-100 microns is usually used. After the reaction is completed, post-treatment is needed to separate the copper-containing catalyst from the catalytic hydrogenation reaction product. The current treatment methods for copper-containing catalysts mainly include direct filtration, precipitation and other methods. However, due to the small size of the copper-containing catalyst particles, these methods often require additional separation equipment and complex operation processes, increasing production costs and energy consumption. In addition, the traditional treatment methods are difficult to effectively improve the recovery rate of the catalyst and are prone to cause environmental pollution. Since the copper-containing catalyst has activity, its residue in the reaction product will affect the subsequent reaction, reducing the purity and stability of the product.
[0003] Therefore, it is urgent to develop an efficient, economical and simple post-treatment method for copper-containing catalysts to achieve high purity and high stability of the catalytic hydrogenation product, while improving the recovery rate of the catalyst and reducing the generation of heavy metal waste. This method should be able to effectively promote the separation of the copper-containing catalyst from the organic reaction system and have good environmental friendliness and economic benefits. SUMMARY
[0004] The purpose of the present application is to promote the separation of the copper-containing catalyst from the organic reaction system in an efficient, economical and simple way, on the one hand to improve the purity and stability of the catalytic hydrogenation product, and on the other hand to enable more copper-containing catalysts to be recycled and reduce the generation of heavy metal waste. The inventors of the present application have found that the use of a specific auxiliary agent can promote the settling of the copper-containing catalyst, thereby completing the present application.
[0005] Therefore, the present application relates to a post-treatment method for copper-containing catalysts, characterized in that it comprises the following steps:
[0006] (1) adding an auxiliary agent to the reaction system of the catalytic hydrogenation reaction and stirring, wherein the reaction system contains a copper-containing catalyst, and the auxiliary agent is an inorganic salt;
[0007] (2) standing.
[0008] Optionally, the method of the present application further comprises the following steps:
[0009] (3) filtering and separating the copper-containing catalyst; and / or
[0010] (4) washing and drying the copper-containing catalyst.
[0011] Compared with the prior art, the method has the following beneficial effects:
[0012] 1. The application can effectively promote the settlement of copper-containing catalyst by adding a specific additive to the reaction system of catalytic hydrogenation reaction and stirring and standing, so that the copper-containing catalyst is quickly separated from the organic reaction system, the separation efficiency of the catalyst is greatly improved, and the problems of additional separation equipment and complex operation process in the traditional method are solved.
[0013] 2. The application adopts the way of static stratification, so that the copper-containing catalyst can be smoothly settled in the lowermost layer, the catalyst residue in the reaction product is avoided, the purity and stability of the catalytic hydrogenation product are significantly improved, and the problems of reduced purity and stability caused by catalyst residue in the traditional method are overcome.
[0014] 3. The copper-containing catalyst is conveniently separated by the conventional method of reduced pressure filtration, the high activity and stability of the catalyst are maintained, the efficient recycling of the catalyst is realized, the resource utilization efficiency is improved, the generation of heavy metal waste is reduced, and the environmental protection requirements are met.
[0015] 4. The additive used in the application has good selectivity and stability, can effectively distinguish the copper-containing catalyst from the reaction product, avoids the mixing of non-specific substances, and improves the selectivity of subsequent reactions and the purity of products.
[0016] 5. The method of the application is simple to operate, the materials used are easy to obtain, and it is easy to scale up production, has significant economic benefits and practical value, can be widely applied to the post-treatment of various copper-containing catalysts, and has good popularization and application prospect. DETAILED DESCRIPTION
[0017] Unless specifically defined, the terms "above", "below" described in the application include the number.
[0018] The skilled person is aware of the meaning and scope of copper-containing catalysts commonly used in catalytic hydrogenation reactions, which include but are not limited to: catalysts with elemental copper as the active component, such as copper powder catalysts, copper wire catalysts; catalysts with copper oxides as the active component, such as cuprous oxide (Cu2O) catalysts, cupric oxide (CuO) catalysts; catalysts with copper compounds as the active component, such as copper sulfate (CuSO4) catalysts, copper chloride (CuCl2) catalysts, copper chromite catalysts; supported copper-containing catalysts, such as copper supported on alumina (Al2O3) catalysts, copper supported on activated carbon (AC) catalysts, copper supported on silica (SiO2) catalysts; composite copper-containing catalysts, such as copper-nickel (Cu-Ni) composite catalysts, copper-zinc (Cu-Zn) composite catalysts, copper-rhodium (Cu-Rh) composite catalysts. Preferred copper-containing catalysts suitable for separation by the method of the present application include: catalysts with copper compounds as the active component, such as copper sulfate (CuSO4) catalysts, copper chloride (CuCl2) catalysts, copper chromite catalysts; and supported copper-containing catalysts, such as copper supported on alumina (Al2O3) catalysts, copper supported on activated carbon (AC) catalysts, copper supported on silica (SiO2) catalysts.
[0019] The auxiliary agent of the present application is preferably a chloride (i.e. hydrochloride) or sulfate of a divalent or trivalent metal. Preferably, the metal is selected from magnesium, iron, aluminium; more preferably, the auxiliary agent is selected from magnesium chloride, aluminium chloride, iron chloride, magnesium sulfate, aluminium sulfate, iron sulfate. Each of the salts described herein includes hydrates thereof, for example "magnesium chloride" includes both anhydrous magnesium chloride and the hexahydrate magnesium chloride and the like. The auxiliary agent can be added directly as a solid powder or as an aqueous solution. In a preferred embodiment, the auxiliary agent is added as an aqueous solution, the concentration of the auxiliary agent in the solution (in terms of the weight of solute (g) per volume of solution (100 ml); in the case of hydrates, the weight of anhydrous solute per volume of solution) being in the range 10 to 35%, preferably 15-30% or 20-30%, at the temperature at which the solution is used.
[0020] Catalytic hydrogenation reactions suitable for post-treatment by the method of the present application include but are not limited to hydrogenation reactions catalysed using supported copper-containing catalysts, such as copper supported on alumina (Al2O3) catalysts, copper supported on activated carbon (AC) catalysts, copper supported on silica (SiO2) catalysts. The reaction system for the catalytic hydrogenation reaction is an organic solvent system, including but not limited to toluene, ethanol, acetone, tetrahydrofuran, ethyl acetate, dichloromethane, n-hexane, isopropanol, acetonitrile, butanone and the like, and there is no particular restriction on the parameters such as density and viscosity of the reaction system, for example the density can be in the range 0.6-1.2 g / cm3.3 a solvent system having a viscosity in the range of 0.5-50 cP (centipoise).
[0021] The amount of the additive (calculated as the content of the solid component of the additive, the same below in the case of using a solution) added to the reaction system can be 20-80%, preferably 30-70%, more preferably 40-60% by weight of the reaction system (including the weight of the reactants, the solvent carrier and the catalyst). The weight ratio of the additive (calculated as the content of the solid anhydrous component of the additive, the same below in the case of using a solution or hydrate) to the copper-containing catalyst used in the reaction is 1:1-50:1, preferably 5:1-30:1, more preferably 10:1-20:1.
[0022] The temperature for the post-treatment is not particularly limited and can be determined by a person skilled in the art according to the actual situation, for example, room temperature. The time for stirring and standing is also not particularly limited and can be determined by a person skilled in the art according to the actual situation.
[0023] After the post-treatment method of the present application is implemented, the reaction system to which the additive is added is allowed to stand and stratify, the upper clear liquid contains the crude product of the reaction product, the middle layer of the additive can be recycled, and the lowermost layer is the copper-containing catalyst. Both the additive and the copper-containing catalyst can be conveniently recovered and reused using conventional methods in the art, for example, in a new catalytic hydrogenation reaction.
[0024] In one specific embodiment, the method of the present application can comprise the following steps:
[0025] Step 1: adding an additive to the reaction system of the catalytic hydrogenation reaction and stirring;
[0026] Step 2: standing and stratifying;
[0027] and optionally comprising the following steps:
[0028] Step 3: filtering and separating the copper-containing catalyst; and / or
[0029] Step 4: washing and drying the copper-containing catalyst.
[0030] The step 1 comprises:
[0031] Step 101: adding an additive to the reaction system, the additive being selected from one or more of a magnesium chloride solution, an aluminum chloride solution, an iron chloride solution, a magnesium sulfate solution, an aluminum sulfate solution, an iron sulfate solution;
[0032] Step 102: stirring at room temperature for 1-2 hours to allow the copper-containing catalyst to be fully mixed with the additive.
[0033] The step 2 comprises:
[0034] Step 201: Let the reaction system stand for 2-4 hours naturally, so that the copper-containing catalyst settles to the bottom of the reaction system;
[0035] Step 202: Observe the layering of the reaction system, and confirm that the intermediate layer is the auxiliary agent layer and the lower layer is the copper-containing catalyst layer;
[0036] Step 203: Take the supernatant, which contains the crude product of the reaction.
[0037] The step 3 includes:
[0038] Step 301: Add the reaction system to a filtering device;
[0039] Step 302: Remove the liquid by filtration, and collect the copper-containing catalyst.
[0040] The step 4 includes:
[0041] Step 401: Wash the copper-containing catalyst with deionized water for 3-5 times;
[0042] Step 402: Dry the copper-containing catalyst at 60-80°C for 4-8 hours to obtain a dried copper-containing catalyst.
[0043] Example
[0044] The following examples are only used to illustrate the present application, and are not intended to limit the protection scope of the application.
[0045] The catalytic hydrogenation reaction was carried out using the method of US4052341A Example III, and the ingredients and their amounts were consistent with the description of Example III, including using 26.3g of copper chromite as the catalyst. After the reaction was completed, 200g of a 30% magnesium chloride solution was added to the reaction liquid, and stirred at room temperature for 1h, and then allowed to stand and layer. The supernatant (organic phase) contained the crude product of the reaction, the intermediate layer (aqueous phase) was the auxiliary agent, and the copper-containing catalyst all settled to the bottom layer. The copper-containing catalyst was separated by vacuum filtration, washed and dried, and the weight was measured to be 25.4g, indicating that the recovery rate of the copper-containing catalyst was as high as 96.6%, and all the operations were completed in a very short time.
[0046] Comparative Example 1
[0047] The catalytic hydrogenation reaction was carried out using the method of US4052341A Example III, and the ingredients and their amounts were consistent with the description of Example III, including using 26.3g of copper chromite as the catalyst. After the reaction was completed, 200g of a 30% magnesium chloride solution was added to the reaction liquid, and stirred at room temperature for 1h, and then allowed to stand and layer. The supernatant (organic phase) contained the crude product of the reaction, the intermediate layer (aqueous phase) was the auxiliary agent, and the copper-containing catalyst all settled to the bottom layer. The copper-containing catalyst was separated by vacuum filtration, washed and dried, and the weight was measured to be 25.4g, indicating that the recovery rate of the copper-containing catalyst was as high as 96.6%, and all the operations were completed in a very short time.
[0048] Comparative Example 2
[0049] The catalytic hydrogenation reaction was carried out using the method of US4052341A Example III, and the ingredients and their amounts were also consistent with the description of Example III, including the use of 26.3g of copper chromite as a catalyst. After the reaction was completed, 200g of a 25% sodium chloride solution was added to the reaction liquid, stirred at room temperature for 1h, and after standing for 8 hours, no obvious solid sedimentation was observed, and the copper-containing catalyst could not be recovered by standing and sedimentation.
Claims
1. A method for the work-up of a copper-containing catalyst, characterized in that comprising the steps of: (1) adding an auxiliary agent to a reaction system for catalytic hydrogenation reaction, wherein the reaction system contains a copper-containing catalyst, and the auxiliary agent is an inorganic salt; (2) standing.
2. The method according to claim 1, further comprising the steps of: (3) separating the copper-containing catalyst by filtration; and / or (4) washing and drying the copper-containing catalyst.
3. The method according to claim 1 or 2, wherein the copper-containing catalyst is selected from the group consisting of a catalyst with copper element as active component, a catalyst with a compound of copper as active component, a supported copper-containing catalyst, a composite copper-containing catalyst.
4. The method according to claim 3, wherein the copper-containing catalyst is selected from the group consisting of copper powder catalyst, copper wire catalyst, cuprous oxide (Cu2C) catalyst, cupric oxide (CuO) catalyst, copper sulfate (CuSO4) catalyst, copper chloride (CuCl2) catalyst, copper chromite catalyst, copper supported on alumina (Al2O3) catalyst, copper supported on activated carbon (AC) catalyst, copper supported on silica (SiO2) catalyst, copper-nickel (Cu-Ni) composite catalyst, copper-zinc (Cu-Zn) composite catalyst, copper-rhodium (Cu-Rh) composite catalyst.
5. The method according to claim 4, wherein the copper-containing catalyst is selected from the group consisting of copper sulfate (CuSO4) catalyst, copper chloride (CuCl2) catalyst, copper chromite catalyst, copper supported on alumina (Al2O3) catalyst, copper supported on activated carbon (AC) catalyst, copper supported on silica (SiO2) catalyst.
6. The method according to any one of claims 1-5, wherein the auxiliary agent is a chloride or sulfate of a divalent or trivalent metal.
7. The method according to claim 6, wherein the metal is selected from the group consisting of magnesium, iron, aluminum.
8. The method according to claim 7, wherein the auxiliary agent is selected from the group consisting of magnesium chloride, aluminum chloride, iron chloride, magnesium sulfate, aluminum sulfate, iron sulfate.
9. The method according to any one of claims 6-8, wherein the auxiliary agent is added in the form of an aqueous solution.