Recovery agents for recovering rhodium-phosphine complex catalysts, their preparation methods and applications

Abstract

This invention discloses a recovery agent for recovering rhodium-phosphine complex catalysts, its preparation method, and its application. The recovery agent comprises a support and a modifier, wherein the modifier is selected from at least one of chitosan and its derivatives. The recovery agent provided by this invention is highly efficient and environmentally friendly, its preparation method is simple, the recovery of rhodium-phosphine complex catalysts is easy to operate, and energy consumption is low. It not only avoids the waste of precious resources, but also effectively reduces the industrial production cost of carbonyl synthesis when applied to carbonyl synthesis reactions.

Description

Technical Field

[0001] This invention relates to a recovery agent for recovering rhodium-phosphine complex catalysts, its preparation method, and its application. Specifically, it relates to a recovery agent for recovering rhodium-phosphine complex catalysts, a method for preparing the recovery agent, a method for recovering rhodium-phosphine complex catalysts using the recovery agent, the recovered catalyst, and its application. Background Technology

[0002] Rhodium-phosphine complex catalysts are the most commonly used catalytic systems in carbonyl synthesis reactions, with wide industrial applications, primarily for the preparation of aldehydes and alcohols. Rhodium-phosphine complex catalysts use the rhodium atom as the active center and triphenylphosphine as the ligand. Rhodium, a precious metal, is expensive, and natural resources are relatively scarce; its price has risen significantly and remained high in recent years. Therefore, in hydroformylation applications, multiple repetitions are necessary to reduce production costs.

[0003] The main reasons for rhodium catalyst deactivation are the introduction of poisons and inhibitors. Additionally, with prolonged operating time and increased reaction temperature, rhodium atoms "bridge" to form chelates, leading to deactivation. One class of substances that reduce catalyst activity are inhibitors, such as 2-hexylhexenal and propyldiphenylphosphine. These substances can compete with olefins for coordination, reducing catalyst activity, but they can only form very weak coordination bonds with rhodium, and the coordination can be reversed. Another class of substances that reduce rhodium catalyst activity includes halides (such as HCl) and sulfides (such as H₂S, COS, and CH₃SH). These are poisons that poison rhodium-phosphine complexes. These substances can form strong coordination bonds with rhodium, occupying the rhodium coordination center and preventing the catalyst from reacting with olefins. Because the concentration of rhodium in the reaction is very low, even a small amount of these compounds can completely deactivate the catalyst.

[0004] Existing technologies disclose several methods for recovering and reusing rhodium-phosphine complex catalysts. For example, Japanese Patent JP 56265948 discloses a method for recovering liquid waste catalysts by incineration. In an apparatus for producing 2-ethylhexanol using a rhodium-phosphine complex as a catalyst, a solution containing the rhodium-phosphine catalyst is separated by distillation and then recycled back into the hydroformylation reactor. However, during recycling, the catalyst activity decreases, and high-boiling-point byproducts gradually accumulate. Therefore, a portion of the catalyst solution must be released to remove high-boiling-point substances and regenerate the catalyst. A method for recovering rhodium involves distilling off the aldehyde from the hydroformylation reaction product, concentrating the bottom fraction, and then sending the concentrated solution into a submerged combustion chamber for combustion at 1150°C for 20 hours. The submerged combustion chamber contains 0.3 m³ of fuel. 3 Water is used to absorb combustion gases. Phosphorus in the catalyst is converted into phosphine oxide and recovered in the form of phosphoric acid aqueous solution. Rhodium is left in the water in a suspended state. After filtration, rhodium is obtained with a recovery rate of up to 95%.

[0005] Patent CN111020200B discloses that rhodium-containing waste liquid is mixed with wood chips for initial incineration, followed by a first acid wash and water wash, then a second incineration, acid wash and water wash, alkali wash and water wash, and then reacted with sulfate to obtain a rhodium-containing filtrate. Finally, an active metal is added to replace the rhodium to obtain elemental rhodium.

[0006] Patent CN110760689B discloses that after concentrating rhodium-containing waste liquid, it is incinerated, and then reacted with chlorine gas to obtain rhodium chloride, which is then purified by washing to obtain rhodium chloride or metallic rhodium.

[0007] Although the above methods have different process steps, the essence of incineration remains unchanged. The main disadvantage of incineration is that it is not environmentally friendly. Incineration produces a large amount of waste gas, and subsequent treatment will produce a large amount of acid water or wastewater. In addition, the process is cumbersome and the operation is complicated. Moreover, incineration will cause some rhodium to sublimate and be lost. Overall, this method is difficult to operate, easily causes rhodium loss, and does not have industrialization advantages.

[0008] The combustion method involves mixing spent rhodium catalyst containing organophosphorus ligands with alkaline compounds of Group IA or IIA elements. During combustion, a large number of bubbles are generated, which can easily cause the molten liquid to overflow the container, resulting in rhodium loss. In addition, the combustion temperature of the combustion method is high, and it is easy to ignite when the organic content is high. The smoke will carry away some rhodium. When the rhodium catalyst is converted into a rhodium-soluble salt solution after combustion, the titration with ammonia water to form rhodium hydroxide precipitate can easily cause an excess of amine to form rhodium complexes, resulting in further loss of rhodium. Therefore, the rhodium recovery rate of the combustion method is low.

[0009] In addition to the methods mentioned above, wet recovery methods are also used to recover rhodium from spent catalysts. These wet recovery methods include extraction, precipitation, oxidative distillation, washing, adsorption separation, and chemical activation.

[0010] Japanese Patent JP 492121793 discloses a method for thoroughly separating a mixture of rhodium-phosphine complex catalyst and high-boiling organic distillation residue from high-boiling organic matter or coke-like distillation residue generated by an organic reaction. Selective adsorbents such as carbonates or alkaline earth metal silicates are added to adsorb the old phosphine complex catalyst. Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, or xylene are used as detergents to thoroughly remove the high-boiling distillation residue. Finally, a polar solvent containing a small amount of phosphine, such as alcohol, ether, tetrahydrofuran, or ethyl acetate, is used to dissolve the rhodium-phosphine complex catalyst from the adsorbent, resulting in a high rhodium recovery rate.

[0011] Patent CN101177306B discloses the use of a mixture of inorganic acid and oxidant to digest a non-catalyst organic solvent to obtain a digestion solution, then neutralizing the digestion solution with alkali to prepare a hydrated rhodium oxide precipitate, dissolving the precipitate with hydrochloric acid to obtain a rhodium chloride solution, removing metal impurity ions such as copper, iron, nickel, calcium and chromium through an ion exchange resin, and then refining by recrystallization to obtain high-purity hydrated rhodium chloride.

[0012] Patent CN103498056B discloses a method of adding reactive metals (magnesium, aluminum, zinc, etc.) to rhodium waste liquid to induce a displacement reaction, thereby displacing rhodium. The excess solid is then dissolved using hydrochloric acid to obtain elemental rhodium. The drawbacks of this method are that not all forms of rhodium can be recovered, resulting in a low rhodium recovery rate. Furthermore, the need for hydrochloric acid dissolution generates waste acid, making industrial-scale application difficult.

[0013] In patent CN111996386B, inorganic acid and oxidant are added to the waste catalyst for acidification and oxidation. Then, a mixture of oxalic acid and formic acid is used to obtain partial precipitation. Sodium sulfide is added to the filtrate to obtain further precipitation. The precipitate is dissolved in aqua regia, and the pH is adjusted to 8-9 to obtain rhodium hydroxide precipitate. This precipitate is then dissolved in acid, and formic acid and hydrogen are used for reduction to obtain rhodium powder. The disadvantages of this method are that it generates a large amount of waste acid solution and wastewater, and the process is relatively cumbersome with a long post-treatment process, which to some extent affects the rhodium recovery rate.

[0014] Patent CN102923796B discloses a method of adding a certain amount of silica solid adsorbent to a waste rhodium catalyst from a carbonyl synthesis reaction, then placing it in a high-temperature furnace for dry distillation and roasting at 550℃ to 650℃. The residue obtained from the dry distillation and roasting is then mixed with 10 to 30 times the weight of the roasting residue in concentrated hydrochloric acid, and sufficient ozone is introduced into the system at a temperature range of 80℃ to 100℃ until no black or gray particles remain. The mixture is then filtered and washed to obtain a crude rhodium chloride solution. The crude rhodium chloride solution is then treated with ion exchange to remove Fe, Ni, Ca, and other ionic impurities, and finally concentrated and dried to obtain hydrated rhodium chloride.

[0015] Existing wet recovery methods suffer from low overall rhodium recovery rates due to factors such as the strong binding affinity between metallic rhodium and organophosphorus ligands, the stability of polynuclear rhodium complexes, the low rhodium concentration in catalysts, and the viscosity of waste liquid. These factors make it difficult for rhodium in the waste liquid to react with precipitants or reducing agents, and it cannot be fully adsorbed by adsorbents.

[0016] Therefore, it is of great significance to develop a highly efficient, environmentally friendly, easy-to-operate, and low-energy-consumption rhodium-phosphine complex catalyst recovery agent and recovery method. Summary of the Invention

[0017] To address the aforementioned problems in existing technologies, the present invention aims to provide a recovery agent for recovering rhodium-phosphine complex catalysts, its preparation method, and its application. The recovery agent provided by this invention is highly efficient and environmentally friendly, its preparation method is simple, the recovery of rhodium-phosphine complex catalysts is easy to operate, and energy consumption is low. This not only avoids the waste of precious resources, but also effectively reduces the industrial production cost of carbonyl synthesis when applied to carbonyl synthesis reactions.

[0018] To achieve the above objectives, the present invention adopts the following technical solution:

[0019] In a first aspect, the present invention provides a recovery agent for recovering rhodium-phosphine complex catalysts, the recovery agent comprising a support and a modifier, wherein the support is a covalent organic framework material and the modifier is selected from at least one of chitosan and its derivatives.

[0020] The recovery agent of this invention is obtained by modifying covalent organic frameworks (COFs) with chitosan-like substances. COFs have a large specific surface area and contain a large number of heteroatoms such as oxygen and nitrogen, which can coordinate and bind with rhodium ions, thus achieving the recovery of rhodium ions from waste liquid. Chitosan molecules contain a large number of hydroxyl and amino groups, which stably bind with COFs through hydrogen bonds, forming cage-like molecules with a network-like structure, further enhancing the adsorption effect on rhodium ions. Therefore, the recovery agent of this invention is used to recover rhodium-phosphine complex catalysts from waste liquid with a high recovery rate. The rhodium content in the treated waste liquid from deactivated rhodium-phosphine complex catalysts (with no limit on concentration, for example, a concentration of 0.1% or more based on rhodium) is <10 ppm.

[0021] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0022] Preferably, the modifier is selected from one or more of chitosan, hydroxymethyl chitosan, hydroxypropyl chitosan, N-methyl chitosan, or β-cyclodextrin-grafted chitosan.

[0023] Preferably, the covalent organic framework material includes one or more of COF-1, COF-2, COF-3, COF-4, or COF-5.

[0024] Preferably, the mass ratio of the carrier to the modifier is 1:(2-10), for example 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:9 or 1:10, etc., preferably 1:(2-6), more preferably 1:(2-4).

[0025] In a second aspect, the present invention provides a method for preparing a recovery agent for recovering a rhodium-phosphine complex catalyst as described in the first aspect, the method comprising the following steps:

[0026] The solvent is treated with a carrier and a modifier to obtain a recoverable agent.

[0027] Preferably, the solvent is water.

[0028] In one implementation, the water is deionized water.

[0029] Preferably, the volume ratio of the solvent to the total mass of the carrier and the modifier is (1-4) mL:1g, for example, 1 mL:1g, 1.2 mL:1g, 1.4 mL:1g, 1.6 mL:1g, 1.8 mL:1g, 2 mL:1g, 2.3 mL:1g, 2.5 mL:1g, 2.8 mL:1g, 3 mL:1g, 3.2 mL:1g, 3.3 mL:1g, 3.6 mL:1g, 3.8 mL:1g, or 4 mL:1g, etc., preferably (1-2.5) mL:1g.

[0030] Preferably, the processing temperature is 80℃~120℃, such as 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃ or 120℃, etc., with 80℃~100℃ being the most preferred.

[0031] Preferably, the processing time is 2 to 8 hours, such as 2 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 6 hours, 7 hours or 8 hours, with 2 to 4 hours being the most preferred.

[0032] Preferably, the processing is accompanied by stirring, and the stirring speed is 150 r / min to 300 r / min, such as 150 r / min, 175 r / min, 200 r / min, 220 r / min, 240 r / min, 260 r / min, 280 r / min or 300 r / min.

[0033] Preferably, the process includes separation, washing, and drying steps.

[0034] Preferably, the separation method is filtration.

[0035] Thirdly, the present invention provides a method for recovering a rhodium-phosphine complex catalyst, the recovery method comprising the following steps:

[0036] The recovery agent described in the first aspect is added to the waste liquid containing the rhodium-phosphine complex catalyst for adsorption treatment, thereby realizing the recovery of the rhodium-phosphine complex catalyst.

[0037] The recovery method of the present invention utilizes the above-mentioned recovery agent to recover the catalyst from the waste liquid containing the rhodium-phosphine complex catalyst. It has the advantages of high recovery rate, simple process and convenient operation, which greatly improves the recovery efficiency of the rhodium-phosphine complex catalyst. Moreover, the recovered catalyst can be used directly, for example, it can be used directly in the carbonyl synthesis reaction, thereby reducing the production cost of the carbonyl synthesis reaction.

[0038] The recovery method of the present invention overcomes the shortcomings of existing rhodium catalyst recovery methods, such as complicated operation and low recovery rate, and has high industrial application value.

[0039] In this invention, the source of the waste liquid containing the rhodium-phosphine complex catalyst is not limited; for example, it can be obtained by concentrating the carbonyl synthesis waste liquid.

[0040] Preferably, the mass concentration of the waste liquid, calculated as rhodium, is 0.1% to 2.0%, for example, 0.1%, 0.12%, 0.13%, 0.15%, 0.17%, 0.18%, or 0.2%.

[0041] Preferably, the temperature of the adsorption treatment is 30℃~60℃, such as 30℃, 35℃, 40℃, 45℃, 50℃, 55℃ or 60℃, and more preferably 30℃~50℃.

[0042] Preferably, the adsorption treatment time is 4 to 12 hours, such as 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, with 4 to 7 hours being the most preferred.

[0043] Preferably, the adsorption treatment is carried out under stirring conditions, and the stirring speed is 50 r / min to 100 r / min, for example, 50 r / min, 60 r / min, 70 r / min, 80 r / min, 90 r / min or 100 r / min.

[0044] Preferably, the adsorption treatment is followed by post-treatment, which includes separation, washing, and drying. The separation method is not limited; for example, it can be filtration.

[0045] Preferably, in the post-processing step, the detergent used for washing can be water.

[0046] Fourthly, the present invention provides a recovered catalyst obtained by the recovery method described in the third aspect.

[0047] Fifthly, the present invention provides the application of the recovered catalyst as described in the fourth aspect in a carbonyl synthesis reaction, wherein the substrate and syngas undergo a carbonyl synthesis reaction in a solvent under the catalysis of the recovered catalyst to obtain a carbonyl synthesis product.

[0048] The recovered catalyst obtained by this invention (which can be referred to as rhodium catalyst) can be directly applied to new carbonyl synthesis reactions. It has the advantages of mild reaction conditions, high olefin conversion rate, good product selectivity, and recyclability, which greatly reduces the catalyst cost in industrial carbonyl synthesis processes.

[0049] Preferably, the substrate includes any one of 1-butene, 1,3-pentadiene, isobutene, 5-methyl-1,4-hexadiene, 2,5-dihydrofuran, or 2,6-dimethyl-1,5-heptadiene.

[0050] Preferably, the synthesis gas is a mixture of H2 and CO.

[0051] Preferably, the molar ratio of H2 to CO in the mixed gas is 1:1.

[0052] Preferably, the total pressure of the synthesis gas is 2.0 MPa-4.0 MPa, such as 2.0 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.5 MPa, 2.6 MPa, 2.8 MPa, 3.0 MPa, 3.5 MPa or 4.0 MPa.

[0053] Preferably, the mass ratio of the recovered catalyst to the substrate is (0.01 to 0.07):1, for example, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1 or 0.07:1, etc.

[0054] Preferably, the temperature of the carbonyl synthesis reaction is 80℃~120℃, such as 80℃, 90℃, 95℃, 100℃, 110℃, 115℃ or 120℃, and more preferably 80℃~100℃.

[0055] In this invention, the type of solvent is not specifically limited, but it is preferable to use solvents that can disperse the solvent. Solvents may be selected from isopropanol, ethanol, methanol, toluene, or a combination thereof.

[0056] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0057] Compared with existing technologies, the present invention has the following beneficial effects:

[0058] (1) The recovery agent provided by the present invention is efficient and environmentally friendly. Its preparation method is simple, and the operation of recovering rhodium-phosphine complex catalyst is simple and energy consumption is low.

[0059] (2) The recovery method of the present invention has the advantages of high recovery rate, simple process and convenient operation, which greatly improves the recovery efficiency of rhodium-phosphine complex catalyst, and the recovered catalyst can be used directly.

[0060] (3) The recovered catalyst obtained by the present invention can be directly applied to new carbonyl synthesis reactions. It has the advantages of mild reaction conditions, high olefin conversion rate, good product selectivity and recyclability, which greatly reduces the catalyst cost of carbonyl synthesis process in industry. Detailed Implementation

[0061] The embodiments of the present invention will be described in detail below with reference to the examples. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0062] Example 1

[0063] (1) Recovery agent and its preparation method:

[0064] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-1 support and the modifier is chitosan, and the mass ratio of the support to the modifier is 1:2.

[0065] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0066] At room temperature, 5.0 g of COF-1 support and 10.0 g of chitosan were added sequentially to 30 mL of deionized water. The mixture was stirred at 200 r / min, heated to 80 °C, and stirred at a constant temperature for 6 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 1.

[0067] (2) Recycling method:

[0068] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0069] Take 10g of 0.1% deactivated rhodium phosphine complex catalyst waste liquid (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 0.1:4:95.9), add recovery agent 1, start stirring at 100r / min, heat to 30℃, and maintain the temperature for 8 hours for adsorption. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 2.8ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled CAT1.

[0070] Example 2

[0071] (1) Recovery agent and its preparation method:

[0072] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-2 support and the modifier is hydroxymethyl chitosan, and the mass ratio of the support to the modifier is 1:4.

[0073] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0074] At room temperature, 5.0 g of COF-2 support and 20.0 g of hydroxymethyl chitosan were added sequentially to 50 mL of deionized water. The mixture was stirred at 200 r / min, heated to 100 °C, and stirred at a constant temperature for 4 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 2.

[0075] (2) Recycling method:

[0076] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0077] Take 10g of waste liquid containing 0.3% deactivated rhodium phosphine complex catalyst (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 0.3:12:87.7), add recovery agent 2, start stirring at 100r / min, heat to 40℃, and maintain the temperature for 8 hours. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 2.5ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled as CAT2.

[0078] Example 3

[0079] (1) Recovery agent and its preparation method:

[0080] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-3 support and the modifier is hydroxypropyl chitosan, and the mass ratio of the support to the modifier is 1:6.

[0081] The preparation method of the recovery agent provided in this embodiment includes the following steps: at room temperature, 5.0 g of COF-3 support and 30.0 g of hydroxypropyl chitosan are added sequentially to 50 mL of deionized water, stirring is started at a speed of 200 r / min, the temperature is raised to 100 °C, and the mixture is stirred at a constant temperature for 6 hours. The water is removed by rotary evaporation under reduced pressure to obtain the recovery agent for recovering the rhodium-phosphine complex catalyst, which is labeled as recovery agent 3.

[0082] (2) Recycling method:

[0083] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0084] Take 10g of 0.5% deactivated rhodium phosphine complex catalyst waste liquid (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 0.5:15:84.5), add recovery agent 3, start stirring at 100r / min, heat to 55℃, and maintain the temperature for 7 hours for adsorption. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 3.7ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled as CAT3.

[0085] Example 4

[0086] (1) Recovery agent and its preparation method:

[0087] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-3 support and the modifier is hydroxypropyl chitosan, and the mass ratio of the support to the modifier is 1:8.

[0088] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0089] At room temperature, 5.0 g of COF-3 support and 40.0 g of hydroxypropyl chitosan were added sequentially to 50 mL of deionized water. Stirring was started at 200 r / min, the temperature was raised to 100 °C, and the mixture was stirred at a constant temperature for 6 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 4.

[0090] (2) Recycling method:

[0091] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0092] Take 10g of waste liquid containing 0.7% deactivated rhodium phosphine complex catalyst (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 0.7:21:78.3), add recovery agent 4, start stirring at 100 r / min, heat to 60℃, and maintain the temperature for 10 hours. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 5.2 ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled CAT4.

[0093] Example 5

[0094] (1) Recovery agent and its preparation method:

[0095] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-3 support and the modifier is hydroxypropyl chitosan, and the mass ratio of the support to the modifier is 1:10.

[0096] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0097] At room temperature, 5.0 g of COF-3 support and 50.0 g of hydroxypropyl chitosan were added sequentially to 60 mL of deionized water. Stirring was started at 200 r / min, the temperature was raised to 100 °C, and the mixture was stirred at a constant temperature for 8 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 5.

[0098] (2) Recycling method:

[0099] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0100] Take 10g of waste liquid containing 0.7% deactivated rhodium phosphine complex catalyst (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 0.7:21:78.3), add recovery agent 5, start stirring at 100r / min, heat to 45℃, and maintain the temperature for 10 hours. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 5.6ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled CAT5.

[0101] Example 6

[0102] (1) Recovery agent and its preparation method:

[0103] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-4 support and the modifier is N-methyl chitosan, and the mass ratio of the support to the modifier is 1:2.

[0104] The preparation method of the recovery agent provided in this embodiment includes the following steps: at room temperature, 5.0 g of COF-4 support and 10.0 g of N-methyl chitosan are added sequentially to 20 mL of deionized water, stirring is started at a speed of 200 r / min, the temperature is raised to 120 °C, and the mixture is stirred at a constant temperature for 6 hours. The water is removed by rotary evaporation under reduced pressure to obtain the recovery agent for recovering the rhodium-phosphine complex catalyst, which is labeled as recovery agent 6.

[0105] (2) Recycling method:

[0106] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0107] Take 10g of waste liquid containing 1.0% deactivated rhodium phosphine complex catalyst (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 1.0:30:69), add recovery agent 6, start stirring at 100r / min, heat to 30℃, and maintain the temperature for 8 hours for adsorption. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 6.8ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled as CAT6.

[0108] Example 7

[0109] (1) Recovery agent and its preparation method:

[0110] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-5 support and the modifier is N-methylchitosan, and the mass ratio of the support to the modifier is 1:4.

[0111] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0112] At room temperature, 5.0 g of COF-5 support and 20.0 g of N-methyl chitosan were added sequentially to 40 mL of deionized water. Stirring was started at 200 r / min, the temperature was raised to 100 °C, and the mixture was stirred at a constant temperature for 6 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 7.

[0113] (2) Recycling method:

[0114] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0115] Take 10g of 1.5% deactivated rhodium phosphine complex catalyst waste liquid (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 1.5:45:53.5), add recovery agent 7, start stirring at 100r / min, heat to 45℃, and maintain the temperature for 8 hours for adsorption. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 6.8ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled as CAT7.

[0116] Example 8

[0117] (1) Recovery agent and its preparation method:

[0118] A recovery agent for recovering rhodium-phosphine complex catalysts includes a support and a modifier, wherein the support is a COF-3 support and the modifier is N-methyl chitosan, and the mass ratio of the support to the modifier is 1:4.

[0119] The method for preparing the recovery agent provided in this embodiment includes the following steps:

[0120] At room temperature, 5.0 g of COF-3 support and 20.0 g of N-methyl chitosan were added sequentially to 30 mL of deionized water. Stirring was started at 200 r / min, the temperature was raised to 100 °C, and the mixture was stirred at a constant temperature for 6 hours. The water was removed by rotary evaporation under reduced pressure to obtain a recovery agent for recovering the rhodium-phosphine complex catalyst, labeled as recovery agent 8.

[0121] (2) Recycling method:

[0122] A method for recovering a rhodium-phosphine complex catalyst includes the following steps:

[0123] Take 10g of 2.0% deactivated rhodium phosphine complex catalyst waste liquid (concentration is based on rhodium, mass ratio of rhodium:ligand:polymer = 2.0:60:38), add recovery agent 8, start stirring at 100r / min, heat to 40℃, and maintain the temperature for 12 hours for adsorption. Take a small amount of waste liquid and use ICP to detect the rhodium content, which is 8.7ppm. Stop the adsorption, filter, wash twice with deionized water, and dry to constant weight in a vacuum drying oven at 80℃ to obtain the recovered catalyst, labeled as CAT8.

[0124] Application Example 1

[0125] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 2.1 g of catalyst CAT-1 is uniformly dispersed in 30 g of toluene to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of 1-butene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 120 °C and stirred for 8 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the conversion rate of 1-butene is 92.4%, and the selectivity for n-pentanal is 97.3%.

[0126] Application Example 2

[0127] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 2.1 g of catalyst CAT-2 is uniformly dispersed in 30 g of isopropanol to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of 1,3-pentadiene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 100 °C and stirred for 8 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the conversion rate of 1,3-pentadiene is 94.6%, and the selectivity for 3-hexenal is 97.9%.

[0128] Application Example 3

[0129] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 1.8 g of catalyst CAT-3 is uniformly dispersed in 30 g of methanol to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of isobutylene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 100 °C and stirred for 8 h. After cooling to room temperature and releasing the pressure, the reaction solution is analyzed using gas chromatography. The results show that the isobutylene conversion rate is 97.1%, and the selectivity for isovaleraldehyde is 98.5%.

[0130] Application Example 4

[0131] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 1.5 g of catalyst CAT-4 is uniformly dispersed in 30 g of methanol to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of isobutylene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 100 °C and stirred for 6 h. After cooling to room temperature and releasing the pressure, the reaction solution is analyzed using gas chromatography. The results show that the isobutylene conversion rate is 98.3% and the isovaleraldehyde selectivity is 98.9%.

[0132] Application Example 5

[0133] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 1.5 g of catalyst CAT-5 is uniformly dispersed in 30 g of ethanol to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of isobutylene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 80 °C and stirred for 6 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the isobutylene conversion rate is 98.5% and the selectivity for isovaleraldehyde is 99.1%.

[0134] Application Example 6

[0135] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 0.9 g of catalyst CAT-6 is uniformly dispersed in 30 g of methanol to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of 5-methyl-1,4-hexadiene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 80 °C and stirred for 6 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the conversion rate of 5-methyl-1,4-hexadiene is 98.6%, and the selectivity of 6-methyl-5-heptenal is 99.3%.

[0136] Application Example 7

[0137] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 0.9 g of catalyst CAT-7 is uniformly dispersed in 30 g of toluene to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of 2,6-dimethyl-1,5-heptadiene are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 80 °C and stirred for 4 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the conversion rate of 2,6-dimethyl-1,5-heptadiene is 99.2%, and the selectivity of citronellol is 99.6%.

[0138] Application Example 8

[0139] An application of a recovered catalyst in a carbonyl synthesis reaction includes the following steps: 0.3 g of catalyst CAT-8 is uniformly dispersed in 30 g of toluene to obtain a catalyst suspension. An autoclave is purged three times with nitrogen and syngas (CO / H2 = 1:1 molar ratio) to fill the autoclave with syngas. The catalyst suspension and 30.0 g of 2,5-dihydrofuran are pumped into the autoclave, and syngas is introduced until the pressure reaches 4.0 MPa. The temperature is raised to 80 °C and stirred for 4 h. After cooling to room temperature and depressurizing, the reaction solution is analyzed using gas chromatography. The results show that the conversion rate of 2,5-dihydrofuran is 98.9%, and the selectivity of tetrahydrofuran-3-carboxaldehyde is 99.3%.

[0140] As can be seen from the above, the recovered catalyst obtained by this invention (which can be referred to as rhodium catalyst) can be directly applied to new carbonyl synthesis reactions. It has the advantages of mild reaction conditions, high olefin conversion rate, good product selectivity, and recyclability, which greatly reduces the catalyst cost of carbonyl synthesis process in industry.

[0141] Application Example 9: This application example is a catalyst reuse experiment. After the reaction in Application Example 7 was completed, the reaction solution was filtered to recover the catalyst CAT-7, which was then used in a reuse experiment, following the same procedure as in Application Example 7. The specific reaction conditions and the results of the reuse experiment are shown in Table 1.

[0142] Table 1

[0143] Apply catalyst concentration Temperature (°C) Time (h) Conversion rate Selective 1 3.0％ 80 4 99.2％ 99.6％ 2 3.0％ 80 4 98.7％ 99.4％ 3 3.0％ 80 6 99.2％ 98.7％ 4 3.0％ 100 4 99.2％ 98.9％ 5 3.0％ 100 4 99.1％ 98.6％ 6 3.0％ 100 4 99.0％ 98.6％

[0144] As shown in Table 1:

[0145] (1) The recovery agent provided by the present invention is efficient and environmentally friendly. Its preparation method is simple, and the operation of recovering rhodium-phosphine complex catalyst is simple and energy consumption is low.

[0146] (2) The recovery method of the present invention has the advantages of high recovery rate, simple process and convenient operation, which greatly improves the recovery efficiency of rhodium-phosphine complex catalyst, and the recovered catalyst can be used directly.

[0147] (3) The recovered catalyst obtained by the present invention can be directly applied to new carbonyl synthesis reactions. It has the advantages of mild reaction conditions, high olefin conversion rate, good product selectivity and recyclability, which greatly reduces the catalyst cost of carbonyl synthesis process in industry.

[0148] It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto.

[0149] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

[0150] The applicant declares that the detailed method of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. The application of a recycled catalyst in a carbonyl synthesis reaction, characterized in that, Under the catalysis of the recovered catalyst, the substrate and syngas undergo a carbonyl synthesis reaction in a solvent to obtain a carbonyl synthesis product; The method for preparing the recycled catalyst includes the following steps: A recovery agent is added to the waste liquid containing the rhodium-phosphine complex catalyst for adsorption treatment. After the adsorption treatment, post-treatment is carried out to obtain the recovered catalyst. The post-processing includes separation, washing, and drying; The recycling agent includes a carrier and a modifier, wherein the carrier is a covalent organic framework material and the modifier is selected from at least one of chitosan and its derivatives; The modifier is selected from one or more of chitosan, hydroxymethyl chitosan, hydroxypropyl chitosan, N-methyl chitosan, and β-cyclodextrin-grafted chitosan; The covalent organic framework material includes one or more of COF-1, COF-2, COF-3, COF-4, and COF-5.

2. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The mass ratio of the carrier to the modifier is 1:(2~10).

3. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The mass ratio of the carrier to the modifier is 1:(2~6).

4. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The mass ratio of the carrier to the modifier is 1:(2~4).

5. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The mass concentration of the waste liquid, calculated using rhodium, is 0.1% to 2.0%.

6. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The adsorption treatment temperature is 30℃~60℃.

7. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The adsorption treatment temperature is 30℃~50℃.

8. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The adsorption treatment time is 4 to 12 hours.

9. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The adsorption treatment time is 4 to 7 hours.

10. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The adsorption treatment is carried out under stirring conditions, and the stirring speed is 50 r / min to 100 r / min.

11. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The method for preparing the recovery agent includes the following steps: The solvent is treated with a carrier and a modifier to obtain a recovered agent.

12. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The solvent is water.

13. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The volume ratio of the solvent to the total mass of the carrier and the modifier is (1~4) mL:1 g.

14. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The volume ratio of the solvent to the total mass of the carrier and the modifier is (1~2.5) mL:1 g.

15. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The processing temperature is 80℃~120℃.

16. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The processing temperature is 80℃~100℃.

17. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The processing time is 2 to 8 hours.

18. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The processing time is 2 to 4 hours.

19. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The process involves stirring at a speed of 150 r / min to 300 r / min.

20. The application of the recovered catalyst according to claim 11 in the carbonyl synthesis reaction, characterized in that, The process involves separation, washing, and drying.

21. The application of the recovered catalyst according to claim 20 in the carbonyl synthesis reaction, characterized in that, The separation method is filtration.

22. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The substrate includes any one of 1-butene, 1,3-pentadiene, isobutene, 5-methyl-1,4-hexadiene, 2,5-dihydrofuran, and 2,6-dimethyl-1,5-heptadiene.

23. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The synthesis gas is a mixture of H2 and CO.

24. The application of the recovered catalyst according to claim 23 in the carbonyl synthesis reaction, characterized in that, In the mixed gas, the molar ratio of H2 to CO is 1:

1.

25. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The total pressure of the synthesis gas is 2.0 MPa-4.0 MPa.

26. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The mass ratio of the recovered catalyst to the substrate is (0.01~0.07):

1.

27. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The carbonyl synthesis reaction is carried out at a temperature of 80℃~120℃.

28. The application of the recovered catalyst according to claim 1 in the carbonyl synthesis reaction, characterized in that, The carbonyl synthesis reaction is carried out at a temperature of 80℃~100℃.