Magnetic catalyst for preparing cyclohexane carboxylic acid compound as well as preparation method and application of magnetic catalyst

Abstract

The invention relates to a magnetic catalyst for preparing cyclohexane carboxylic acid compounds and a preparation method and application thereof.The catalyst comprises an active metal A, an auxiliary metal B and a carrier material, the active metal A is one or more of ruthenium, rhodium and palladium, and the auxiliary metal B is one or more of copper, nickel and cobalt; the carrier material is one or more of ferric oxide, aluminum oxide and titanium dioxide; the method comprises the following steps: adding a catalyst and benzene carboxylic acid salt into a high-pressure reaction kettle, introducing hydrogen to replace air, introducing hydrogen with a certain pressure, stirring, heating, reacting, cooling, separating the catalyst, and finally acidifying the reaction liquid to obtain the cyclohexane carboxylic acid compound, and the benzene carboxylic acid salt is generated from benzene carboxylic acid and alkali in water. The catalyst disclosed by the invention has extremely high catalytic activity and selectivity in preparation of the cyclohexane carboxylic acid compound by hydrogenation of the benzene carboxylic acid compound, the reaction condition is mild, the catalyst cost is low, and the catalyst can be directly separated after the reaction is finished.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds and a preparation method and application thereof. Background Art

[0002] Cyclohexanecarboxylic acid compounds are an important class of chemical raw materials. As key monomers of polyester resins, they can significantly improve the performance of polyester products, such as heat resistance, chemical corrosion resistance and mechanical strength. Their unique molecular structure makes the coating resin containing this raw material have excellent weather resistance and adhesion, and has a wide range of applications in the fields of automobiles, construction, industrial protection, etc. In addition, cyclohexanecarboxylic acids can be used as precursors or intermediates for drug synthesis in the pharmaceutical field, and participate in the synthesis of compounds with specific activities; in the pesticide field, their special structure helps to improve the stability and medicinal properties of pesticide molecules.

[0003] Among the preparation methods of cyclohexanecarboxylic acid compounds, there are mainly esterification hydrogenation-hydrolysis method and direct hydrogenation method. In the esterification hydrogenation-hydrolysis method, benzene carboxylic acid reacts with alcohol (commonly methanol) to obtain benzene carboxylic acid methyl ester, the first step is to hydrogenate the benzene carboxylic acid methyl ester to obtain cyclohexane carboxylic acid methyl ester, and the second step is to hydrolyze the cyclohexane carboxylic acid methyl ester to obtain cyclohexane carboxylic acid. For example, CN1042327C reported earlier a method for hydrogenating dimethyl terephthalate to produce the corresponding dimethyl cyclohexanedicarboxylate, using alumina as a catalyst carrier, and palladium and nickel, platinum, ruthenium or a mixture of the second group VIII metal deposited on the alumina carrier. CN118063314A recently reported an ionic liquid catalyst prepared by using alkyl imidazole halides and Ru, Co, Al metal halides, and the conversion rate of dimethyl terephthalate hydrogenation and the selectivity of dimethyl cyclohexanedicarboxylate can reach more than 99%. CN104926649B discloses a method for preparing hydrogenated pyromellitic acid by hydrogenating tetrapropyl pyromellitic acid, which uses coconut shell activated carbon as a carrier, Ru, Pd, and Ce as active components, and the product yield reaches 97.4%, but the catalyst preparation method is complicated and is not conducive to industrial production, and too much metal content easily causes metal residues in the product, which brings difficulties to the purification of the product. Esterification hydrogenation-hydrolysis method has few side reactions and high reaction yield, but due to the need to undergo esterification first, hydrogenation, and final hydrolysis, the process steps are cumbersome and the reaction process usually requires higher pressure and temperature, and the reaction equipment has high requirements, resulting in high production costs and more energy consumption. And the direct hydrogenation method of benzene carboxylic acids, usually using water as a solvent, directly reacts with hydrogen under the action of a catalyst to generate cyclohexane carboxylic acids. For example, CN116023252A discloses a method for hydrogenating terephthalic acid, wherein terephthalic acid reacts with hydrogen in the presence of a catalyst, wherein the catalyst is a molecular sieve catalyst loaded with an active metal additive and an active metal palladium, wherein the active metal additive is selected from one or more of Ru, Rh, Os, Ir, Pt, Ag and Au, and after the molecular sieve is subjected to hydrothermal treatment and the active metal additive is added, the reaction activity of the catalyst and the selectivity of trans-1,4-cyclohexanedicarboxylic acid are significantly enhanced; this method has the advantages of fewer process steps and a simple process, but the acidity of the benzene carboxylic acid-water system is relatively strong, which can easily cause the deactivation of the catalyst and corrosion of the process equipment, and the solubility of benzene carboxylic acids in water is relatively low, making it difficult to achieve large-scale industrialization. In addition, the catalysts required for this process are mostly precious metal catalysts and the large loading amount leads to a high catalyst cost.

[0004] In order to solve the solubility problem of benzene carboxylic acids in water, US5118841A Eastman Company of the United States first reported a method for preparing 1,4-cyclohexanedicarboxylic acid by hydrogenation of terephthalate, taking terephthalic acid as an example, using 1% Ru / C as a catalyst, controlling the temperature at 200°C, and the reaction pressure at 10-14MPa, and reacting disodium terephthalate with hydrogen to generate disodium cyclohexanedicarboxylic acid. After the reaction, 1,4-cyclohexanedicarboxylic acid can be obtained by acidification with sulfuric acid. The yield of this method is about 90%, and the catalyst performance is still far from industrial production. In addition, the temperature and pressure required by this method are relatively harsh, and there are high requirements for the reaction equipment. The separation of the ruthenium carbon catalyst used after the reaction is also a thorny problem. CN111886217A Mitsubishi Corporation of Japan also reported that terephthalic acid was dissolved in an ammonia solution to obtain diammonium terephthalate, which was reacted with hydrogen under the action of a 2% Ru / C catalyst, and finally heated and concentrated to obtain 1,4-cyclohexanedicarboxylic acid. The reaction temperature was 60-90°C, the hydrogen pressure was 3-8MPa, and the yield of 1,4-cyclohexanedicarboxylic acid could reach 99%. The method reported in this patent has a good yield of 1,4-cyclohexanedicarboxylic acid, but the ammonia water used is extremely corrosive to the equipment, and the carboxylic acid ammonium salt generated by terephthalic acid and ammonia water is easily decomposed at high temperature, resulting in uncontrollable reaction. In addition, the catalyst in this patent has a high content of precious metals, resulting in a high catalyst cost. Summary of the invention

[0005] The purpose of the present invention is to provide a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds, which has extremely high catalytic activity and selectivity in the hydrogenation of benzenecarboxylic acid compounds to prepare cyclohexanecarboxylic acid compounds, and the catalyst cost is low, and the catalyst can be directly separated after the reaction is completed.

[0006] The technical solution adopted by the present invention to solve the above problems is: a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds, the magnetic catalyst comprising an active metal A, an auxiliary metal B and a carrier material, the active metal A is one or more of ruthenium, rhodium and palladium, the auxiliary metal B is one or more of copper, nickel and cobalt, and the carrier material is one or more of iron oxide, aluminum oxide and titanium dioxide.

[0007] Preferably, the active metal A is ruthenium and / or rhodium, the auxiliary metal B is copper and / or nickel, and the carrier material is iron oxide.

[0008] Preferably, the mass percentage content of active metal A in the magnetic catalyst is 0.1-20%; the mass percentage content of auxiliary metal B is 0.1-20%.

[0009] More preferably, the mass percentage content of active metal A in the magnetic catalyst is 0.5-3%; the mass percentage content of auxiliary metal B is 0.5-3%.

[0010] Another object of the present invention is to provide a method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds, comprising the following steps: (1) preparing a catalyst loaded with active metal A; (2) preparing an ammonia-coordinated metal hydroxide solution of auxiliary metal B; (3) In an inert gas protective atmosphere, the catalyst loaded with active metal A obtained in step (1) is mixed with the ammonia coordinated metal hydroxide solution of auxiliary metal B obtained in step (2), and stirred evenly at room temperature. A reducing agent is added dropwise under the protection of an inert gas atmosphere, and stirred until the ammonia coordinated metal hydroxide solution of metal B is completely adsorbed, thereby obtaining a catalyst loaded with both active metal A and auxiliary metal B.

[0011] Preferably, the specific steps of preparing the catalyst loaded with active metal A in step (1) are: preparing nanoparticle colloid of active metal A by using a polyol reduction method or a sol-gel method; dispersing the carrier material in a solvent, then adding the nanoparticle colloid of active metal A, centrifuging after loading, and obtaining the catalyst loaded with active metal A by vacuum freeze drying.

[0012] Preferably, the specific steps of preparing the ammonia-coordinated metal hydroxide solution of the auxiliary metal B in step (2) are: dissolving the metal salt corresponding to the auxiliary metal B in a solvent, adding an alkali to obtain a hydroxide precipitate, and after centrifugal separation, adding the hydroxide precipitate to ammonia water and stirring until dissolved to obtain an ammonia-coordinated metal hydroxide solution.

[0013] Preferably, the inert atmosphere in step (3) is one or more of nitrogen, argon and helium; the reducing agent is one or more of sodium borohydride, hydrazine hydrate and ascorbic acid; and the solvent in step (3) is water or alcohol.

[0014] More preferably, the reducing agent in step (3) is sodium borohydride; and the solvent in step (3) is one or more of methanol, ethanol, and ethylene glycol.

[0015] Another method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds comprises the following steps: (1) preparing an ammonia-coordinated metal hydroxide solution of auxiliary metal B; (2) preparing nanoparticle colloids of active metal A; (3) mixing the ammonia-coordinated metal hydroxide solution of the promoter metal B obtained in step (1) with the carrier, evaporating the solution in the system to dryness under magnetic stirring, and adding a reducing agent dropwise to the obtained solid powder under the protection of an inert atmosphere to obtain a catalyst loaded with the promoter metal B; (4) The nanoparticle colloid of active metal A prepared in step (2) is mixed with the catalyst loaded with promoter metal B prepared in step (3), stirred at room temperature until the nanoparticle colloid is completely adsorbed, and then centrifuged to obtain a catalyst loaded with both promoter metal B and active metal A.

[0016] Another object of the present invention is to provide an application of a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds, wherein the magnetic catalyst is used for hydrogenating benzenecarboxylic acid compounds to prepare cyclohexanecarboxylic acid compounds, comprising the following steps: (1) Benzene carboxylic acid compounds react with alkali in water to form benzoic acid salts; (2) adding a magnetic catalyst into a reaction device and adding the benzene carboxylic acid salt prepared in step (1); (3) Seal the reaction device and introduce hydrogen to replace the air in the reaction device, and fill the reaction device with hydrogen at a certain pressure; (4) heating the temperature to the reaction temperature under stirring, and obtaining a reaction solution after the reaction is completed; (5) The reaction solution is acidified to obtain cyclohexanecarboxylic acid compounds.

[0017] Preferably, the benzene carboxylic acid compound is one or more of benzoic acid, terephthalic acid, isophthalic acid, phthalic acid, trimesic acid, trimellitic acid, pyromellitic acid, pyromellitic acid, pyromellitic acid, pyromellitic acid, More preferably, the benzene carboxylic acid compound is terephthalic acid.

[0018] Preferably, the alkali is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.

[0019] More preferably, the base is sodium hydroxide.

[0020] Preferably, in step (1), the molar ratio of the benzene carboxylic acid compound to the base is 1:1.0-4.1; water is used as a solvent during salt formation, and the mass ratio of the benzene carboxylic acid compound to water is 1:3-20; in step (2), the mass ratio of the magnetic catalyst to the benzene carboxylic acid salt is 1:1-1000; in step (3), the hydrogen pressure is 0.05-20 MPa; in step (4), the reaction temperature is 50-220°C; in step (5), the acid used for acidification is hydrochloric acid, and the molar ratio of hydrochloric acid to benzene carboxylic acid is 1-4.5:1.

[0021] More preferably, in step (1), the molar ratio of the benzene carboxylic acid compound to the base is 1:1.05-4.05; the mass ratio of the benzene carboxylic acid compound to water is 1:5-10; the mass ratio of the metal catalyst to the benzene carboxylic acid salt in step (2) is 1:1-200; the hydrogen pressure in step (3) is 1-5 MPa; the reaction temperature in step (4) is 80-150°C; and the molar ratio of hydrochloric acid to the benzene carboxylic acid compound in step (5) is 1.5-4:1.

[0022] Compared with the prior art, the advantages of the present invention are: (1) The magnetic catalyst of the present invention comprises an active metal A, a promoter metal B and a carrier material, wherein the active metal A is one or more of ruthenium, rhodium and palladium, and the promoter metal B is one or more of copper, nickel and cobalt. The addition of the promoter metal reduces the content of the precious metal and thus reduces the cost of the catalyst. On the other hand, the addition of the promoter metal can improve the performance of the catalyst due to the electronic effect and the geometric effect. The carrier material is magnetic iron oxide, which can be directly separated after the reaction is completed, thereby reducing the production cost.

[0023] (2) The magnetic catalyst of the present invention has high catalytic activity, high selectivity of reaction products, high conversion rate of raw materials and mild reaction conditions in the reaction of hydrogenating benzene carboxylic acid compounds to prepare cyclohexane carboxylic acid compounds.

[0024] (3) The magnetic catalyst of the present invention is used for hydrogenating benzene carboxylic acid compounds to prepare cyclohexane carboxylic acid compounds. Before the reaction, the benzene carboxylic acid compounds are salted with a base to significantly improve their solubility in water, and the benzene carboxylic acid salts have little corrosiveness to equipment. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below with reference to the embodiments. Example 1

[0026] Ruthenium copper / iron oxide (1%Ru / Fe 2 O 3 Application of -0.1%Cu) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). Add 10 g of iron oxide into a 2000 mL beaker, then add about 350 mL of ethylene glycol, and stir at room temperature for half an hour to make it evenly dispersed; add 26.32 g of Ru colloidal solution (0.38 wt%) using a constant pressure dripping hole, add 1200 mL of deionized water after stirring at room temperature for three hours, and continue stirring overnight; filter out the mixed solution of ethylene glycol and water, wash it alternately with anhydrous ethanol and deionized water three times, and then freeze-dry it to obtain a ruthenium / iron oxide (1% Ru / Fe2O3) catalyst.

[0027] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0028] (3) The ruthenium / iron oxide (1%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 3.4 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium copper / iron oxide (1% Ru / Fe 2 O 3 -0.1%Cu) catalyst.

[0029] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water and freeze-dried to obtain disodium terephthalate for later use.

[0030] (5) 0.05 g of the catalyst ruthenium copper / iron oxide (1% Ru / Fe 2 O 3 -0.1% Cu), 10.00g of the above-mentioned disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and then the temperature is lowered, and the catalyst is separated by a magnet to obtain a hydrogenation filtrate, 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate, and the mixture is stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then subjected to qualitative and quantitative analysis by liquid chromatography. Example 2

[0031] Ruthenium copper / iron oxide (1%Ru / Fe 2 O 3 Application of -0.3%Cu) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 26.32 g of Ru colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixture of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain ruthenium / iron oxide (1% Ru / Fe 2 O 3 )catalyst.

[0032] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0033] (3) The ruthenium / iron oxide (1%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 10.2 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium copper / iron oxide (1% Ru / Fe 2 O 3 -0.3%Cu) catalyst.

[0034] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water and freeze-dried to obtain disodium terephthalate for later use.

[0035] (5) 0.05 g of the catalyst ruthenium copper / iron oxide (1% Ru / Fe 2 O 3 -0.3% Cu), 10.00g of the above-mentioned disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and then the temperature is lowered, and the catalyst is separated by a magnet to obtain a hydrogenation filtrate, 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate, and the mixture is stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0036] Example 3 Ruthenium copper / iron oxide (2%Ru / Fe 2 O 3 Application of -0.1%Cu) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 52.63 g of Ru colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixture of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain ruthenium / iron oxide (2% Ru / Fe 2 O 3 )catalyst.

[0037] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0038] (3) The ruthenium / iron oxide (2%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 3.4 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium copper / iron oxide (2% Ru / Fe 2 O 3 -0.1%Cu) catalyst.

[0039] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0040] (5) 0.05 g of the catalyst ruthenium copper / iron oxide (2% Ru / Fe 2 O 3 -0.1% Cu), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0041] Example 4 Ruthenium copper / iron oxide (2%Ru / Fe 2 O 3 Application of -0.3%Cu) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 52.63 g of Ru colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixture of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain ruthenium / iron oxide (10% Ru / Fe 2 O 3 )catalyst.

[0042] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0043] (3) The ruthenium / iron oxide (2%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 10.2 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium copper / iron oxide (2% Ru / Fe 2 O 3 -0.3%Cu) catalyst.

[0044] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0045] (5) 0.05 g of the catalyst ruthenium copper / iron oxide (2% Ru / Fe 2 O 3 -0.3% Cu), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0046] Example 5 Copper Ruthenium / Iron Oxide (0.1%Cu / Fe 2 O 3 Application of -1%Ru) catalyst in terephthalic acid hydrogenation (1) Dissolve 9.6 g of anhydrous cupric chloride in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue cuprammonia solution (0.003 g / ml).

[0047] (2) Disperse 10 g of iron oxide carrier into 100 mL of deionized water, add 3.4 mL of the copper ammonia solution prepared in step (1) and continue stirring for two hours. Then heat to 60 °C and continue stirring to evaporate the liquid in the system and naturally cool to room temperature. Add 500 ml of 0.1 mol / L NaOH solution to the obtained solid powder and stir at room temperature to disperse it evenly. Add 50 ml of 0.27 mol / L NaBH under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain copper / iron oxide (0.1% Cu / Fe 2 O 3 )catalyst.

[0048] (3) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added to a 1000 mL three-necked flask, and about 250 mL of ethylene glycol was added thereto. The mixture was stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added thereto (drop by drop) until the pH of the solution was about 10-11. The mixture was stirred for half an hour at room temperature and under an inert atmosphere, and then heated to 160°C. After maintaining the temperature for 3 h, the mixture was cooled to room temperature to obtain a brown, stable, and uniform Ru colloidal solution (wtRu% = 0.38%). The copper / iron oxide (0.1% / Fe 2 O) prepared in step (2) was added to the mixture. 2 O 3 ) was added to a 2000mL beaker, and then about 350mL of ethylene glycol was added, and stirred at room temperature for half an hour to make it evenly dispersed; 26.32g of Ru colloidal solution (0.38wt%) was added thereto using a constant pressure dripping hole, and 1200mL of deionized water was added after stirring at room temperature for three hours, and stirring was continued overnight; the mixed solution of ethylene glycol and water was removed by suction filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times, and then freeze-dried to obtain copper ruthenium / iron oxide (0.1%Cu / Fe 2 O 3 -1%Ru) catalyst.

[0049] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0050] (5) 0.05 g of the above-prepared catalyst copper ruthenium / iron oxide (0.1% Cu / Fe 2 O 3 -1%Ru), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and then the temperature is lowered, and the catalyst is separated by a magnet to obtain a hydrogenation filtrate, 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate, and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0051] Example 6 Ruthenium Nickel / Iron Oxide (1%Ru / Fe 2 O 3 Application of -0.1%Ni) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 26.32 g of Ru colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixture of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain ruthenium / iron oxide (1% Ru / Fe 2 O 3 )catalyst.

[0052] (2) 9.3 g of anhydrous nickel chloride was completely dissolved in 1500 ml of deionized water and ultrasonically dispersed for 1 h. 600 ml of 0.1 mol / L NaOH solution was added to obtain a light green precipitate. The mixture was stirred for half an hour. The precipitate obtained by centrifugation was washed with water. 1500 ml of ammonia water (wt% = 25.0%-28%) was added to the transferred precipitate. The mixture was magnetically stirred until completely dissolved to obtain a blue-purple nickel-ammonia solution (0.003 g / ml).

[0053] (3) The ruthenium / iron oxide (1%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 3.4 mL of the nickel-ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium nickel / iron oxide (1% Ru / Fe 2 O 3 -0.1%Ni) catalyst.

[0054] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0055] (5) 0.05 g of the above-prepared catalyst ruthenium nickel / iron oxide (1% Ru / Fe 2 O 3 -0.1% Ni), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0056] Example 7 Ruthenium Nickel / Iron Oxide (1%Ru / Fe 2 O 3 Application of -0.3%Ni) catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 hours, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10g of iron oxide was added to a 2000mL beaker, and then about 350mL of ethylene glycol was added, and the mixture was stirred at room temperature for half an hour to make it uniformly dispersed; 26.32g of Ru colloidal solution (0.38wt%) was added thereto using a constant pressure dripping hole, and after stirring at room temperature for three hours, 1200mL of deionized water was added, and stirring was continued overnight; the mixed solution of ethylene glycol and water was removed by suction filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water three times, and then freeze-dried to obtain ruthenium / iron oxide (1%Ru / Fe 2 O 3 )catalyst.

[0057] (2) 9.3 g of anhydrous nickel chloride was completely dissolved in 1500 ml of deionized water and ultrasonically dispersed for 1 h. 600 ml of 0.1 mol / L NaOH solution was added to obtain a light green precipitate. The mixture was stirred for half an hour. The precipitate obtained by centrifugation was washed with water. 1500 ml of ammonia water (wt% = 25.0%-28%) was added to the transferred precipitate. The mixture was magnetically stirred until completely dissolved to obtain a blue-purple nickel-ammonia solution (0.003 g / ml).

[0058] (3) The ruthenium / iron oxide (1%Ru / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 10.2 mL of the nickel-ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain ruthenium nickel / iron oxide (1% Ru / Fe 2 O 3 -0.3%Ni) catalyst.

[0059] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0060] (5) 0.05 g of the above-prepared catalyst ruthenium nickel / iron oxide (1% Ru / Fe 2 O 3 -0.3% Ni), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0061] Example 8 Ruthenium Cobalt / Iron Oxide (1%Ru / Fe 2 O 3 Application of -0.1%Co) catalyst in terephthalic acid hydrogenation The specific preparation process, reaction process and detection method of the catalyst are the same as those in Example 1, except that the anhydrous copper chloride in step (2) is replaced with cobalt chloride of the corresponding mass ratio, and the catalyst is replaced with 1% Ru / Fe 2 O 3 -0.1%Co.

[0062] Example 9 Rhodium copper / iron oxide (1%Rh / Fe 2 O 3 Application of -0.1%Cu) catalyst in terephthalic acid hydrogenation (1) 5.0 g RhCl 3 ·xH 2O (wtRh% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. Thereafter, 0.25 mol / L freshly prepared ethylene glycol solution of sodium hydroxide was added (drop by drop) until the pH value of the solution was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 hours, and then cooled to room temperature to obtain a brown, stable and uniform Rh colloidal solution (wtRh% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 26.32 g of Rh colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixed solution of ethylene glycol and water was removed by suction filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain rhodium / iron oxide (1% Rh / Fe 2 O 3 )catalyst.

[0063] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0064] (3) The rhodium / iron oxide (1% Rh / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 3.4 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and freeze-dried in vacuum to obtain rhodium copper / iron oxide (1% Rh / Fe 2 O 3 -0.1%Cu) catalyst.

[0065] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0066] (5) 0.05 g of the catalyst prepared above, rhodium copper / iron oxide (1% Rh / Fe 2 O 3 -0.1% Cu), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0067] Example 10 Rhodium Nickel / Iron Oxide (1%Rh / Fe 2 O 3 Application of -0.1%Ni) catalyst in terephthalic acid hydrogenation The specific preparation process, reaction process and detection method of the catalyst are the same as those in Example 11, except that the anhydrous cupric chloride in step (2) is replaced with nickel chloride of the corresponding mass ratio, and the catalyst is replaced with 1% Rh / Fe 2 O 3 -0.1%Ni.

[0068] Embodiment 11 Rhodium Cobalt / Iron Oxide (1% Rh / Fe 2 O 3 Application of -0.1%Co) catalyst in terephthalic acid hydrogenation The specific preparation process, reaction process and detection method of the catalyst are the same as those in Example 11, except that the anhydrous copper chloride in step (2) is replaced with cobalt chloride of the corresponding mass ratio, and the catalyst is replaced with 1% Rh / Fe 2 O 3 -0.1%Co.

[0069] Example 12 Palladium copper / iron oxide (1%Pd / Fe 2 O 3 Application of -0.1%Cu) catalyst in terephthalic acid hydrogenation (1) 0.6 g H 2 PdCl 6Dissolve in 100 ml of deionized water, mix with 10 g of iron oxide after complete dissolution, soak for 24 hours, centrifuge and dry to obtain palladium / iron oxide (1% Pd / Fe 2 O 3 )catalyst.

[0070] (2) Dissolve 9.6 g of anhydrous cupric chloride completely in 1500 ml of deionized water and disperse by ultrasonic for 1 h. Add 600 ml of 0.1 mol / L NaOH solution to obtain a blue precipitate. Stir for half an hour. Wash the precipitate obtained by centrifugation with water. Add 1500 ml of ammonia water (wt% = 25.0%-28%) to the transferred precipitate and stir magnetically until it is completely dissolved to obtain a dark blue copper ammonia solution (0.003 g / ml).

[0071] (3) The palladium / iron oxide (1% Pd / Fe) prepared in step (1) 2 O 3 ) The catalyst was dispersed in 100 mL of deionized water, and 3.4 mL of the copper ammonia solution prepared in step (2) was added and stirred for two hours. Then, the mixture was heated to 60 °C and stirred continuously to evaporate the liquid in the system and then naturally cooled to room temperature. 50 mL of 0.1 mol / L NaOH solution was added to the obtained solid powder and stirred at room temperature to disperse it uniformly. 50 mL of 0.27 mol / L NaBH was added under inert atmosphere. 4 The solution was reacted for 2 h, washed alternately with deionized water and anhydrous ethanol, and vacuum freeze-dried to obtain palladium copper / iron oxide (1% Pd / Fe 2 O 3 -0.1%Cu) catalyst.

[0072] (4) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals, and the obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0073] (5) 0.05 g of the catalyst prepared above, palladium copper / iron oxide (1% Pd / Fe 2 O 3 -0.1% Cu), 10.00g of disodium terephthalate and 30ml of water are added into a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h. The temperature is lowered and the catalyst is separated by a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension is diluted with deionized water and then qualitative and quantitative analysis is performed by liquid chromatography.

[0074] Example 13 Palladium Nickel / Iron Oxide (1%Pd / Fe 2 O 3 Application of -0.1%Ni) catalyst in terephthalic acid hydrogenation The specific preparation process, reaction process and detection method of the catalyst are the same as those in Example 14, except that the anhydrous cupric chloride in step (2) is replaced with nickel chloride of the corresponding mass ratio, and the catalyst is replaced with 1% Pd / Fe 2 O 3 -0.1%Ni.

[0075] Embodiment 14 Palladium cobalt / iron oxide (1%Pd / Fe 2 O 3 Application of -0.1%Co) catalyst in terephthalic acid hydrogenation The specific preparation process, reaction process and detection method of the catalyst are the same as those in Example 14, except that the anhydrous copper chloride in step (2) is replaced with cobalt chloride of the corresponding mass ratio, and the catalyst is replaced with 1% Pd / Fe 2 O 3 -0.1%Co.

[0076] Comparative Example 1 Ruthenium / Iron Oxide (1%Ru / Fe 2 O 3 )Application of catalyst in terephthalic acid hydrogenation (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it dispersed evenly. 26.32 g of Ru colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixture of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times and then freeze-dried to obtain ruthenium / iron oxide (1% Ru / Fe 2 O 3 )catalyst.

[0077] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0078] (3) 0.05 g of the above-prepared catalyst ruthenium / iron oxide (1% Ru / Fe 2 O 3 ), 10.00g of disodium terephthalate and 30ml of water are added to a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and the temperature is lowered, and the catalyst is separated with a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0079] Comparative Example 2 Rhodium / Iron Oxide (1%Rh / Fe 2 O 3 )Application of catalyst in terephthalic acid hydrogenation (1) 5.0 g RhCl 3 ·xH 2 O (wtRh% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared ethylene glycol solution of sodium hydroxide was added (drop by drop) until the pH of the solution was around 10-11. Stirring was continued for half an hour at room temperature and under the protection of an inert atmosphere, and then the temperature was raised to 160°C, maintained for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Rh colloidal solution (wtRh% = 0.38%). 10 g of iron oxide was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added, and the mixture was stirred at room temperature for half an hour to make it dispersed evenly; 26.32 g of Rh colloidal solution (0.38 wt%) was added to the mixture using a constant pressure dropping funnel, and 1200 mL of deionized water was added after stirring at room temperature for three hours, and the mixture was stirred overnight; the mixed solution of ethylene glycol and water was removed by suction filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times, and then freeze-dried to obtain rhodium / iron oxide (1% Rh / Fe 2 O 3 )catalyst.

[0080] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0081] (3) 0.05 g of the above-prepared catalyst rhodium / iron oxide (1% Rh / Fe 2 O 3 ), 10.00g of disodium terephthalate and 30ml of water are added to a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and the temperature is lowered, and the catalyst is separated with a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0082] Comparative Example 3 Palladium / Iron Oxide (1%Pd / Fe 2 O 3 )Application of catalyst in terephthalic acid hydrogenation (1) 0.6 g H 2 PdCl 6 Dissolve in 100 ml of deionized water, mix with 10 g of iron oxide after complete dissolution, soak for 24 hours, centrifuge and dry to obtain palladium / iron oxide (1% Pd / Fe 2 O 3 )catalyst.

[0083] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0084] (3) 0.05 g of the above-prepared catalyst palladium / iron oxide (1% Pd / Fe 2 O 3), 10.00g of disodium terephthalate and 30ml of water are added to a 100ml high-pressure reactor, hydrogen is passed through to replace the air in the reactor for more than 5 times, and then 4MPa of hydrogen is filled in, and then stirring is started and the temperature is raised to 120°C for reaction for 2h, and the temperature is lowered, and the catalyst is separated with a magnet to obtain a hydrogenation filtrate. 3.6g of hydrochloric acid is added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid, which is diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0085] Comparative Example 4 Application of Ruthenium / Carbon (1%Ru / C) Catalyst in Hydrogenation of Terephthalic Acid (1) 5.0 g RuCl 3 ·xH 2 O (wtRu% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared sodium hydroxide ethylene glycol solution was added (drop by drop) until the solution pH was about 10-11. After continuous stirring for half an hour at room temperature and under the protection of an inert atmosphere, the mixture was heated to 160°C, kept for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Ru colloidal solution (wtRu% = 0.38%). 10 g of activated carbon was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it evenly dispersed. 26.32 g of Ru colloidal solution (0.38 wt%) was added into the beaker using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixed solution of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times, and then freeze-dried to obtain a ruthenium / carbon (1% Ru / C) catalyst.

[0086] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0087] (3) 0.05 g of the above-prepared catalyst ruthenium / carbon (1% Ru / C), 10.00 g of disodium terephthalate and 30 ml of water were added to a 100 ml high-pressure reactor, and the air in the reactor was replaced by hydrogen for more than 5 times. Then 4 MPa of hydrogen was filled in. Then stirring was started and the temperature was raised to 120°C for reaction for 2 h. The temperature was lowered and the catalyst was separated by a magnet to obtain a hydrogenation filtrate. 3.6 g of hydrochloric acid was added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension was diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0088] Comparative Example 5 Application of Rhodium / Carbon (1% Rh / C) Catalyst in Hydrogenation of Terephthalic Acid (1) 5.0 g RhCl 3 ·xH 2 O (wtRh% ≥37.0%) was added into a 1000 mL three-necked flask, to which was added about 250 mL of ethylene glycol, and stirred at room temperature until it was completely dissolved. A 0.25 mol / L freshly prepared ethylene glycol solution of sodium hydroxide was added (drop by drop) until the pH of the solution was around 10-11. Stirring was continued for half an hour at room temperature and under the protection of an inert atmosphere, and then the temperature was raised to 160°C, maintained for 3 h, and then cooled to room temperature to obtain a brown, stable and uniform Rh colloidal solution (wtRh% = 0.38%). 10 g of activated carbon was added to a 2000 mL beaker, and then about 350 mL of ethylene glycol was added. The mixture was stirred at room temperature for half an hour to make it evenly dispersed. 26.32 g of Rh colloidal solution (0.38 wt%) was added into the beaker using a constant pressure dripping hole. After stirring at room temperature for three hours, 1200 mL of deionized water was added and the mixture was stirred overnight. The mixed solution of ethylene glycol and water was removed by filtration, and the mixture was washed alternately with anhydrous ethanol and deionized water for three times, and then freeze-dried to obtain a rhodium / carbon (1% Rh / C) catalyst.

[0089] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0090] (3) 0.05 g of the above-prepared catalyst rhodium / carbon (1% Rh / C), 10.00 g of disodium terephthalate and 30 ml of water were added to a 100 ml high-pressure reactor, and hydrogen was passed through the reactor to replace the air in the reactor for more than 5 times. Then 4 MPa of hydrogen was filled in. Then stirring was started and the temperature was raised to 120°C for reaction for 2 h. The temperature was lowered and the catalyst was separated by a magnet to obtain a hydrogenation filtrate. 3.6 g of hydrochloric acid was added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension was diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0091] Comparative Example 6 Application of Palladium / Carbon (1%Pd / C) Catalyst in Hydrogenation of Terephthalic Acid (1) 0.6 g H 2 PdCl 6 The catalyst was dissolved in 100 ml of deionized water, mixed with 10 g of activated carbon after being completely dissolved, and centrifuged and dried after being immersed for 24 hours to obtain a palladium / carbon (1% Pd / C) catalyst.

[0092] (2) 84 g of sodium hydroxide was completely dissolved in 5000 mL of deionized water to obtain a colorless and transparent solution. Then 166 g of terephthalic acid was added to the above solution, heated to 50°C and stirred for one hour. The obtained reaction solution was rotary evaporated to obtain disodium terephthalate crystals. The obtained crystals were recrystallized with deionized water, freeze-dried and set aside.

[0093] (3) 0.05 g of the above-prepared catalyst palladium / carbon (1% Pd / C), 10.00 g of disodium terephthalate and 30 ml of water were added to a 100 ml high-pressure reactor, and hydrogen was passed through the reactor to replace the air in the reactor for more than 5 times. Then 4 MPa of hydrogen was filled in. Then stirring was started and the temperature was raised to 120°C for reaction for 2 h. The temperature was lowered and the catalyst was separated by a magnet to obtain a hydrogenation filtrate. 3.6 g of hydrochloric acid was added to the obtained hydrogenation filtrate and stirred at room temperature for 30 minutes to obtain a suspension containing cyclohexanedicarboxylic acid. The suspension was diluted with deionized water and then qualitatively and quantitatively analyzed by liquid chromatography.

[0094] The products of the examples and comparative examples were qualitatively and quantitatively analyzed by liquid chromatography. The reaction results are shown in Table 1.

[0095] Table 1 PTA conversion and 1,4-CHDA selectivity of Examples 1-14 and Comparative Examples 1-6

[0096] In addition to the above embodiments, the present invention also includes other implementation modes. Any technical solutions formed by equivalent transformation or equivalent replacement should fall within the protection scope of the claims of the present invention.

Claims

1. A magnetic catalyst for preparing cyclohexanecarboxylic acid compounds, characterized in that: The magnetic catalyst comprises an active metal A, an auxiliary metal B and a carrier material, wherein the active metal A is one or more of ruthenium, rhodium and palladium, the auxiliary metal B is one or more of copper, nickel and cobalt, and the carrier material is one or more of iron oxide, aluminum oxide and titanium dioxide.

2. The magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 1, characterized in that: The active metal A is ruthenium and / or rhodium, the auxiliary metal B is copper and / or nickel, and the carrier material is iron oxide.

3. The magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 1, characterized in that: The mass percentage content of active metal A in the magnetic catalyst is 0.1-20%; the mass percentage content of auxiliary metal B is 0.1-20%.

4. The method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) preparing a catalyst loaded with active metal A; (2) preparing an ammonia-coordinated metal hydroxide solution of auxiliary metal B; (3) In an inert gas protective atmosphere, the catalyst loaded with active metal A obtained in step (1) is mixed with the ammonia coordinated metal hydroxide solution of auxiliary metal B obtained in step (2), and stirred evenly at room temperature. A reducing agent is added dropwise under the protection of an inert gas atmosphere, and stirred until the ammonia coordinated metal hydroxide solution of metal B is completely adsorbed, thereby obtaining a catalyst loaded with both active metal A and auxiliary metal B.

5. The method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) preparing an ammonia-coordinated metal hydroxide solution of auxiliary metal B; (2) preparing nanoparticle colloids of active metal A; (3) mixing the ammonia-coordinated metal hydroxide solution of the promoter metal B obtained in step (1) with the carrier, evaporating the solution in the system to dryness under magnetic stirring, and adding a reducing agent dropwise to the obtained solid powder under the protection of an inert atmosphere to obtain a catalyst loaded with the promoter metal B; (4) The nanoparticle colloid of active metal A prepared in step (2) is mixed with the catalyst loaded with promoter metal B prepared in step (3), stirred at room temperature until the nanoparticle colloid is completely adsorbed, and then centrifuged to obtain a catalyst loaded with both promoter metal B and active metal A.

6. The method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 4, characterized in that: The specific steps of step (1) preparing a catalyst loaded with active metal A are as follows: using a polyol reduction method or a sol-gel method to prepare a nanoparticle colloid of active metal A; dispersing a carrier material in a solvent, then adding the nanoparticle colloid of active metal A, centrifuging after loading, and vacuum freeze-drying to obtain a catalyst loaded with active metal A.

7. The method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 4, characterized in that: The specific steps of step (2) preparing the ammonia-coordinated metal hydroxide solution of auxiliary metal B are as follows: dissolving the metal salt corresponding to the auxiliary metal B in a solvent, adding an alkali to obtain a hydroxide precipitate, and after centrifugal separation, adding the hydroxide precipitate into ammonia water and stirring until dissolved to obtain an ammonia-coordinated metal hydroxide solution.

8. The method for preparing a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 4, characterized in that: The inert atmosphere of step (3) is one or more of nitrogen, argon and helium; the reducing agent is one or more of sodium borohydride, hydrazine hydrate and ascorbic acid; and the solvent of step (3) is water or alcohol.

9. An application of a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to any one of claims 1 to 3, wherein the magnetic catalyst is used for hydrogenating benzenecarboxylic acid compounds to prepare cyclohexanecarboxylic acid compounds, characterized in that: The following steps are involved: (1) Benzene carboxylic acid compounds react with alkali in water to form benzoic acid salts; (2) adding a magnetic catalyst into a reaction device and adding the benzene carboxylic acid salt prepared in step (1); (3) Seal the reaction device and introduce hydrogen to replace the air in the reaction device, and fill the reaction device with hydrogen at a certain pressure; (4) heating the temperature to the reaction temperature under stirring, and obtaining a reaction solution after the reaction is completed; (5) The reaction solution is acidified to obtain cyclohexanecarboxylic acid compounds.

10. The use of a magnetic catalyst for preparing cyclohexanecarboxylic acid compounds according to claim 1, characterized in that: In the step (1), the molar ratio of the benzene carboxylic acid compound to the base is 1:1.0-4.1; water is used as a solvent during salt formation, and the mass ratio of the benzene carboxylic acid compound to water is 1:3-20; in the step (2), the mass ratio of the magnetic catalyst to the benzene carboxylic acid salt is 1:1-1000; in the step (3), the hydrogen pressure is 0.05-20 MPa; in the step (4), the reaction temperature is 50-220° C.; in the step (5), the acid used for acidification is hydrochloric acid, and the molar ratio of hydrochloric acid to the benzene carboxylic acid compound is 1-4.5:1.

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