Cobalt-ruthenium bimetallic DINP hydrogenation catalyst and preparation method and application thereof

Abstract

The invention belongs to the field of catalysts, and particularly discloses a cobalt-ruthenium bimetallic DINP hydrogenation catalyst and a preparation method and application thereof. The DINP hydrogenation catalyst is a cobalt-ruthenium bimetallic catalyst, and has the characteristics that the preparation method is simple, the hydrogenation catalytic reaction condition is mild, the catalytic activity is high, the cycle service life is long, metal active components are not easy to fall off or lose, and the chromaticity of the product can reach the standard without post-treatment.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and in particular relates to a cobalt-ruthenium bimetallic DINP hydrogenation catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] Because dialkyl cyclohexanedicarboxylates are non-toxic, non-carcinogenic, non-peroxisome proliferating, non-bioaccumulative, and non-reproductive, they are used in the production of children's toys, medical supplies, PVC plastic particles, and cable and wire materials. In industrial production, dialkyl cyclohexanedicarboxylates are primarily produced through the one-step hydrogenation of phthalates.

[0003] At present, the following problems still exist in the hydrogenation of phthalates to dialkyl cyclohexanedicarboxylates: (1) the reaction temperature is high, and the reaction conversion rate and selectivity are insufficient; (2) the hydrogenation catalyst is usually a noble metal-loaded catalyst, and the amount of noble metal used is large. The noble metal content in commercial hydrogenation catalysts can be as high as 3%-5%; (3) the noble metal in the noble metal-loaded catalyst is easily lost during the hydrogenation reaction, and the lost part cannot be recovered, resulting in a waste of noble metal resources; (4) the noble metal lost in the catalyst will contaminate the hydrogenated product. Because the particle size is only tens of nanometers, it is difficult to adsorb or filter it out, resulting in problems such as substandard product color and affecting the quality of the obtained product. Therefore, based on the above-mentioned existing defects, it is still necessary to continue to develop a new noble metal hydrogenation catalyst to solve the above-mentioned problems. Summary of the Invention

[0004] In response to the problems of insufficient reaction conversion and selectivity, high usage of precious metals in the catalyst and difficulty in recovery in the above-mentioned prior art for the preparation of diisononyl cyclohexanedicarboxylate (DINCH), the present invention provides a cobalt-ruthenium bimetallic DINP (diisononyl phthalate) hydrogenation catalyst, its preparation method and application.

[0005] To achieve the above objectives, the following technical solutions are specifically included:

[0006] In a first aspect, the present invention provides a method for preparing a two-dimensional carbon skeleton material carrier, comprising the following steps:

[0007] (1) mixing a solvent, hexadecyltrimethylammonium bromide, cobalt acetate, and 2-methylimidazole, and performing a solvothermal reaction to obtain a carrier precursor;

[0008] (2) calcining the carrier precursor under an inert gas atmosphere to obtain a two-dimensional carbon skeleton material carrier.

[0009] The present invention first uses a solvothermal method to react cobalt acetate with 2-methylimidazole in the presence of a surfactant, cetyltrimethylammonium bromide, to obtain a cobalt-containing sheet-like zeolitic imidazolate framework-67 (ZIF-67) precursor. This precursor is then calcined under an inert atmosphere to convert it into a cobalt-inlaid two-dimensional carbon framework. This two-dimensional carbon framework, derived from ZIF-67, has ample accessible surface area, ensuring sufficient contact between the metal catalyst and the reactants.

[0010] Preferably, in step (1), the solvent includes at least one of water and ethanol.

[0011] Preferably, in step (1), the mass ratio of cetyltrimethylammonium bromide to cobalt acetate is (0.4-0.8):(1-2.5).

[0012] Preferably, in step (1), the mass ratio of 2-methylimidazole to cobalt acetate is (20-30): (1-2.5).

[0013] Preferably, in step (1), the mass ratio of the solvent to cobalt acetate is (300-600):(1-2.5).

[0014] Preferably, in step (1), the solvent thermal temperature is 100-160° C., and the solvent thermal time is 8-12 h.

[0015] Preferably, in step (2), the calcination temperature is 600-1000° C., and the calcination time is 1-6 hours.

[0016] In a second aspect, the present invention provides a two-dimensional carbon skeleton material carrier prepared by the preparation method of the two-dimensional carbon skeleton material carrier.

[0017] In a third aspect, the present invention provides a diisononyl phthalate hydrogenation catalyst, comprising the two-dimensional carbon skeleton material carrier and cobalt and ruthenium embedded in the two-dimensional carbon skeleton material carrier.

[0018] Preferably, the diisononyl phthalate hydrogenation catalyst has a hollow nanosphere morphology.

[0019] Preferably, the cobalt and ruthenium are embedded in the carbon material in the form of hollow spheres.

[0020] Preferably, in the diisononyl phthalate hydrogenation catalyst, the mass content of ruthenium is 0.5% to 1.5%, and the mass content of cobalt is 0.1% to 2.5%.

[0021] Further preferably, in the diisononyl phthalate hydrogenation catalyst, the mass content of ruthenium is 1% to 1.6%, and the mass content of cobalt is 0.2% to 0.5%.

[0022] In a fourth aspect, the present invention provides a method for preparing a diisononyl phthalate hydrogenation catalyst, comprising the following steps:

[0023] (1) adding a two-dimensional carbon skeleton material support to a ruthenium metal salt solution for electrochemical replacement to obtain a catalyst precursor;

[0024] (2) calcining the catalyst precursor under a hydrogen atmosphere to obtain the diisononyl phthalate hydrogenation catalyst.

[0025] The present invention first adopts a solvothermal method, and with the assistance of a surfactant, hexadecyltrimethylammonium bromide, cobalt acetate and 2-methylimidazole undergo a solvothermal reaction to obtain a cobalt-containing sheet-like zeolite imidazolate framework-67 (ZIF-67) precursor. The precursor is then calcined under an inert atmosphere to convert it into a cobalt-embedded two-dimensional carbon framework material. The cobalt metal is then replaced by ruthenium ions in a ruthenium metal salt through an electrochemical replacement reaction, removing the cobalt particle core while forming hollow cobalt-ruthenium bimetallic spheres embedded in the two-dimensional carbon framework, thereby obtaining a hollow cobalt-ruthenium bimetallic hydrogenation catalyst protected by the two-dimensional carbon framework. The bimetallic catalyst, with ruthenium as the active ingredient and cobalt as the auxiliary, has a synergistic effect. The hollow structure of the bimetallic catalyst provides abundant exposed sites, ensuring the catalyst's hydrogenation catalytic activity. The outer two-dimensional carbon skeleton protects the bimetallic catalyst, avoiding the problem of precious metal and auxiliary agent shedding that exists in supported catalysts. At the same time, the abundant contact area of the two-dimensional carbon material derived from ZIF-67 also ensures sufficient contact between the internal bimetallic catalyst and the reactants. Based on this unique structure, the catalyst, as a catalyst for the hydrogenation of diisononyl phthalate, has high catalytic activity, a long cycle life, and is not prone to shedding or loss of the metal active component. It does not contaminate the product and does not require adsorption or filtration post-treatment. It can reduce the temperature, pressure and other conditions required for the DINP hydrogenation reaction, thereby reducing the difficulty of the hydrogenation catalytic reaction. It can solve the problems of harsh reaction conditions required by the existing technology, low catalyst activity, precious metal shedding and the resulting substandard product color, thereby improving product quality and reducing energy consumption. Therefore, the catalyst prepared by the present invention has the characteristics of simple preparation method, mild hydrogenation catalytic reaction conditions, high catalytic activity, long cycle life, metal active components are not easy to fall off or lose, and the product can achieve color standards without post-treatment.

[0026] Preferably, in step (1), the mass concentration of ruthenium metal ions in the ruthenium metal salt solution is 1-5 g / L.

[0027] Preferably, the ruthenium metal salt includes but is not limited to the corresponding chloride salt and nitrate salt.

[0028] Preferably, in step (1), the electrochemical replacement time is 2-6 hours. The electrochemical replacement is a replacement reaction between Co and ruthenium ions, whereby part of Co replaces Ru to form a cobalt-ruthenium bimetallic.

[0029] Preferably, in step (1), the mass concentration of the carrier in the ruthenium metal salt solution is 150-300 g / L.

[0030] Preferably, in step (2), the calcination temperature is 150-200° C., and the calcination time is 1-5 h.

[0031] In a fifth aspect, the present invention provides a method for synthesizing diisononyl cyclohexanedicarboxylate, comprising the following steps: in the presence of the diisononyl phthalate hydrogenation catalyst, diisononyl phthalate is subjected to a hydrogenation reaction with hydrogen to obtain diisononyl cyclohexanedicarboxylate.

[0032] Preferably, the temperature of the hydrogenation reaction is 130-150°C, and more preferably, the temperature of the hydrogenation reaction is 135-140°C.

[0033] Preferably, the pressure of the hydrogenation reaction is 3.5 to 5 MPa, and more preferably, the pressure of the hydrogenation reaction is 3.8 to 4 MPa.

[0034] Preferably, the raw liquid space velocity of the hydrogenation reaction is 0.2 to 0.45 h -1 ; Further preferably, the raw liquid space velocity of the hydrogenation reaction is 0.25~0.35h -1 .

[0035] Preferably, the volume ratio of hydrogen in the hydrogenation reaction to diisononyl phthalate is (15-50):1; further preferably, the volume ratio of hydrogen in the hydrogenation reaction to diisononyl phthalate is (20-30):1.

[0036] Preferably, the hydrogenation reaction is carried out using a fixed-bed continuous hydrogenation reactor.

[0037] The present invention uses a hollow cobalt-ruthenium bimetallic hydrogenation catalyst protected by a two-dimensional carbon skeleton to carry out a diisononyl phthalate hydrogenation reaction. The DINP conversion rate can reach as high as 99.6%, the DINCH selectivity can reach as high as 99.6%, and the obtained DINCH product can achieve a color of less than 30 without filtering. The catalyst has the characteristics of high selectivity, high activity and low ruthenium loss. Based on the catalyst, the difficulty of post-processing of the hydrogenation product can be reduced.

[0038] Compared with the prior art, the present invention has the following beneficial effects: the catalyst prepared by the present invention has the characteristics of simple preparation method, mild hydrogenation catalytic reaction conditions, high catalytic activity, long cycle life, metal active components are not easy to fall off or lose, and the product can achieve color standards without post-treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 TEM image of the catalyst prepared in Example 1 (scale 0.5 μm).

[0040] Figure 2 TEM image of the catalyst prepared in Example 1 (scale: 100 nm). DETAILED DESCRIPTION

[0041] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention will be further described below with reference to specific examples. The experimental methods used in the examples and / or comparative examples are conventional methods unless otherwise specified; the materials and reagents used are commercially available unless otherwise specified.

[0042] Brief description of the following examples and comparative examples:

[0043] Example 1 is a method for preparing a diisononyl phthalate hydrogenation catalyst based on a hollow cobalt-ruthenium bimetallic protected by a two-dimensional carbon skeleton;

[0044] Examples 2 to 5 are experiments to investigate the process conditions for using the catalyst;

[0045] Example 6 shows the effect of the content of the two metal components in the cobalt-ruthenium bimetallic catalyst on the catalytic activity of the hydrogenation reaction;

[0046] Examples 7 and 8 are analysis of metal content in the catalyst before and after use and analysis of product color;

[0047] Comparative Example 1 is a catalyst prepared by a method other than the present invention;

[0048] The selectivities mentioned in the following examples and comparative examples are all selectivities of DINCH, and the conversion rates are all conversion rates of DINP.

[0049] Example 1

[0050] The specific preparation steps of the hydrogenation catalyst are as follows:

[0051] (1) 0.6 g of hexadecyltrimethylammonium bromide and 2.4 g of cobalt(II) acetate tetrahydrate (1.7 g of cobalt(II) acetate) were weighed and dissolved in 400 mL of deionized water. Under stirring, 100 mL of aqueous solution containing 24 g of 2-methylimidazole was quickly injected. After stirring at room temperature, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and heated at 120°C for 10 h. After the reaction was completed, the product was collected, washed with ethanol, and dried to obtain a precursor.

[0052] (2) The precursor was placed in an inert gas (nitrogen) atmosphere and calcined at 800°C for 3 h to obtain a two-dimensional carbon framework embedded with cobalt;

[0053] (3) Weigh 0.181 g of RuCl3·xH2O (containing approximately 37% Ru) and completely dissolve it in 20 mL of deionized water; add 5 g of the cobalt-embedded two-dimensional carbon skeleton to the above solution and electrochemically replace it for 4 h. After washing with deionized water and ethanol, it is dried and ground to obtain a two-dimensional carbon skeleton-protected cobalt-ruthenium bimetallic.

[0054] (4) Finally, the catalyst was calcined in a hydrogen atmosphere for activation at 150°C for 2 hours before use. The active components of the hydrogenation catalyst obtained were ruthenium accounting for 1% of its total mass and cobalt accounting for 0.5% of its total mass (ICP test).

[0055] The catalyst was characterized by transmission electron microscopy (TEM). Figure 1 and 2 , by the attached Figure 1 It can be observed that the catalyst prepared by the present invention is a two-dimensional material, the outer layer of which is a carbon material, in which a uniformly distributed cobalt-ruthenium bimetallic is embedded. Figure 2 The higher magnification TEM image shows that the cobalt-ruthenium bimetallic material has a hollow nanosphere morphology.

[0056] Example 2

[0057] Investigation of reaction temperature

[0058] Adopt tubular fixed-bed reactor to investigate the catalytic property of catalyst, fixed-bed reactor length is 1500mm, internal diameter is 32mm.In reactor, upper and lower parts are filled with quartz sand, and the catalyst obtained in embodiment 1 is installed in the middle, catalyst loading amount is 200mL, and conditions such as required reaction temperature, pressure, hydrogen and diisopropyl phthalate feed amount are regulated to carry out catalytic reaction, and reaction mass is cooled and sampled and analyzed at regular intervals.Based on area normalization method, by liquid chromatography, sampling is carried out qualitative and quantitative analysis, and the test instrument used is U.S. Agilent1260 high performance liquid chromatograph, chromatographic separation condition: chromatographic column is Agilent ZORBAX SB-C18 5μm (4.6*150mm), mobile phase is HPLC methanol, flow velocity is 1.2mL / min, sample size is 5μL, column temperature is 30 ℃, and ultraviolet detection wavelength is 207nm.

[0059] The effect of different reaction temperatures on the catalytic hydrogenation of diisopropyl phthalate was investigated by changing only the reaction temperature. Other reaction conditions were: pressure 4 MPa, space velocity 0.30 h -1 , hydrogen ester molar ratio is 30:1, and the results are shown in Table 1 below.

[0060] Table 1

[0061] Temperature / ℃ Conversion rate / % Selectivity / % 130 99.0 99.0 135 99.3 99.2 140 99.6 99.6 150 99.1 98.9

[0062] The hydrogenation reaction of diisopropyl phthalate is an exothermic reaction, but appropriately increasing the temperature within a certain range is conducive to the progress of the catalytic hydrogenation reaction. It can be found that when the temperature is increased to 140°C, the catalytic reaction effect reaches the optimal effect.

[0063] Example 3

[0064] Investigation of reaction pressure

[0065] Compared with Example 2, the variable of this example is the reaction pressure. The effect of different reaction pressures on the catalytic hydrogenation of diisopropyl phthalate was investigated. The reaction conditions were: temperature 140°C, space velocity 0.30h -1 , hydrogen ester molar ratio is 30:1, and the results are shown in Table 2 below.

[0066] Table 2

[0067] Pressure / MPa Conversion rate / % Selectivity / % 3.5 98.5 99.1 3.8 99.1 99.2 4 99.6 99.6 5 99.2 99.3

[0068] The above results show that the catalytic effect improves with increasing pressure. When it reaches 4 MPa, the catalytic effect reaches its optimal level, and further increasing the pressure keeps the catalytic effect basically unchanged. This is because when the system pressure increases, the concentration of hydrogen in the reaction medium increases, the amount of hydrogen adsorbed by the catalyst increases, and thus the reaction rate of the system increases. When the pressure rises to a certain level, the amount of hydrogen on the catalyst surface reaches saturation, and the raw material conversion rate is no longer affected. However, excessive pressure increases the reaction cost.

[0069] Example 4

[0070] Investigation of raw material liquid space velocity

[0071] Compared with Example 2, the variable in this example is the raw material liquid space velocity, and the effect of different raw material liquid space velocities on the catalytic hydrogenation of diisopropyl phthalate is investigated. The reaction conditions are: temperature 140°C, hydrogen ester molar ratio 30:1, and pressure 4 MPa. The results are shown in Table 3 below.

[0072] Table 3

[0073] <![CDATA[Air speed / h -1 > Conversion rate / % Selectivity / % 0.20 98.8 99.4 0.30 99.6 99.6 0.40 99.4 96.2 0.45 99.3 93.3

[0074] From the above results, it can be found that with the increase of the liquid space velocity of the raw material, the conversion of diisopropyl phthalate first increases and then decreases. This is because when the space velocity is low, the reaction heat is less, the reaction temperature rise is low, resulting in a low internal temperature of the catalyst and incomplete reaction conversion. With the increase of the liquid space velocity of the raw material, the reaction heat increases, resulting in a lower reaction temperature rise and an increase in conversion rate. With the further increase of the liquid space velocity, the contact time between the material and the catalyst is reduced, resulting in a decrease in reaction conversion rate and the appearance of hydrogenation intermediates. Taking all factors into consideration, the system of the present invention selects 0.30h -1 The catalytic hydrogenation effect of diisopropyl phthalate is optimal under space velocity conditions.

[0075] Example 5

[0076] Investigation of hydrogen-ester ratio

[0077] Compared with Example 2, the variable of this example is the hydrogen-ester ratio, and the effect of different hydrogen-ester ratios on the catalytic hydrogenation of diisopropyl phthalate is investigated. The reaction conditions are: temperature 140°C, pressure 4 MPa, space velocity 0.30 h -1 , the results are shown in Table 4 below.

[0078] Table 4

[0079]

[0080]

[0081] From the above results, it can be found that when the hydrogen-ester ratio is 15:1, an intermediate exists in the reaction, and when the hydrogen-ester volume ratio is 30:1, the conversion rate of diisopropyl phthalate and the selectivity of diisopropyl cyclohexanedicarboxylate are optimal.

[0082] Example 6

[0083] Investigation of Ru and Co loading in hydrogenation catalysts

[0084] The content of catalytically active component ruthenium and cobalt as a co-catalyst in the catalyst will significantly affect the catalytic hydrogenation effect of the catalyst on diisononyl phthalate. In the process of preparing a hollow cobalt-ruthenium bimetallic protected by a two-dimensional carbon skeleton, the present invention uses ruthenium salt to electrochemically replace cobalt metal to prepare a ruthenium bimetallic. The content of the two metals in the cobalt-ruthenium bimetallic can be changed by adjusting the concentration of the ruthenium salt. Therefore, the inventors prepared a series of hollow cobalt-ruthenium bimetallics based on two-dimensional carbon skeleton protection by regulating the concentration of the ruthenium salt. The remaining steps are the same as in Example 1. The influence of the content of the two metal components in the cobalt-ruthenium bimetallic on the catalytic activity of the catalyst was explored, and the active components of the catalyst samples were quantitatively analyzed using inductively coupled plasma analysis (ICP). Wherein, the test instrument: Vista-AX plasma emission spectrometer of Varian, USA.

[0085] Five catalysts with different Ru and Co contents were selected from Table 5. The reaction conditions were temperature 140 °C, pressure 4 MPa, and space velocity 0.30 h -1 The hydrogenation reaction of diisopropyl phthalate was carried out at a volume ratio of 30:1, and the other conditions were the same as those in Example 2. The results are shown in Table 5 below.

[0086] Table 5

[0087]

[0088] The above-mentioned catalyst groups 1-4 show that the catalytic activity of the catalysts is extremely weak when only the Co promoter is present. As the amount of Ru catalytically active increases, the Co promoter gradually decreases, and the hydrogenation catalytic activity gradually increases, reaching its highest concentration at the Co promoter in group 3. Further increases in the amount of Ru precious metal do not significantly improve the catalytic activity. To conserve precious metal resources and enhance catalytic effectiveness, the optimal content of the hydrogenation catalysts obtained is 1% of the total mass of ruthenium as the active component and 0.5% of cobalt as the active component. Furthermore, in group 5, the catalytic activity of the catalyst was significantly reduced when the cobalt metal, the promoter component of the cobalt-ruthenium bimetallic, was removed using nitric acid, demonstrating that the synergistic catalytic effect between cobalt and ruthenium can indeed significantly improve the catalytic activity of the catalyst and reduce the amount of precious metal used.

[0089] Example 7

[0090] Investigation of the changes in metal content before and after catalytic reaction for 6 months

[0091] The conditions for the hydrogenation catalytic reaction were temperature 140 °C, pressure 4 MPa, and space velocity 0.30 h -1 The raw materials were introduced into a tubular fixed-bed reactor loaded with the catalyst of Example 1 for hydrogenation of dihexyl nonyl phthalate at a molar ratio of 30:1 for 6 consecutive months. The other conditions were referred to Example 2.

[0092] The Ru and Co contents of the catalyst of Example 1 before reaction and after 6 months of continuous reaction were tested by ICP. The results are shown in Table 6.

[0093] Table 6

[0094] Ru mass fraction / % Co mass fraction / % Example 1: Fresh measured value of catalyst 1.01 0.49 The measured value after the catalyst of Example 1 was used continuously for 6 months 1.01 0.49

[0095] From the above results, it can be seen that even if the catalyst of the present invention reacts for a long time, Ru and Co therein are not easily lost or removed.

[0096] Example 8

[0097] After hydrogenation of diisononyl phthalate using the catalyst described in Example 1 (reaction conditions: 140°C, pressure 4 MPa, space velocity 0.30 h -1 The chromaticity of the obtained diisononyl cyclohexanedicarboxylate sample was directly measured by platinum-cobalt colorimetry, and the specific process was as follows:

[0098] Platinum-cobalt standard solution: The color of a solution containing 1 mg of platinum and 0.5 mg of cobalt per 1000 mL of water is called 1 degree.

[0099] Preparation of standard color series: Add 0mL, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, 1.0mL, 2.0mL, 3.0mL, and 4.0mL of 500-degree platinum-cobalt standard solution into a colorimetric tube and dilute to 10mL with pure water. The color numbers of each colorimetric tube are 0, 5, 10, 15, 20, 25, 50, 100, 150, and 200 degrees, respectively.

[0100] Sample determination: Add the liquid to the colorimetric tube to the 10mL standard line and compare it with the solutions of each color number to determine the color number of the sample. The results of three experimental determinations are shown in the following table. The results are shown in Table 7.

[0101] Table 7

[0102] Measurement group Chroma 1 10 2 15 3 10

[0103] The results in the above table show that the diisononyl cyclohexanedicarboxylate sample obtained by the method of the present invention can be obtained without filtering and the chromaticity of the product is lower than 30, and the chromaticity of the product meets the standard.

[0104] Comparative Example 1

[0105] In order to further illustrate the superiority of the hollow cobalt-ruthenium bimetallic catalyst based on two-dimensional carbon skeleton protection of the present invention in terms of protection of the noble metal as its active component, as well as the color of the product after hydrogenation of the catalyst, a conventional supported catalyst was synthesized as a comparative catalyst in this comparative example. The specific preparation steps are as follows:

[0106] (1) 0.6 g of hexadecyltrimethylammonium bromide and 2.4 g of cobalt(II) acetate tetrahydrate were weighed and dissolved in 400 mL of deionized water. Under stirring, 100 mL of aqueous solution containing 24 g of 2-methylimidazole was quickly injected into the mixture. After stirring at room temperature, the mixture was transferred to a polytetrafluoroethylene-lined autoclave and heated at 120°C for 10 h. After the reaction was completed, the product was collected, washed with ethanol, and dried to obtain a precursor.

[0107] (2) The precursor was placed in an inert gas (nitrogen) atmosphere and calcined at 800°C for 3 h to obtain a two-dimensional carbon framework embedded with cobalt;

[0108] (3) placing the cobalt-embedded two-dimensional carbon framework in 0.1 M nitric acid and stirring overnight to remove the cobalt, thereby obtaining a two-dimensional carbon framework as a support;

[0109] (4) Weigh 0.181 g of RuCl3·xH2O (containing approximately 37% Ru) and 0.426 g of cobalt(II) acetate and completely dissolve them in 20 mL of deionized water; place 5 g of the support in the above solution, reflux and immerse for 4 h, rinse with deionized water and ethanol, dry, and grind to obtain a catalyst precursor;

[0110] (5) Finally, the precursor was placed in a hydrogen atmosphere for calcination activation at a temperature of 150° C. for 8 h to obtain the catalyst of Comparative Example 1.

[0111] Based on the conventional supported catalyst in Comparative Example 1 as a comparison, the service life of the catalysts of Example 1 and Comparative Example 1 was explored by an intermittent process to verify the superiority of the cobalt-ruthenium bimetallic catalyst of the present invention. The intermittent process experiment used 50g of diisopropyl phthalate as a raw material and 0.5g of catalyst. The reaction conditions were: 300r / min (stirring rate), continuous introduction of hydrogen and maintaining a pressure of 4MPa (reaction pressure), 120°C (reaction temperature), and 5h (reaction time). The product yield, change in ruthenium content, and chromaticity of the product after eight cycles of use of the catalyst were explored, as well as the product after only high-speed centrifugation and single filtration.

[0112] Table 9

[0113]

[0114] From the above results, it can be found that compared with conventional supported catalysts, the catalyst of the present invention can be recycled multiple times with high efficiency, and the metal active components are not easily separated, the color of the hydrogenation product is better, and the difficulty of post-processing of the product is effectively reduced.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a two-dimensional carbon skeleton material carrier, characterized in that: The steps include: (1) mixing a solvent, hexadecyltrimethylammonium bromide, cobalt acetate, and 2-methylimidazole, and performing a solvothermal reaction to obtain a carrier precursor; (2) calcining the carrier precursor under an inert gas atmosphere to obtain a two-dimensional carbon skeleton material carrier.

2. The method for preparing a two-dimensional carbon skeleton material carrier according to claim 1, wherein: In step (2), the calcination temperature is 600-1000° C., and the calcination time is 1-6 hours.

3. A two-dimensional carbon skeleton material carrier obtained by the preparation method of the two-dimensional carbon skeleton material carrier as described in claim 1 or 2.

4. A diisononyl phthalate hydrogenation catalyst, characterized in that It comprises the two-dimensional carbon skeleton material carrier according to claim 3 and cobalt and ruthenium embedded in the two-dimensional carbon skeleton material carrier.

5. The diisononyl phthalate hydrogenation catalyst according to claim 4, wherein The diisononyl phthalate hydrogenation catalyst is in the shape of a hollow nanosphere.

6. The diisononyl phthalate hydrogenation catalyst according to claim 4, wherein In the diisononyl phthalate hydrogenation catalyst, the mass content of ruthenium is 0.5% to 1.5%, and the mass content of cobalt is 0.1% to 2.5%.

7. A method for preparing the diisononyl phthalate hydrogenation catalyst according to any one of claims 4 to 6, characterized in that: The steps include: (1) adding a two-dimensional carbon skeleton material support to a ruthenium metal salt solution for electrochemical replacement to obtain a catalyst precursor; (2) calcining the catalyst precursor under a hydrogen atmosphere to obtain the diisononyl phthalate hydrogenation catalyst.

8. The method for preparing the diisononyl phthalate hydrogenation catalyst according to claim 7, wherein In step (2), the calcination temperature is 150-200° C., and the calcination time is 1-5 hours; in step (1), the electrochemical replacement time is 2-6 hours.

9. A method for synthesizing diisononyl cyclohexanedicarboxylate, characterized in that: The method comprises the following steps: in the presence of the diisononyl phthalate hydrogenation catalyst according to any one of claims 4 to 6, carrying out a hydrogenation reaction between diisononyl phthalate and hydrogen to obtain diisononyl cyclohexanedicarboxylate.

10. The method for synthesizing diisononyl cyclohexanedicarboxylate according to claim 9, wherein: Include at least one of the following: The temperature of the hydrogenation reaction is 130-150°C; The pressure of the hydrogenation reaction is 3.5-5 MPa; the volume ratio of hydrogen to diisononyl phthalate in the hydrogenation reaction is (15-50):1; The hydrogenation reaction is carried out using a fixed-bed continuous hydrogenation reactor.

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