DINP hydrogenation catalyst based on carbon material carrier as well as preparation method and application of DINP hydrogenation catalyst

Abstract

The invention belongs to the field of catalysts, and particularly discloses a DINP hydrogenation catalyst based on a carbon material carrier as well as a preparation method and application of the DINP hydrogenation catalyst. The DINP hydrogenation catalyst taking the carbon material as the carrier has the characteristics of high selectivity and high activity, the reaction difficulty of the hydrogenation catalytic reaction of diisononyl phthalate can be remarkably reduced, and higher raw material conversion rate and target product selectivity can be realized at lower temperature and pressure.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and in particular relates to a DINP hydrogenation catalyst based on a carbon material carrier, a preparation method and an application thereof. Background Art

[0002] Because dialkyl cyclohexanedicarboxylates are non-environmentally toxic, non-carcinogenic, non-peroxisome proliferating, non-bioaccumulative, and non-reproductive, they are widely 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 via a one-step hydrogenation of phthalates. BASF (US Pat. Nos. 6,284,917, 6,248,924, and 7,355,084) first proposed the use of a Ru-loaded eggshell hydrogenation catalyst to hydrogenate the benzene ring of diisononyl phthalate (DINP) at 20 MPa, achieving industrialized production of DINP and becoming the largest producer of DINP in China. However, my country currently produces almost zero dialkyl cyclohexanedicarboxylates, with the country still relying primarily on imports. At present, the technology for preparing diisononyl cyclohexanedicarboxylate using a catalyst for hydrogenation of diisononyl phthalate still has problems such as high reaction temperature, high reaction pressure, insufficient reaction conversion rate and selectivity, even when a precious metal catalyst is added, which limits its development. Summary of the Invention

[0003] In view of the drawback of the harsh reaction conditions in the preparation of diisononyl cyclohexanedicarboxylate in the above-mentioned prior art, the present invention provides a DINP hydrogenation catalyst based on a carbon material support, a preparation method thereof, and an application thereof.

[0004] To achieve the above objectives, the following technical solutions are specifically included:

[0005] In a first aspect, the present invention provides a method for preparing a carbon material carrier, comprising the following steps:

[0006] (1) etching ZIF-8 using a tannic acid alcohol-water mixed solution, and then washing and drying to obtain etched ZIF-8;

[0007] (2) mixing the etched ZIF-8, the soft film plate agent, dopamine hydrochloride, mesitylene, a base and a solvent to carry out a polymerization reaction to obtain a carrier precursor;

[0008] (3) The carrier precursor is calcined in an inert gas atmosphere and then acid-washed to obtain a carbon material carrier.

[0009] The above-mentioned preparation method of the present invention first adopts the acid etching method to obtain the hollow MOF, and then controls polydopamine to form a macroporous nanoshell on the surface of the hollow MOF through the soft membrane method, so as to obtain the hollow MOF coated with the macroporous polydopamine shell as a precursor. After calcination treatment in an inert atmosphere, a multi-level porous hollow carbon cubic carrier is obtained.

[0010] Preferably, in step (1), the preparation method of ZIF-8 can be obtained using a commercially available or homemade method, such as a homemade method comprising the following steps: mixing 2-methylimidazole, hexadecyltrimethylammonium bromide, zinc nitrate and a solvent, reacting to obtain the ZIF-8; preferably, the mass ratio of 2-methylimidazole, hexadecyltrimethylammonium bromide, zinc nitrate and solvent is 2-methylimidazole: hexadecyltrimethylammonium bromide: zinc nitrate: solvent = (5-15): (0.1-0.5): (0.5-1.5): (100-200); and the reaction time is 1-5h.

[0011] Preferably, in step (1), the concentration of the tannic acid is 1-10 g / L, and the etching time is 2-20 min.

[0012] Preferably, in step (1), the volume percentage of water in the alcohol aqueous solution is 10-30%.

[0013] Preferably, in step (2), the mass ratio of ZIF-8, soft film plate agent, dopamine hydrochloride, mesitylene, alkali and solvent is ZIF-8:soft film plate agent:dopamine hydrochloride:mesitylene:alkali:solvent=(0.5-2):(0.1-0.3):(0.3-0.8):(0.5-2):(1-10):(0.1-1):(30-100).

[0014] Preferably, in step (2), the polymerization reaction time is 1-10 hours.

[0015] Preferably, in step (2), the soft film sheet comprises at least one of F123 and F127.

[0016] Preferably, in step (2), the alkalinity includes an inorganic base, such as at least one of ammonia water, sodium hydroxide, and potassium hydroxide.

[0017] Preferably, in step (2), the solvent includes ethanol and water.

[0018] Preferably, in step (3), the calcination temperature is 700-900° C., and the calcination time is 1-5 h.

[0019] Preferably, in step (3), the inert gas includes at least one of nitrogen, argon and helium.

[0020] In a second aspect, the present invention provides a carbon material carrier prepared by the method for preparing the carbon material carrier.

[0021] Preferably, the carbon material carrier has a multi-level pore structure of mesopores and macropores and a hollow cubic structure.

[0022] In a third aspect, the present invention provides a diisononyl phthalate hydrogenation catalyst, comprising the carbon material carrier and an active component and an auxiliary agent loaded on the carbon material carrier; the active component is ruthenium, and the auxiliary agent is at least one of copper, iron, cobalt, nickel, and chromium.

[0023] The above-mentioned preparation method of the present invention first adopts the acid etching method to obtain a hollow MOF, and then controls polydopamine to form a macroporous nanoshell on the surface of the hollow MOF through the soft membrane plate method, so as to obtain a hollow MOF coated with a macroporous polydopamine shell as a precursor. After calcination in an inert atmosphere, a multi-level porous hollow carbon cubic carrier is obtained. Thereafter, the active ingredients and auxiliary agents are loaded on the carrier through processes such as impregnation, drying, roasting and reduction to obtain the supported catalyst loaded with precious metals of the present invention.

[0024] Preferably, in the diisononyl phthalate hydrogenation catalyst, the mass percentage of the active component is 0.1-1%.

[0025] Further preferably, in the diisononyl phthalate hydrogenation catalyst, the mass percentage of the active component is 0.2-0.5%.

[0026] The loading amount of the noble metal ruthenium in the catalyst of the present invention is relatively small, thereby reducing the cost of catalyst preparation.

[0027] Preferably, in the diisononyl phthalate hydrogenation catalyst, the mass percentage of the auxiliary agent is 1-10%.

[0028] In a fourth aspect, the present invention provides a method for preparing the diisononyl phthalate hydrogenation catalyst, comprising the following steps:

[0029] The active components and metal ions in the auxiliary agent are loaded on a carbon material carrier by impregnation, and then calcined under a hydrogen gas atmosphere to obtain the diisononyl phthalate hydrogenation catalyst.

[0030] Preferably, the calcination temperature is 150-350° C., and the calcination time is 5-12 hours.

[0031] Preferably, the immersion temperature is 90-120° C., and the immersion time is 2-48 hours.

[0032] Preferably, the impregnation further includes the steps of washing, drying and grinding, and the drying temperature is 60-100°C.

[0033] Preferably, the raw materials of the metal ions in the active components and the auxiliary agents are all corresponding soluble metal salts.

[0034] Preferably, the soluble metal salt includes but is not limited to the corresponding chloride salt, nitrate salt or sulfate salt, such as ruthenium trichloride, aluminum chloride, copper nitrate and the like.

[0035] Preferably, the pickling acid is hydrochloric acid with a mass percentage of 5-15%, and the pickling time is 0.5-2 hours.

[0036] In a fifth aspect, the present invention provides a method for synthesizing diisononyl cyclohexanedicarboxylate, comprising the steps of: hydrogenating diisononyl phthalate with hydrogen in the presence of the diisononyl phthalate hydrogenation catalyst to obtain diisononyl cyclohexanedicarboxylate.

[0037] Preferably, the temperature of the hydrogenation reaction is 60-120°C, and more preferably, the temperature of the hydrogenation reaction is 80-100°C.

[0038] Preferably, the pressure of the hydrogenation reaction is 0.5 to 1.3 MPa, and more preferably, the pressure of the hydrogenation reaction is 0.7 to 1 MPa.

[0039] Preferably, the raw liquid space velocity of the hydrogenation reaction is 0.2 to 0.4 h -1 .

[0040] Preferably, the volume ratio of hydrogen in the hydrogenation reaction to diisononyl phthalate is (15-50):1.

[0041] Preferably, the hydrogenation reaction is carried out using a fixed-bed continuous hydrogenation reactor.

[0042] In the diisononyl phthalate hydrogenation reaction carried out by adopting the fixed-bed continuous hydrogenation reactor of the present invention, the DINP conversion rate can be as high as 99.9%, and the DINCH selectivity can be as high as 99.8%.

[0043] The hydrogenation catalyst of the present invention uses the precious metal ruthenium as an active ingredient, uses at least one metal selected from copper, iron, cobalt, nickel, and chromium as an auxiliary agent, and uses a carbon material having a multi-level pore structure of mesopores and macropores and a hollow carbon cubic structure as a carrier. The carrier has abundant accessible surface, large specific surface area, and a special structure of a multi-level pore structure of mesopores and macropores and a hollow carbon cubic structure, which can make the loaded precious metal more dispersed, so that the final hydrogenation catalyst has a rich mesopore-macropore multi-level pore structure, wherein the outer macropores serve as a storage reservoir for the reaction liquid to shorten the diffusion distance, and the inner mesopore structure provides a high-pressure gas. The invention provides a rich specific surface area and accelerates the rapid mass transfer of reactants. Therefore, the hydrogenation catalyst of the present invention has the characteristics of high activity and high selectivity, can effectively reduce the pressure and temperature conditions required for the reaction, significantly improve the activity and efficiency of the catalyst in catalyzing or promoting the reaction, and reduce the reaction difficulty of the catalytic reaction. Specifically, it can effectively reduce the temperature and pressure conditions required for the DINP hydrogenation reaction to compensate for the harsh reaction conditions and low catalyst activity required in the prior art, thereby reducing the production difficulty of diisononyl cyclohexanedicarboxylate (DINCH) plasticizer and reducing energy consumption. The catalyst preparation method of the present invention is simple, has good catalytic activity, mild hydrogenation catalytic reaction conditions, high product yield, and few by-products.

[0044] Compared with the prior art, the present invention has the following beneficial effects: the DINP hydrogenation catalyst using carbon material as a carrier has the characteristics of high selectivity and high activity, can significantly reduce the reaction difficulty of the catalytic hydrogenation reaction of diisononyl phthalate, and achieve a higher raw material conversion rate and target product selectivity at lower temperature and pressure. DETAILED DESCRIPTION

[0045] 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.

[0046] Brief description of the following examples and comparative examples:

[0047] Example 1 is a method for preparing a diisononyl phthalate hydrogenation catalyst using a multi-level porous hollow carbon cube as a carrier;

[0048] Examples 2 to 5 are experiments to investigate the process conditions for using the catalyst;

[0049] Examples 6 and 7 are catalyst characterization and optimization;

[0050] Comparative Example 1 shows the performance of other types of catalysts;

[0051] 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.

[0052] Example 1

[0053] The specific preparation steps of the hydrogenation catalyst are as follows:

[0054] (1) 10.8 g of 2-methylimidazole and 200 mg of hexadecyltrimethylammonium bromide were added to 100 mL of deionized water, mixed with 100 mL of an aqueous solution containing 0.7 g of zinc nitrate, stirred vigorously for 5 min, and allowed to stand at room temperature for 3 h;

[0055] (2) The obtained white solid was washed with deionized water, redispersed in 200 mL of ethanol, and etched with 50 mL of 20 g / L tannic acid aqueous solution for 5 min. The product was washed with water and then dried.

[0056] (3) 1 g of the product was redispersed in a mixed solution of water and ethanol (50 mL in total), and 0.15 g of P123, 0.65 g of F127, 1.4 g of dopamine hydrochloride, and 4 mL of mesitylene were added. After all substances were fully dissolved, 2 mL of concentrated ammonia (25% to 28%) was added and stirred for 3 h. The product was washed with water, dried, and calcined in a nitrogen atmosphere for 3 h at 800°C. The black solid powder obtained after calcination was added to a 10% aqueous hydrochloric acid solution and reacted for half an hour to remove residual zinc. After washing and drying, a multi-level porous hollow carbon cubic support was obtained;

[0057] (4) Weigh 0.081 g of RuCl3·xH2O (containing approximately 37% Ru) and 0.382 g of Cu(NO3)2·3H2O and completely dissolve them in 20 mL of deionized water. Add 2 g of the support to the impregnation solution, stir for 3 h, and then reflux in a reflux apparatus at 110°C for 18 h. Rinse with deionized water, dry, and grind to obtain a catalyst precursor.

[0058] (5) Finally, the catalyst precursor was activated by calcination in a hydrogen atmosphere at a temperature of 150°C for 8 hours. Quantitative analysis was performed using inductively coupled plasma analysis technology. The active component in the obtained hydrogenation catalyst accounted for 0.3% of its total mass, and the auxiliary component accounted for 3.5% of the total mass. The test instrument used was a Vista-AX plasma emission spectrometer produced by Varian, USA.

[0059] Example 2

[0060] Investigation of reaction temperature

[0061] 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.

[0062] 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 1 MPa, space velocity 0.30 h -1 , hydrogen ester molar ratio is 30:1, and the results are shown in Table 1 below.

[0063] Table 1

[0064] Temperature / ℃ Conversion rate / % Selectivity / % 60 86.1 89.0 80 99.4 99.3 100 99.9 99.8 120 99.2 98.8

[0065] Thanks to the excellent hydrogenation catalytic performance of the catalyst of the present invention, a high hydrogenation reaction of diisopropyl phthalate can be achieved at a relatively low temperature. Although the hydrogenation reaction is an exothermic reaction, appropriately increasing the temperature is conducive to the catalytic hydrogenation reaction. It can be found that when the temperature is increased to 100° C., the catalytic reaction effect reaches the optimal effect. When the temperature is further increased to 120° C., the conversion rate and selectivity of the hydrogenation begin to deteriorate. The catalyst of the present invention has the optimal catalytic hydrogenation effect of diisopropyl phthalate under the hydrogenation temperature condition of 100° C.

[0066] Example 3

[0067] Investigation of reaction pressure

[0068] 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 100°C, space velocity 0.30h -1 , hydrogen ester molar ratio is 30:1, and the results are shown in Table 2 below.

[0069] Table 2

[0070] Pressure / MPa Conversion rate / % Selectivity / % 0.5 98.6 99.1 0.7 99.2 99.2 1 99.9 99.8 1.3 99.9 99.8

[0071] By the above results, it can be found that, benefiting from the excellent hydrogenation catalytic performance of the catalyst of the present invention, higher diisopropyl phthalate hydrogenation can be realized under relatively low pressure, and along with pressure increase, catalytic effect improves, and after reaching 1Mpa, catalytic effect reaches optimum, and further increasing pressure catalytic effect is constant. This is because when system pressure becomes large, the concentration of hydrogen in the reaction medium increases, and the amount of hydrogen of catalyst adsorption becomes many, thereby system reaction rate improves, and when pressure is increased to a certain degree, the catalyst surface amount of hydrogen reaches saturation, and feed conversion is no longer affected, but pressure is too high to increase reaction cost, and under comprehensive consideration, catalyst of the present invention has optimum diisopropyl phthalate catalytic hydrogenation effect under 1Mpa hydrogenation pressure condition.

[0072] Example 4

[0073] Investigation of raw material liquid space velocity

[0074] 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 100°C, hydrogen-ester molar ratio 30:1, and pressure 1 MPa. The results are shown in Table 3 below.

[0075] Table 3

[0076] <![CDATA[Air speed / h -1 > Conversion rate / % Selectivity / % 0.20 98.5 99.1 0.30 99.9 99.8 0.40 99.3 96.1

[0077] From the above results, it can be found that with the increase of the raw liquid space velocity, 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 raw liquid space velocity, 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 the reaction conversion rate and the appearance of hydrogenation intermediates. Under comprehensive consideration, the catalyst of the present invention has a high reaction temperature at 0.3h. -1 The catalytic hydrogenation effect of diisopropyl phthalate is optimal under space velocity conditions.

[0078] Example 5

[0079] Investigation of hydrogen-ester ratio

[0080] Compared with Example 2, the variable of this example is the hydrogen-ester ratio. The effect of different hydrogen-ester ratios on the catalytic hydrogenation of diisopropyl phthalate is investigated. The reaction conditions are: temperature 100°C, space velocity 0.30h -1 , pressure 1MPa, and the results are shown in Table 4 below.

[0081] Table 4

[0082] Hydrogen ester ratio Conversion rate / % Selectivity / % 15:1 99.1 98.8 20:1 99.4 99.2 30:1 99.9 99.8 40:1 99.1 99.2 50:1 99.3 99.1

[0083] From the above results, it can be found that when the hydrogen-ester ratio is 15:1, an intermediate exists in the reaction. When the hydrogen-ester volume ratio is 30:1, the conversion rate of dihexyl nonyl phthalate and the selectivity of dihexyl nonyl cyclohexanedicarboxylate are higher.

[0084] Example 6

[0085] Investigation of Ru loading in hydrogenation catalysts

[0086] Compared with Example 1, this example makes appropriate increases or decreases when adding RuCl3·xH2O (which contains about 37% Ru) or the carrier, while keeping other conditions unchanged, to prepare a series of catalysts with different Ru loadings. The active components in the catalyst samples of various catalysts finally prepared are quantitatively analyzed by inductively coupled plasma analysis (ICP). Three catalysts, including catalysts with Ru contents of 0.10% and 0.50% and the catalyst with a Ru content of 0.30% prepared in Example 1, are selected to investigate the effect of different Ru contents on the hydrogenation catalytic reaction.

[0087] The catalysts with Ru contents of 0.10%, 0.30%, and 0.50% were used to hydrogenate diisopropyl phthalate to analyze the effect of different Ru loadings on the hydrogenation of diisopropyl phthalate. The conditions for the hydrogenation catalytic reactions were: temperature 100°C, pressure 1 MPa, and space velocity 0.30 h-1. -1 , hydrogen ester molar ratio is 30:1, and the rest refers to Example 2. The results are shown in the following Table 5.

[0088] Table 5

[0089] Ru mass fraction / % Conversion rate / % Selectivity / % 0.10 96.7 98.8 0.30 99.9 99.8 0.50 99.8 99.8

[0090] The above results show that as the Ru loading in the catalyst increases, the effect of the catalyst on the hydrogenation of diisopropyl phthalate also increases, and the catalytic effect reaches the best when the loading reaches 0.3%.

[0091] Example 7

[0092] This example investigates the effects of different additives. Compared with Example 1, this example uses nitrates corresponding to iron, cobalt, nickel, and chromium instead of Cu(NO3)2·3H2O to prepare different catalysts, where the atomic masses of iron, cobalt, nickel, and chromium are equal to the mass of Cu atoms, and all other conditions are the same.

[0093] Referring to the catalyst activity evaluation method of Example 2, the conditions for the hydrogenation catalytic reaction were: temperature 100°C, pressure 1 MPa, space velocity 0.30 h -1 The catalytic hydrogenation reaction of diisopropyl phthalate was carried out at a molar ratio of 30:1, and the results are shown in Table 6.

[0094] Table 6

[0095] co-catalyst Conversion rate / % Selectivity / % Cu 99.9 99.8 Fe 99.7 99.6 Co 99.9 99.8 Ni 99.8 99.8 Cr 99.4 99.7

[0096] Comparative Example 1

[0097] MOF-derived carbon cubes (without etching and without dopamine coating):

[0098] (1) 10.8 g of 2-methylimidazole and 200 mg of hexadecyltrimethylammonium bromide were added to 100 mL of deionized water, mixed with 100 mL of an aqueous solution containing 0.7 g of zinc nitrate, stirred vigorously for 5 min, and allowed to stand at room temperature for 3 h;

[0099] (2) After washing the obtained white solid with deionized water, the product was dried and calcined in a nitrogen atmosphere at 800° C. for 3 h. The black solid powder obtained after calcination was added to a 10% hydrochloric acid aqueous solution and reacted for half an hour to remove residual zinc. After washing and drying, a multi-level porous hollow carbon cubic support was obtained;

[0100] (3) Weigh 0.081 g of RuCl3·xH2O (containing approximately 37% Ru) and 0.382 g of Cu(NO3)2·3H2O and completely dissolve them in 20 mL of deionized water. Add 2 g of the support to the impregnation solution, stir for 3 h, and then reflux in a reflux apparatus at 110°C for 18 h. Rinse with deionized water, dry, and grind to obtain a catalyst precursor.

[0101] (4) Finally, the catalyst precursor was calcined in a hydrogen atmosphere for activation at a temperature of 150 °C for 8 h.

[0102] The Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution of the catalysts prepared in Example 1 and Comparative Example 1 were characterized by an ASAP 2020 V4.02 (V4.02J) physical adsorption instrument (Micromeritics, USA). The results are shown in Table 7 below:

[0103] Table 7

[0104]

[0105] The catalysts prepared in Example 1 and Comparative Example 1 were heated under the following reaction conditions: temperature 100°C, pressure 1 MPa, space velocity 0.30 h -1 The catalytic hydrogenation reaction of diisopropyl phthalate was carried out under the conditions of a molar ratio of 30:1 between phthalate and hydrogen. The effects of various catalysts on the hydrogenation of diisopropyl phthalate are shown in Table 8 below.

[0106] Table 8

[0107] catalyst catalyst carrier Conversion rate / % Selectivity / % Example 1 Multi-level pore hollow carbon cube 99.9 99.8 Comparative Example 1 MOF-derived carbon cubes 83.1 81.7

[0108] The above results indicate that the hierarchical carbon cube exhibits superior catalytic hydrogenation performance compared to the MOF-derived carbon cube of Comparative Example 1. This is due to the newly added macropores within the hierarchical structure acting as a reservoir for the reaction liquid, overcoming the problem of insufficient contact between the catalyst and the reaction liquid caused by surface tension in the pores of a single mesoporous catalyst. The hierarchical hollow carbon cube-supported catalyst prepared by the present invention exhibits excellent hydrogenation catalytic performance due to its combination of the advantages of both a hollow and hierarchical structure.

[0109] 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 carbon material carrier, characterized in that: The steps include: (1) etching ZIF-8 using a tannic acid alcohol-water mixed solution, and then washing and drying to obtain etched ZIF-8; (2) mixing the etched ZIF-8, the soft film plate agent, dopamine hydrochloride, mesitylene, a base and a solvent to carry out a polymerization reaction to obtain a carrier precursor; (3) The carrier precursor is calcined in an inert gas atmosphere and then acid-washed to obtain a carbon material carrier.

2. The method for preparing a carbon material carrier according to claim 1, wherein: In step (3), the calcination temperature is 700-900° C., and the calcination time is 1-5 hours.

3. A carbon material carrier obtained by the method for preparing a carbon material carrier according to claim 1 or 2.

4. The carbon material carrier according to claim 3, characterized in that The carbon material carrier has a multi-level pore structure of mesopores and macropores and a hollow cubic structure.

5. A diisononyl phthalate hydrogenation catalyst, characterized in that The invention comprises the carbon material carrier according to claim 3 or 4, and an active component and an auxiliary agent loaded on the carbon material carrier; the active component is ruthenium, and the auxiliary agent is at least one of copper, iron, cobalt, nickel, and chromium.

6. The diisononyl phthalate hydrogenation catalyst according to claim 5, wherein In the diisononyl phthalate hydrogenation catalyst, the mass percentage of the active component is 0.1-1%, and the mass percentage of the auxiliary agent is 1-10%.

7. A method for preparing the diisononyl phthalate hydrogenation catalyst according to claim 5 or 6, characterized in that: The steps include: The active components and metal ions in the auxiliary agent are loaded on the carbon material carrier by impregnation, and then calcined under a hydrogen gas atmosphere to obtain the diisononyl phthalate hydrogenation catalyst.

8. The method for preparing the diisononyl phthalate hydrogenation catalyst according to claim 7, wherein The calcination temperature is 150-350° C., and the calcination time is 5-12 hours.

9. A method for synthesizing diisononyl cyclohexanedicarboxylate, characterized in that: The steps include: In the presence of the diisononyl phthalate hydrogenation catalyst according to claim 5 or 6, diisononyl phthalate is subjected to a hydrogenation reaction with 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 60 to 120°C; The pressure of the hydrogenation reaction is 0.5 to 1.3 MPa; The volume ratio of hydrogen gas to diisononyl phthalate in the hydrogenation reaction is (15-50):1.

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