A dinp hydrogenation catalyst based on a metal oxide carrier, and a preparation method and application thereof

Abstract

The application belongs to the field of catalysts, and specifically discloses a DINP hydrogenation catalyst based on a metal oxide carrier, a preparation method and application thereof. The catalyst has a hollow spherical structure and mesoporous structure and a noble metal nanocluster active component. The catalyst preparation method is simple, can significantly reduce the use amount of noble metal, hydrogenation catalytic reaction difficulty and production cost while maintaining high DINP hydrogenation catalytic activity and high DINCH selectivity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysts, and particularly relates to a DINP hydrogenation catalyst based on a metal oxide carrier and a preparation method and application thereof. BACKGROUND

[0002] The cyclohexane dicarboxylic acid dialkyl ester plasticizer has the characteristics of no environmental toxicity, no carcinogenicity, no peroxisome proliferation, no biological accumulation, and no reproductive toxicity, and can be applied to the production of children's toys, medical supplies, PVC plastic particles, and cable and wire materials. In industrial production, the cyclohexane dicarboxylic acid dialkyl ester plasticizer is mainly prepared by one-step hydrogenation of phthalate.

[0003] At present, the preparation of cyclohexane dicarboxylic acid dialkyl ester by hydrogenation of phthalate mainly has the problems of high reaction temperature, insufficient reaction conversion rate and selectivity, and large amount of noble metal used in the catalyst (the content of noble metal in commercial hydrogenation catalysts reaches more than 3%).

[0004] How to reduce the use of noble metal while maintaining the catalytic effect of the catalyst is one of the focuses of current research. Among them, preparing noble metal into nanoclusters is an effective way to improve the catalytic effect of noble metal and reduce the use of noble metal. Nanoclusters are particles with a size of less than 10 nm and a high degree of dispersion, which are a typical zero-dimensional nanomaterial. The small size can improve the atomic utilization rate and the specific surface area, thereby providing more active sites and achieving the reduction of the use of noble metal while improving the catalytic activity. However, noble metal nanocluster materials are usually difficult to prepare and prone to agglomeration. In the application of actual industrial catalysts, the preparation process of noble metal nanocluster catalysts is generally complex, the required catalytic reaction conditions are harsh, and the catalysts are prone to deactivation. SUMMARY

[0005] In view of the problem of high use of noble metal in the preparation of cyclohexane dimethyl ester (DINCH) by the existing catalysts, the present application provides a phthalic acid diisononyl ester (DINP) hydrogenation catalyst based on a metal oxide carrier and a preparation method and application thereof.

[0006] To achieve the above-mentioned purpose, the specific technical solutions include the following:

[0007] A diisononyl phthalate hydrogenation catalyst includes a support and an active component and an auxiliary agent supported on the support. The active component is a noble metal nanocluster, and the auxiliary agent includes at least one of copper, iron, cobalt, nickel, and chromium. The diisononyl phthalate hydrogenation catalyst has a hollow spherical morphology and a mesoporous structure. The support is a metal oxide, and the metal oxide includes at least one of alumina, zirconium oxide, and titanium oxide.

[0008] Preferably, the noble metal in the noble metal nanocluster includes at least one of ruthenium, platinum, palladium, and gold.

[0009] Preferably, in the diisononyl phthalate hydrogenation catalyst, the mass content of the active component is 0.02% to 0.15%, and the mass percentage of the auxiliary agent is 0.5% to 2%.

[0010] Within the aforementioned content range, high activity and high selectivity are ensured while significantly reducing the amount of precious metals used.

[0011] More preferably, the active component in the diisononyl phthalate hydrogenation catalyst has a mass content of 0.05% to 0.1%.

[0012] This invention utilizes hollow mesoporous metal oxide spheres, which possess advantages such as abundant exposed and accessible surfaces and a large specific surface area, as a carrier to load highly dispersed, highly atomically efficient, and highly reactive noble metal nanoclusters and additives, thus forming the diisononyl phthalate hydrogenation catalyst of this invention. The hollow spheres and mesoporous structure of this catalyst provide a large exposed active surface area, promoting liquid-mass exchange and achieving high catalytic activity. It effectively reduces the temperature and pressure requirements for the DINP hydrogenation reaction, thereby reducing the production difficulty of diisononyl cyclohexanedicarboxylate (DINCH) plasticizer and lowering energy consumption. This catalyst overcomes the problems of existing diisononyl phthalate hydrogenation catalysts, such as harsh reaction conditions, low catalyst activity, and high noble metal usage. In other words, the catalyst of this invention features mild hydrogenation catalytic reaction conditions, low noble metal usage, and high catalytic activity.

[0013] The present invention also provides a method for preparing the diisononyl phthalate hydrogenation catalyst, comprising the following steps:

[0014] (1) Add ammonia to dopamine aqueous solution to react, collect the solid and wash it to obtain polydopamine balls;

[0015] (2) The metal ions in the carrier, active component and additive are loaded onto the polydopamine sphere by impregnation and then calcined in air to obtain the catalyst precursor;

[0016] (3) The catalyst precursor is calcined in a hydrogen atmosphere to obtain the diisononyl phthalate hydrogenation catalyst.

[0017] This invention uses polydopamine as a sacrificial hard template (precursor) and adsorbent. After polydopamine adsorbs the active components, additives, and metal ions in the support, the template is removed through a one-step calcination process. Simultaneously, the precursor metal ions of the support are converted into hollow spheres and mesoporous oxide supports, and the metal ions of the active components are converted into highly dispersed noble metal nanoclusters on the support. The abundant precursor ions of the support can effectively protect the noble metal from agglomeration that may occur during the nanocluster formation process during calcination, improving the dispersibility and stability of the nanoclusters. After one-step calcination, the catalyst with the supported noble metal nanoclusters is obtained. The final catalyst has a mesoporous pore structure and a hollow spherical morphology, with the noble metal nanoclusters uniformly and stably dispersed therein. Based on the hollow sphere and mesoporous structure of the catalyst, as well as the noble metal nanoclusters with high atomic utilization and catalytic activity, the catalyst can provide a large exposed active surface, which can promote liquid-mass exchange. Therefore, the catalyst has high catalytic activity and extremely low noble metal loading, which can effectively reduce the temperature, pressure and other conditions required for the DINP hydrogenation reaction, thereby reducing the production difficulty of diisononyl cyclohexanedicarboxylate (DINCH) plasticizer, reducing energy consumption, significantly reducing the catalyst preparation cost, and the catalyst preparation method is simple.

[0018] Preferably, in step (1), the reaction time is 1-6 hours.

[0019] Preferably, in step (1), the mass concentration of dopamine in the aqueous solution is 200-1000 g / L.

[0020] Preferably, in step (1), the mass ratio of ammonia to dopamine is (0.006-0.02):1.

[0021] Preferably, in step (2), the calcination temperature is 450-650℃ and the calcination time is 2-4h.

[0022] Preferably, in step (2), the mass ratio of metal ions to polydopamine spheres in the active component is (0.001-0.05):(8-15).

[0023] Preferably, in step (2), the mass ratio of metal ions to polydopamine spheres in the additive is (0.05-2):(8-15).

[0024] Preferably, in step (2), the mass ratio of metal ions to polydopamine spheres in the carrier is (4-8):(8-15).

[0025] Preferably, in step (2), the time of the impregnation is 2-48h.

[0026] Preferably, in the impregnation of step (2), the mass concentration of the polydopamine spheres in the impregnation solution is 50-120g / L.

[0027] Preferably, in step (3), the temperature of the calcination is 150-250℃, and the time of the calcination is 2-5h.

[0028] Preferably, the metal ions in the carrier, the active component and the adjuvant are added to water in the form of water-soluble metal salts to prepare a metal ion solution required for the impregnation, wherein the water-soluble metal salts include, but are not limited to, corresponding chloride salts, nitrate salts or sulfate salts.

[0029] The application also provides an application of the diisononyl phthalate hydrogenation catalyst, and the diisononyl phthalate hydrogenation catalyst is used as a catalyst for preparing diisononyl cyclohexanedicarboxylate by hydrogenation reaction of diisononyl phthalate.

[0030] Preferably, the temperature of the hydrogenation reaction is 140-160℃.

[0031] Preferably, the pressure of the hydrogenation reaction is 2-4MPa.

[0032] Preferably, the liquid space velocity of the raw material of the hydrogenation reaction is 0.2-0.45h -1 ; further preferably, the liquid space velocity of the raw material of the hydrogenation reaction is 0.3-0.4h -1 .

[0033] Preferably, the volume ratio of hydrogen to diisononyl phthalate in the hydrogenation reaction is (20-50):1; further preferably, the volume ratio of hydrogen to diisononyl phthalate in the hydrogenation reaction is (10-40):1.

[0034] Preferably, the hydrogenation reaction is carried out by using a fixed-bed continuous hydrogenation reactor.

[0035] In the application, the diisononyl phthalate hydrogenation reaction is carried out by using a DINP hydrogenation catalyst based on a metal oxide carrier, and the DINP conversion rate can be as high as 99.4%, and the DINCH selectivity can be as high as 99.6%.

[0036] Compared with the prior art, the application has the following beneficial effects: the catalyst has a hollow spherical morphology, a mesoporous structure and a noble metal nanocluster active component, the catalyst preparation method is simple, and the catalyst can significantly reduce the use amount of noble metal, the difficulty of hydrogenation catalytic reaction and the production cost while maintaining high DINP hydrogenation catalytic activity and high DINCH selectivity. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 TEM image of the catalyst prepared for Example 1 (scale 50 nm).

[0038] Figure 2 TEM image of the catalyst prepared for Example 1 (scale 20 nm). DETAILED DESCRIPTION

[0039] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described below through specific examples. The test methods used in the examples and / or comparative examples are all conventional methods unless otherwise specified; and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0040] Brief descriptions of the following examples and comparative examples:

[0041] Example 1 is a preparation method of a diisononyl phthalate hydrogenation catalyst with hollow mesoporous metal oxide supported highly dispersed noble metal nanoclusters prepared by one-step calcination;

[0042] Examples 2-5 are catalyst process condition investigation experiments;

[0043] Example 6 is a Ru loading amount investigation experiment of the catalyst;

[0044] Examples 7 and 8 are catalyst investigation experiments of different additives and metal oxides, respectively;

[0045] Comparative Examples 1-2 are catalysts prepared by a non-one-step calcination method of the present application and commercially available noble metal-based catalysts, respectively;

[0046] The selectivity mentioned in the following examples and comparative examples is all the selectivity of DINCH, and the conversion rate is all the conversion rate of DINP.

[0047] Example 1

[0048] The specific preparation steps of the hydrogenation catalyst are as follows:

[0049] (1) 50 g of dopamine was weighed and dissolved in 100 mL of deionized water, 2.56 mL of concentrated ammonia water (25-28%) was added dropwise under stirring, and stirring was maintained for 2 h, the precipitate was collected and centrifuged and washed with water to obtain polydopamine (PDA) spheres;

[0050] (2) Weigh 38.3g Al(Cl)3, 0.027g RuCl3·xH2O (containing about 37% Ru), and 0.271g Cu(NO3)2·3H2O, dissolve them in water to prepare a 100mL mixed solution, add 10g PDA balls, mix well, and stir vigorously overnight (12h). Centrifuge and wash with water to remove excess soluble salts, collect the precipitate, and dry it at 60℃ for 24h.

[0051] (3) After crushing, the particles were calcined in air for 2 hours at a temperature of 450℃ to obtain a hollow mesoporous alumina sphere supported on a highly dispersed noble metal nanocluster catalyst.

[0052] (4) Before use, the catalyst is calcined and activated in a hydrogen atmosphere at a temperature of 150°C for 3 hours to obtain a hydrogenation catalyst. The active component Ru accounts for 0.05% of the total mass of the hydrogenation catalyst, and the auxiliary agent Cu accounts for 0.6% of the total mass.

[0053] The Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution of the catalyst prepared above were characterized using an ASAP 2020V4.02 (V4.02J) physical adsorption analyzer (Micromeritics, USA), and the results are shown in Table 1 below.

[0054] Table 1

[0055] <![CDATA[Specific surface area / m 2 ·g -1 > Pore volume / mL-g -1 ]] Pore diameter / nm 153.6 0.64 7.55

[0056] The above results indicate that the hydrogenation catalyst prepared by the one-step calcination method has a typical mesoporous structure with an average pore size of 7.55 nm.

[0057] The catalyst described above was characterized by transmission electron microscopy (TEM), and the results are shown in the attached figure. Figure 1 and 2 , by appendix Figure 1 It can be observed that the catalyst prepared by this invention has a hollow nanosphere morphology. The hollow nanospheres are uniformly dispersed and of uniform size, with a diameter between 40-120 nm. Meanwhile, from the attached... Figure 2 TEM images at higher magnification show that noble metal nanoclusters are uniformly distributed on the hollow nanospheres (in brighter areas). This indicates that the catalyst of the present invention is a catalyst with a hollow sphere morphology and mesoporous structure of uniformly dispersed noble metal nanoclusters.

[0058] Example 2

[0059] Investigation of reaction temperature:

[0060] The catalytic properties of the catalyst were investigated using a tubular fixed bed reactor. The fixed bed reactor had a length of 1500 mm and an inner diameter of 32 mm. The upper and lower parts of the reactor were filled with quartz sand, and the middle part was filled with the catalyst prepared in Example 1. The catalyst loading was 200 mL. The reaction temperature, pressure, hydrogen and dihexyl naphthalene phthalate feed amount were adjusted, and the catalytic reaction was carried out. The reaction material was cooled and sampled at regular intervals for analysis. Based on the area normalization method, the samples were qualitatively and quantitatively analyzed by liquid chromatography. The test instrument used was an American Agilent 1260 high performance liquid chromatograph. The chromatographic separation conditions were as follows: the chromatographic column was Agilent ZORBAX SB-C18 5 μm (4.6*150 mm), the mobile phase was HPLC methanol, the flow rate was 1.2 mL / min, the sample size was 5 μL, the column temperature was 30°C, and the ultraviolet detection wavelength was 207 nm.

[0061] The effect of different reaction temperatures on the catalytic hydrogenation of dihexyl naphthalene phthalate was investigated by changing only the reaction temperature. The other reaction conditions were as follows: pressure 3 MPa, space velocity 0.40 h -1 , hydrogen to ester molar ratio 40:1. The results are shown in Table 2 below.

[0062] Table 2

[0063] Temperature / °C Conversion / % Selectivity / % 140 99.1 99.4 150 99.4 99.6 160 99.0 98.8

[0064] The dihexyl naphthalene phthalate hydrogenation reaction is an exothermic reaction, but appropriate temperature increase within a certain range is beneficial to the catalytic hydrogenation reaction. It can be found that when the temperature is increased to 150°C, the catalytic reaction effect reaches the optimum.

[0065] Example 3

[0066] Investigation of reaction pressure:

[0067] Compared with Example 2, the variable of this example is the reaction pressure. The effect of different reaction pressures on the catalytic hydrogenation of dihexyl naphthalene phthalate was investigated. The reaction conditions were as follows: temperature 150°C, space velocity 0.40 h -1 , hydrogen to ester molar ratio 40:1. The results are shown in Table 3 below.

[0068] Table 3

[0069] Pressure / MPa Conversion / % Selectivity / % 2 99.1 99.3 3 99.4 99.6 4 99.3 99.4

[0070] From the above results, it can be found that with the increase of pressure, the catalytic effect is improved, and when the pressure reaches 3 MPa, the catalytic effect reaches the optimum, and further increasing the pressure, the catalytic effect is basically unchanged. This is because when the system pressure becomes large, the concentration of hydrogen in the reaction medium increases, and the amount of hydrogen adsorbed by the catalyst increases, thereby the reaction rate of the system increases. When the pressure increases to a certain extent, the amount of hydrogen on the surface of the catalyst reaches saturation, and the conversion rate of the raw material is no longer affected, but the high pressure increases the reaction cost.

[0071] Example 4

[0072] Investigation of raw material liquid space velocity:

[0073] Compared with Example 2, the variable of this example is the raw material liquid space velocity, and the influence of different raw material liquid space velocities on the catalytic hydrogenation of dihexyl naphthalene-1, 2-dicarboxylate is investigated. The reaction conditions are: temperature 150℃, pressure 3 MPa, space velocity 0.40h -1 , hydrogen-ester molar ratio 40:1, and the results are shown in Table 4.

[0074] Table 4

[0075] airspeed / h -1 ]] Conversion / % Selectivity / % 0.30 99.1 99.2 0.40 99.4 99.6 0.45 99.2 92.1

[0076] From the above results, it can be found that with the increase of the raw material liquid space velocity, the conversion rate of dihexyl naphthalene-1, 2-dicarboxylate 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, and the internal temperature of the catalyst is low, which leads to incomplete reaction conversion. With the increase of the raw material liquid space velocity, the reaction heat increases, which leads to lower reaction temperature rise, and the conversion rate rises. With the further increase of the liquid space velocity, the contact time of the material with the catalyst is reduced, which leads to the decrease of the reaction conversion rate and the appearance of hydrogenation intermediates.

[0077] Example 5

[0078] Investigation of hydrogen-ester ratio:

[0079] Compared with Example 2, the variable of this example is the hydrogen-ester ratio, and the influence of different hydrogen-ester ratios on the catalytic hydrogenation of dihexyl naphthalene-1, 2-dicarboxylate is investigated. The reaction conditions are: temperature 150℃, pressure 3 MPa, space velocity 0.40h -1 , and the results are shown in Table 5.

[0080] Table 5

[0081] Hydroester ratio Conversion / % Selectivity / % 20:1 89.1 87.3 30:1 99.0 99.1 40:1 99.4 99.6 50:1 99.4 99.5

[0082] From the above results, it can be found that when the hydrogen-ester ratio is 40:1, there are intermediates in the reaction, and when the hydrogen-ester volume ratio is 20:1, the conversion rate of dihexyl naphthalene-1, 2-dicarboxylate and the selectivity of dihexyl cyclohexane-1, 2-dicarboxylate are higher.

[0083] Example 6

[0084] Investigation of Ru loading in hydrogenation catalyst:

[0085] Compared with Example 1, a series of catalysts with different Ru loadings were prepared by appropriately increasing or decreasing the amount of RuCl3xH2O and appropriately increasing the amount of the support while keeping other conditions unchanged. The active components in the catalyst samples were quantitatively analyzed by inductively coupled plasma analysis (ICP). Three catalysts with the mass percentage of Ru being 0.02%, 0.1% and 0.15% respectively were selected, and the catalyst of Example 1 was added, thus four catalysts in total.

[0086] Meanwhile, the effects of the catalysts with the content of Ru being 0.05% in Example 1 and the content of Ru being 0.02%, 0.1% and 0.15% respectively in this example on the hydrogenation reaction of dihexyl naphthalene were investigated under the same conditions, so as to analyze the effects of catalysts with different Ru loadings on the hydrogenation of dihexyl naphthalene. The hydrogenation catalytic reaction conditions were as follows: temperature 150°C, pressure 3 MPa, space velocity 0.40h -1 , hydrogen-ester molar ratio 40:1. The results are shown in Table 6.

[0087] Table 6

[0088] Ru mass fraction / % Conversion / % Selectivity / % 0.02 95.6 97.1 0.05 99.4 99.6 0.1 99.4 99.5 0.15 98.7 95.1

[0089] The above results show that within a certain range, increasing the content of the loaded Ru nanoclusters can improve the hydrogenation performance of the catalyst, but when the loaded Ru is too much, the Ru nanoclusters may agglomerate during the calcination stage, thus the catalytic effect is reduced.

[0090] Example 7

[0091] In this example, the effects of different additives were investigated. Compared with Example 1, different catalysts were prepared by using nitrate salts of iron, cobalt, nickel and chromium instead of Cu(NO3)2·3H2O, and the atomic mass of iron, cobalt, nickel and chromium was equal to the mass of Cu atom, and other conditions were the same.

[0092] The catalyst activity evaluation method of Example 2 was referred to, and the hydrogenation catalytic reaction of dihexyl naphthalene was carried out under the conditions of temperature 150°C, pressure 3 MPa, space velocity 0.40h -1 , hydrogen-ester molar ratio 40:1. The results are shown in Table 7.

[0093] Table 7

[0094] Promoter Conversion / % Selectivity / % Cu 99.4 99.6 Fe 99.2 99.3 Co 99.4 99.5 Ni 99.4 99.6 Cr 99.1 99.2

[0095] Example 8

[0096] This example investigates the influence of different metal oxides. Compared with Example 1, this example uses the corresponding chloride salt of zirconium and titanium to replace AlCl3·6H2O to prepare different catalysts, and the atomic mass of zirconium and titanium in them is equal to the mass of Al atom, and the rest of the conditions are the same.

[0097] Referring to the catalyst activity evaluation method of Example 2, the hydrogenation catalytic reaction of dihexyl naphthalene dicarboxylate was carried out under the conditions of 150℃, 3MPa of pressure, 0.40h-1 of space velocity and 40:1 of hydrogen ester molar ratio. The results are shown in Table 8. -1

[0098] Table 8

[0099]

[0100]

[0101] Comparative Example 1

[0102] The preparation method of Example 1 is to prepare the catalyst by one-step calcination method. Compared with this, the catalyst of this comparative example is prepared by first preparing a hollow mesoporous oxide carrier and then loading Ru by impregnation method. The specific steps include the following:

[0103] (1) 50g of dopamine was dissolved in 100mL of deionized water, 2.56mL of concentrated ammonia water (25-28%) was added dropwise under stirring, and stirring was maintained for 2h. The precipitate was collected and washed with water by centrifugation to obtain polydopamine (PDA) spheres;

[0104] (2) 38.3g of Al(Cl)3 was dissolved in water to prepare a 100mL solution, 10g of PDA spheres was added, mixed uniformly, and continuously stirred overnight (12h). The excess soluble salt was removed by centrifugation and water washing, and the precipitate was collected and dried at 60℃ for 24h;

[0105] (3) After crushing, it was calcined at 450℃ for 2h in air atmosphere to obtain a hollow mesoporous alumina carrier;

[0106] (4) 0.014g of RuCl3·xH2O (containing about 37% Ru) and 0.062g of Cu(NO3)2·3H2O were weighed and completely dissolved in 20mL of deionized water; the prepared alumina carrier was put into the above impregnation solution, stirred for 3h, and then refluxed at 110℃ in a cooling reflux device for 18h. The solid was collected, washed with deionized water, dried, and ground to obtain a catalyst precursor.

[0107] ​(5) Finally, the catalyst precursor is activated by calcination in a hydrogen atmosphere at a temperature of 150°C for 3h to obtain the catalyst of Comparative Example 1.

[0108] Meanwhile, the prepared catalyst of Comparative Example 1 is subjected to a hydrogenation catalytic reaction under the conditions of a temperature of 150°C, a pressure of 3MPa, a space velocity of 0.40h-1, a hydrogen-ester molar ratio of 40:1, and the remaining steps are the same as those of Example 2, and the results are shown in Table 9. -1

[0109] Comparative Example 2

[0110] In this example, two different Ru-based catalysts with different Ru contents available on the market, Al2O3 / 3%Ru and Al2O3 / 5%Ru, are purchased as catalysts for hydrogenation reaction under the conditions of a temperature of 150°C, a pressure of 3MPa, a space velocity of 0.40h-1, a hydrogen-ester molar ratio of 40:1, and the remaining steps are the same as those of Example 2, and the results are shown in Table 9. -1

[0111] Table 9

[0112] Catalyst type Conversion / % Selectivity / % Example 1 catalyst 99.2 99.3 Comparative example 1 84.3 80.6 Al2O3 / 3% Ru of Comparative Example 2 99.3 99.5 Al203 / 5% Ru of Comparative Example 2 99.7 99.6

[0113] From the above results, it can be found that since the catalyst of Comparative Example is not prepared by one-step calcination, it is a common nano noble metal particle type catalyst, and the utilization rate of noble metal atoms is not high, so the hydrogenation catalytic effect is not good under low Ru loading. However, the nano cluster type catalyst of the present application can effectively exert the catalytic effect of Ru, and exhibits good hydrogenation catalytic performance. The catalyst can have a catalytic effect comparable to that of the mainstream hydrogenation catalyst on the market, and the catalyst of the present application can significantly reduce the use amount of Ru noble metal, greatly reducing the cost of the catalyst, and has market application potential.

[0114] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.​​

Claims

1. A method for preparing a hydrogenation catalyst for diisononyl phthalate, characterized in that, Includes the following steps: (1) Add ammonia to the dopamine aqueous solution to carry out the reaction, collect the solid and wash it to obtain polydopamine balls; (2) The metal ions in the carrier, active component and additive are loaded onto the polydopamine spheres by impregnation and then calcined in air to obtain the catalyst precursor; (3) The catalyst precursor is calcined in a hydrogen atmosphere to obtain the diisononyl phthalate hydrogenation catalyst; The diisononyl phthalate hydrogenation catalyst comprises a support and an active component and an auxiliary agent supported on the support. The active component is a noble metal nanocluster, and the auxiliary agent includes at least one of copper, iron, cobalt, nickel, and chromium. The diisononyl phthalate hydrogenation catalyst has a hollow spherical morphology and a mesoporous structure. The support is a metal oxide, and the metal oxide includes at least one of alumina, zirconium oxide, and titanium oxide.

2. The method for preparing the diisononyl phthalate hydrogenation catalyst as described in claim 1, characterized in that, In step (2), the calcination temperature is 450-650℃ and the calcination time is 2-4h.

3. The method for preparing the diisononyl phthalate hydrogenation catalyst as described in claim 1, characterized in that, In step (3), the roasting temperature is 150-250℃ and the roasting time is 2-5h.

4. The method for preparing the diisononyl phthalate hydrogenation catalyst as described in claim 1, characterized in that, Includes at least one of the following: In step (1), the reaction time is 1-6 hours; In step (1), the mass concentration of dopamine in the aqueous solution is 200-1000 g / L; In step (1), the mass ratio of ammonia to dopamine is (0.006-0.02):1; In step (2), the mass ratio of metal ions to polydopamine spheres in the active component is (0.001-0.05):(8-15); In step (2), the mass ratio of metal ions to polydopamine spheres in the additive is (0.05-2):(8-15); In step (2), the mass ratio of metal ions to polydopamine spheres in the carrier is (4-8):(8-15); In step (2), the soaking time is 2-48 hours.

5. A catalyst prepared by the method for preparing the diisononyl phthalate hydrogenation catalyst according to any one of claims 1-4, characterized in that, The catalyst includes a support and an active component and an additive loaded on the support. The active component is a noble metal nanocluster, and the additive includes at least one of copper, iron, cobalt, nickel, and chromium. The diisononyl phthalate hydrogenation catalyst has a hollow spherical morphology and a mesoporous structure. The support is a metal oxide, and the metal oxide includes at least one of alumina, zirconium oxide, and titanium oxide.

6. The catalyst as described in claim 5, characterized in that, The noble metal in the noble metal nanoclusters includes at least one of ruthenium, platinum, palladium, and gold.

7. The catalyst as described in claim 5, characterized in that, In the diisononyl phthalate hydrogenation catalyst, the mass content of the active component is 0.02%~0.15%, and the mass percentage of the auxiliary agent is 0.5%~2%.

8. The application of the catalyst according to any one of claims 5-7, characterized in that, The catalyst according to any one of claims 5-7 is used as a catalyst for the hydrogenation reaction of diisononyl phthalate to prepare diisononyl cyclohexanedicarboxylate.

9. The application of the catalyst as described in claim 8, characterized in that, Includes at least one of the following: The hydrogenation reaction is carried out at a temperature of 140~160℃; The pressure of the hydrogenation reaction is 2-4 MPa; The liquid space velocity (LHSV) of the feedstock for the hydrogenation reaction is 0.2–0.45 h⁻¹. -1 .

10. The application of the catalyst as described in claim 8, characterized in that, Includes at least one of the following: The volume ratio of hydrogen gas to diisononyl phthalate in the hydrogenation reaction is (20~50):1; The hydrogenation reaction is carried out in a fixed-bed continuous hydrogenation reactor.

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