Catalyst for phthalate hydrogenation, method for preparing the same, and use thereof

Abstract

The application relates to the field of catalysts, and discloses a catalyst for phthalate ester hydrogenation, a preparation method and application thereof. The catalyst comprises a primary catalyst precursor and Fe coated on the surface of the primary catalyst precursor; the primary catalyst precursor comprises a carrier and Ru loaded on the surface of the carrier; the carrier comprises a primary modified carrier and a modulated metal oxide loaded on the primary modified carrier; and the primary modified carrier is a mixed metal oxide of Al and Ti. The catalyst has high catalytic activity, high selectivity and good stability.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to a catalyst for the hydrogenation of phthalic acid esters, its preparation method and application, and a method for preparing diisononyl cyclohexane-1,2-dicarboxylate from diisononyl phthalate. Background Technology

[0002] Plasticizers, also known as phthalates, are polymeric material additives, with phthalates being the most common. Phthalate esters have long held a dominant position in the industry, widely used in children's toys, medical devices, and food packaging. However, studies have shown that phthalates are persistent organic pollutants, exhibiting reproductive toxicity and potentially causing birth defects and cancer. The application of phthalate plasticizers carries significant risks, making the development and research of novel, non-toxic, and environmentally friendly plasticizers a current focus. Cyclohexane 1,2-dicarboxylate, a product of the selective hydrogenation of phthalates, is a non-toxic and environmentally friendly plasticizer, and is poised to become the preferred alternative to phthalates in the future plasticizer market.

[0003] CN114797924A discloses a Ni2P / SiC porous catalyst prepared using pollen as a template via a sol-gel and carbothermal reduction reaction. This catalyst has a large specific surface area and strong loading capacity. In a fixed-bed quartz tube reactor, the hydrogen pressure is 2-4 MPa, the reaction temperature is 120-130℃, and the space velocity is 0.4-0.8 h⁻¹. -1 Under these conditions, the catalyst's activity and selectivity both reached over 99%. However, the experimental data obtained under these reaction conditions did not include the reaction time, making it impossible to determine whether the catalyst's activity and selectivity decreased after a period of use. Consequently, the catalyst's stability remains unknown.

[0004] CN113651694A discloses a supported diisononyl phthalate hydrogenation catalyst with Rh or Ru as the active component and template-modified alumina as the support. This catalyst is suitable for hydrogenation at a hydrogen-to-ester ratio of 250, a reaction pressure of 6 MPa, a reaction temperature of 150 °C, and a liquid hourly space velocity of 0.6 h⁻¹. -1 Under these conditions, the DINP conversion rate was 90.2-100%, and the DINCH selectivity was 95.0-99.9%, but the loss rate of precious metals from the active components of the catalyst was not mentioned, and the stability of the catalyst could not be determined.

[0005] CN111036194A discloses a method for preparing a catalyst for the hydrogenation of phthalic acid esters. At least one of Ru, Pd, Pt, Ag, Au, Ni, and Rh is selected as the active component, and one of Al2O3, SiO2, ZrO2, TiO2, CeO2, and molecular sieve is selected as the support. Under the conditions of a fixed-bed reactor with a reaction temperature of 180℃, a reaction pressure of 8MPa, and a hydrogen-to-ester ratio of 50, the catalyst exhibits low noble metal loss and good stability, with both conversion and selectivity exceeding 99%. However, the reaction conditions do not mention the liquid space velocity (LHSV), and the stability data measured under what reaction load is unknown.

[0006] CN106984310A discloses a method for preparing a phthalate hydrogenation catalyst, using the noble metal Ru as the active component and one of zirconium oxide, magnesium oxide, silicon oxide, or aluminum oxide as the support. The method employs a batch hydrogenation process, requiring the catalyst to be reduced in a hydrogen atmosphere at 100-300℃ for 3-10 hours, with a product yield of 99.49%. However, the reduction time is long, and the batch process has disadvantages compared to the fixed-bed reaction process, such as the inability to produce continuously, low product stability, and difficulty in online detection.

[0007] Currently, in the hydrogenation of phthalic acid esters, those skilled in the art aim to prepare highly active, highly selective, and stable catalysts in a fixed-bed reaction process under relatively mild reaction conditions in order to achieve large-scale industrial applications. However, under these conditions, the high reaction pressure and temperature, as well as the continuous passage of raw materials through the catalyst bed, can easily lead to the sintering and loss of the precious metal active components. Therefore, the selectivity and stability of the catalyst are important issues that researchers need to address. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of high loss rate of the active component noble metal Ru and poor catalyst stability in the existing technology of catalyst running for a long time in a fixed trickle bed reactor. The invention provides a catalyst for the hydrogenation of phthalic acid esters, its preparation method and application, and a method for preparing diisononyl phthalate diisononyl 1,2-dicarboxylate from diisononyl phthalate. The catalyst has high catalytic activity, high selectivity and good stability.

[0009] To achieve the above objectives, a first aspect of the present invention provides a catalyst for the hydrogenation of phthalic acid esters, the catalyst comprising: a primary catalyst precursor and Fe coated on the surface of the primary catalyst precursor; wherein, the primary catalyst precursor comprises a support and Ru supported on the surface of the support; wherein...

[0010] The support comprises a primary modified support and a modulated metal oxide loaded on the primary modified support; the primary modified support is a mixed metal oxide of Al and Ti.

[0011] A second aspect of this invention provides a method for preparing a catalyst for the hydrogenation of phthalic acid esters, the method comprising the following steps:

[0012] (1) Boehmite and TiO2 were mixed and heat-treated to obtain a primary modified support;

[0013] (2) The primary modified carrier is mixed with an aqueous solution containing modulating metal elements, and then neutralized and precipitated with an alkaline solution. The precipitate is then subjected to a first calcination to obtain a secondary modified carrier.

[0014] (3) The secondary modified support is first impregnated with a hydrated hydrazine solution containing Ru, and the resulting solid is second-calcined to obtain a primary catalyst precursor;

[0015] (4) The primary catalyst precursor is impregnated a second time with a solution containing Fe, the resulting solid is then calcined a third time and subjected to a reduction reaction to obtain the catalyst.

[0016] A third aspect of the present invention provides a catalyst for the hydrogenation of phthalic acid esters prepared by the preparation method provided by the present invention.

[0017] The fourth aspect of the present invention provides the application of the catalyst for hydrogenation of phthalic acid esters provided by the present invention in the catalytic hydrogenation reaction of phthalic acid esters to prepare cyclohexane 1,2-dicarboxylate.

[0018] The fifth aspect of the present invention provides a method for preparing diisononyl cyclohexane 1,2-dicarboxylate from diisononyl phthalate, the method comprising: hydrogenating diisononyl phthalate in a hydrogen atmosphere in the presence of a catalyst for hydrogenation of phthalic acid esters provided by the present invention.

[0019] The conditions for the hydrogenation reaction include: a molar ratio of diisononyl phthalate to H2 of 1:(40-160), a temperature of 145-155℃, a pressure of 5-7 MPa, a time of 80-600 h, and a liquid hourly space velocity (LISH) of diisononyl phthalate of 0.5-0.7 h⁻¹. -1 .

[0020] The beneficial effects of the present invention through the above technical solution are as follows:

[0021] A primary modified support was obtained by heat-treating boehmite and TiO2 with good γ-AlOOH crystal form, which gave the primary modified support a suitable specific surface area and pore volume. Subsequently, a secondary modified support was obtained by modifying the specific metal oxide components. This support can have a good binding degree with the noble metal active component Ru, so that the catalyst has a good structure-activity relationship, thereby improving the activity and stability of the catalyst.

[0022] In the catalyst of this invention, a bimetallic compound of Ru and Fe is used as the active component. The Ru active component is uniformly distributed on the support and subsequently undergoes calcination, resulting in a high degree of bonding with the support. The Fe active component encapsulates the Ru, forming a localized bimetallic structure. The Fe element not only encapsulates the Ru but also penetrates to the surface of the support unloaded with Ru, thus binding with it. It acts as both an active component and a structure modifier, ensuring that the Ru is not lost or is lost in very small amounts even after prolonged use, exhibiting good stability. The phthalate hydrogenation catalyst prepared using this invention, when used in a trickle bed reactor, exhibits short reduction time, low hydrogen-to-ester ratio, high catalyst activity, and good selectivity. During long-term operation, the Fe active component not only encapsulates the Ru, preventing or minimizing its loss and establishing a stable structure-activity relationship, but also exhibits a synergistic effect with the Ru, enhancing the reactivity. In the preparation of diisononyl cyclohexane-1,2-dicarboxylate by the catalytic hydrogenation of diisononyl phthalate, when the H2 / ester molar ratio was 150, the DINP conversion was above 96% and the DINCH selectivity was above 95% after 100 h and 500 h of reaction, and the loss rate of the precious metal Ru did not exceed 0.04 ppm%. When the H2 / ester molar ratio was 50, the DINP conversion was above 96% and the DINCH selectivity was above 95% after 100 h and 500 h of reaction, and the loss rate of the precious metal Ru did not exceed 0.03 ppm.

[0023] In a preferred embodiment of the present invention, by selecting a suitable ratio of boehmite and TiO2, and heat treatment conditions, a multidimensional support structure with γ-Al2O3 as the main component and other crystal forms as auxiliary components is formed, thereby obtaining a more suitable specific surface area and pore volume for the primary modified support. By selecting appropriate modulating amounts and types of metal elements, the amounts of Ru and Fe elements, the impregnation method, and the three-stage calcination conditions, the activity, selectivity, and stability of the catalyst are further improved. After use, the precious metal Ru is not lost, and the amount of precious metal Ru is low, only 0.015-0.032% of the total mass of the catalyst. Attached Figure Description

[0024] Figure 1 These are the XRD patterns of the catalyst products S1-S4 obtained in Examples 1-4 of this invention.

[0025] Explanation of reference numerals in the attached figures

[0026] a. XRD pattern of catalyst product S1 b. XRD pattern of catalyst product S2

[0027] c. XRD pattern of catalyst product S3 d. XRD pattern of catalyst product S4 Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] A first aspect of the present invention provides a catalyst for the hydrogenation of phthalic acid esters, the catalyst comprising: a primary catalyst precursor and Fe coated on the surface of the primary catalyst precursor; wherein, the primary catalyst precursor comprises a support and Ru supported on the surface of the support; wherein,

[0030] The support comprises a primary modified support and a modulated metal oxide loaded on the primary modified support; the primary modified support is a mixed metal oxide of Al and Ti.

[0031] The primary modified support of this invention is a mixed metal oxide of Al and Ti, which enables the support precursor (primary modified support) to obtain a suitable specific surface area and pore volume. Subsequently, the secondary modified support is obtained by modifying the metal composition. The binding degree between such support and the noble metal active component Ru gives the catalyst a good structure-activity relationship, thereby improving the activity and stability of the catalyst.

[0032] This invention uses Ru and Fe bimetals as active components. The active component Ru is distributed on the support, while the active component Fe encapsulates the noble metal active component Ru, forming a local bimetallic structure. The Fe element not only encapsulates Ru but also penetrates to the surface of the support that is not loaded with Ru, thus combining with the support. It acts as both an active component and a structure modifier, ensuring that the noble metal Ru is not lost or is lost in very small amounts after long-term use of the catalyst, resulting in good stability.

[0033] According to the present invention, preferably, the Ru element is uniformly loaded on the surface of the carrier.

[0034] According to the present invention, preferably, based on the total weight of the catalyst, the contents of Ru and Fe in the catalyst are 0.015-0.032 wt% and 0.1-0.2 wt%, respectively.

[0035] According to the present invention, preferably, the modulating metal oxide is selected from at least one of Zr oxide, Cu oxide, Mg oxide, K oxide, Na oxide, and Ca oxide. Selecting these modulating metal oxides allows for more suitable support stability and surface acidity, and enables better and more uniform loading of the active substance Ru onto the support. This results in a higher selectivity of DINCH in the hydrogenation reaction of phthalic acid esters by the prepared catalyst, while other metal oxides cannot simultaneously achieve both of these effects.

[0036] According to the present invention, a portion of the modulated metal oxide is loaded on the surface of the primary modified support, and another portion is loaded inside the pores of the primary modified support.

[0037] According to the present invention, preferably, the content of the modulating metal element in the support is 5.45-6.55 wt%, based on the total weight of the catalyst. The modulating metal element is the technical element provided by the modulating metal oxide contained in the catalyst. The content of the modulating metal element can also refer to the content of the modulating metal oxide in terms of the metal element it contains. A modulating metal element content in the support within this range allows the surface acidity of the support to be in the range of 0.2-0.4 mmol / g, which is more suitable for the activity of this type of hydrogenation catalyst.

[0038] According to the present invention, preferably, the content of γ-Al2O3 crystal form in the primary modified support is 80-89 wt%, based on the total weight of the catalyst. The primary modified support is mainly composed of γ-Al2O3 crystal form, with other crystal forms as auxiliary components. This crystal form ratio of the primary modified support has a more suitable specific surface area and pore volume.

[0039] According to the present invention, preferably, based on the total weight of the catalyst, the contents of Al and Ti in the primary modified support are 44.26-48.21 wt% and 5.14-9.44 wt%, respectively.

[0040] In this invention, the contents of Ru and Fe elements, the contents of Al and Ti elements, and the contents of modulated metal elements can all be determined using an AA6300F atomic absorption spectrometer.

[0041] According to the present invention, preferably, the content of the primary modified support is 93.22-94.44 wt% based on the total weight of the catalyst.

[0042] According to the present invention, preferably, the catalyst has a specific surface area of ​​200-230 m². 2 / g, pore volume 0.2-0.3cm 3 / g, with an average pore size of 4.1-5.1nm.

[0043] In this invention, the specific surface area, pore volume, and average pore size of the catalyst can be determined using a NOVA2200e physical adsorption instrument via a low-temperature N2 adsorption-desorption method.

[0044] A second aspect of the present invention provides a method for preparing a catalyst for the hydrogenation of phthalic acid esters, the method comprising the following steps:

[0045] (1) Boehmite and TiO2 are mixed and heat-treated to obtain a primary modified support.

[0046] (2) The primary modified carrier is mixed with an aqueous solution containing a modulating metal element, and then neutralized and precipitated with an alkaline solution. The precipitate is then subjected to a first calcination to obtain a secondary modified carrier.

[0047] (3) The secondary modified support is first impregnated with a hydrated hydrazine solution containing Ru, and the resulting solid is second-calcined to obtain a primary catalyst precursor.

[0048] (4) The primary catalyst precursor is impregnated a second time with a solution containing Fe, the resulting solid is then calcined a third time and subjected to a reduction reaction to obtain the catalyst.

[0049] This invention obtains a primary modified support by heat-treating boehmite and TiO2 with good crystal structure, forming a multidimensional support structure containing various crystal forms such as γ-Al2O3, γ-Al-O-Ti, Al-O-Al, Ti-O-Ti, Al-OO-Al, Al-OO-Ti, and O-Ti-O, thereby achieving a suitable specific surface area and pore volume for the primary modified support. Subsequently, a secondary modified support is obtained by modifying the metal composition. The binding degree between this support and the noble metal active component Ru gives the catalyst a good structure-activity relationship, thereby improving the catalyst's activity and stability, and reducing Ru loss rate.

[0050] In step (2), the primary modified support is mixed with an aqueous solution containing a modulating metal element, and then neutralized and precipitated using an alkaline solution. The resulting precipitate is then subjected to a first calcination to obtain a secondary modified support. The primary modified support forms a metastable state. The addition of the modulating metal element, followed by neutralization and precipitation, allows for thorough and uniform mixing of the modulating metal element with the primary modified support, forming a stable mixture. This results in a portion of the modulating metal element being loaded within the pores of the primary modified support, and another portion being uniformly loaded on its surface. During the calcination process, the modulating metal element within the pores and on the surface of the primary modified support is oxidized to modulating metal oxides, thus yielding the secondary modified support.

[0051] The secondary modified support is first impregnated with a hydrazine hydrate solution containing Ru. Under the action of hydrazine hydrate, Ru is reduced, and Ru in a reduced state is loaded onto the surface of the secondary modified support. A second calcination process then slightly oxidizes the Ru on the surface of the secondary modified support, resulting in a high degree of binding between Ru and the secondary modified support. After the Ru is slightly oxidized, Fe can more easily acquire oxygen to combine with Ru during the third calcination, bringing Ru to a critically reduced state. Ru and Fe need to catalyze the hydrogenation of phthalates in a reduced state. After Fe combines with Ru, subsequent reduction reactions of the catalyst only require sufficient reduction of Fe. Coating the surface of the primary catalyst precursor with Fe not only encapsulates Ru but also penetrates to the surface of the unloaded support, thus combining with the support. Fe acts as both an active component and a structure modifier, ensuring that the precious metal Ru is not lost or is lost in very small amounts after long-term use, exhibiting good stability.

[0052] The Ru and Fe in the catalyst need to catalyze the hydrogenation of phthalates in a reduced state. Therefore, the product after the third calcination needs to be reduced to the reduced state of Fe, thus becoming a catalyst for phthalate hydrogenation. This reduction reaction can be carried out during catalyst preparation, or, considering the effects of oxidative deterioration during storage and transportation before use, the reduction reaction can be performed in situ in the reaction apparatus before the catalytic hydrogenation reaction. This should not be construed as a limitation of the invention by those skilled in the art.

[0053] In the preparation method of the catalyst for hydrogenation of phthalic acid esters in the second aspect of the present invention, the types and compositions of the primary modified support, the secondary modified support, and the primary catalyst precursor are exactly the same as those of the primary modified support, support, and primary catalyst precursor in the catalyst for hydrogenation of phthalic acid esters described in the first aspect of the present invention. In order to avoid repetition, the present invention will not repeat the description in this second aspect, and those skilled in the art should not understand it as a limitation of the present invention.

[0054] According to the present invention, preferably, in step (1), the heat treatment temperature is 400-600℃ and the time is 2-4h. When the heat treatment conditions meet this range, it is possible to obtain a multiphase crystal form with γ-Al2O3 as the main crystal form. Otherwise, obtaining more other crystal forms will not meet the requirements of the catalyst for activity and stability.

[0055] According to the present invention, preferably, in step (1), boehmite is calculated as Al, TiO2 is calculated as Ti, and the molar ratio of boehmite to TiO2 is (8-16):1. Boehmite and TiO2 are mixed in this ratio and heat-treated under the aforementioned conditions to form a primary modified support with a multidimensional support structure dominated by γ-Al2O3 crystal form and supplemented by other crystal forms. This results in a primary modified support with a more suitable specific surface area and pore volume, achieving a specific surface area of ​​228-250 m². 2 / g, pore volume 0.29-0.41cm 3 / g, a primary modified support with an average pore size of 5.3-6.1nm.

[0056] According to the present invention, preferably, the heat treatment is carried out in an air atmosphere.

[0057] According to the present invention, preferably, in step (2), the content of the modulating metal element in the aqueous solution is 0.02-0.1 mol / L. The content of the modulating metal element in the salt solution within this range allows the modulating metal element to be better dispersed on the surface and inside the pores of the primary modified carrier, thereby enhancing the structural stability of the carrier.

[0058] According to the present invention, preferably, in step (2), the modulating metal element is selected from at least one of Zr, Cu, Mg, K, Na and Ca.

[0059] According to the present invention, preferably, the temperature of the neutralization precipitation is 45-60°C, and the pH value of the precipitate is 8-9.5.

[0060] According to the present invention, preferably, in step (2), the alkaline solution is selected from sodium hydroxide and / or potassium hydroxide.

[0061] According to the present invention, preferably, in step (2), the obtained precipitate is first dried and then calcined; wherein the temperature of the first drying is 150-180℃ and the time is 1.5-2.5h; the most preferred time is 2h. When the conditions of the first drying meet this range, the physical water contained in the carrier can be better removed, and a material with a suitable moisture content can be obtained.

[0062] According to the present invention, preferably, the temperature of the first calcination is 500-600°C and the time is 2-4 hours. When the conditions for the first calcination meet this range, a secondary modified carrier with suitable specific surface area and pore structure can be obtained more effectively.

[0063] According to the present invention, preferably, step (2) further includes: compressing the first calcined product into tablets to obtain the secondary modified carrier.

[0064] According to the present invention, preferably, the content of hydrazine hydrate in the Ru-containing hydrazine hydrate solution is 15-25 wt%, and most preferably 20 wt%.

[0065] According to the present invention, preferably, in the Ru-containing hydrazine hydrate solution, the Ru element is derived from at least one of RuCl3, RuI3, and potassium ruthenium chloride, preferably RuCl3; the Ru element content is 3-6.4 mmol / L. Controlling the Ru element content in the Ru-containing solution within this range allows for a suitable loading of Ru element on the secondary modification support.

[0066] According to the present invention, preferably, the first impregnation is a supersaturated impregnation. Supersaturated impregnation involves immersing the secondary modified support in an excess of an impregnation solution containing Ru, such that the volume of the impregnation solution exceeds the absorbable volume of the secondary modified support, allowing the support to eventually reach adsorption equilibrium. Supersaturated impregnation ensures uniform contact between the Ru-containing impregnation solution and the secondary modified support, resulting in a uniform distribution of the active component Ru on the secondary modified support. The remaining impregnation solution can be reused in subsequent catalyst preparation, preventing waste of precious metals.

[0067] According to the present invention, preferably, the temperature of the first impregnation is 25-40°C and the time is 1.5-2.5 h. When the conditions of the first impregnation meet this range, more dispersed Ru element with good reduction can be obtained.

[0068] According to the present invention, preferably, the first impregnation is carried out under a stirring speed of 100-300 rpm.

[0069] According to the present invention, preferably, in step (3), the obtained solid is first subjected to a second drying and then to a second calcination; wherein the temperature of the second drying is 110-130°C and the time is 1.5-2.5 h; the most preferred time is 2 h. When the conditions for the second drying meet this range, the physical water contained in the primary catalyst precursor can be better removed, and a material that is easy to obtain for subsequent second calcination can be obtained.

[0070] According to the present invention, preferably, the second calcination temperature is 300-400°C and the time is 1-2 hours. When the conditions for the second calcination meet this range, the residual hydrazine hydrate solution can be effectively decomposed, allowing Ru element to be better loaded onto the support.

[0071] According to the present invention, preferably, the specific surface area of ​​the primary catalyst precursor is 215-240 m². 2 / g, pore volume is 0.26-0.35cm³ 3 / g, with an average pore size of 4.3-5.3nm.

[0072] The specific surface area of ​​the primary modified carrier without modulated metal oxide loading on the surface and inside the pores is 228-250 m². 2 / g, pore volume 0.29-0.41cm 3 / g, with an average pore size of 5.3-6.1 nm; while the specific surface area of ​​the primary catalyst precursor after loading and modulating the metal oxide is 215-240 m² / g. 2 / g, pore volume is 0.26-0.35cm³ 3 / g, with an average pore size of 4.3-5.3nm. This indicates that modulating the metal oxide plays a role in structural modulation.

[0073] According to the present invention, preferably, in step (4), the Fe element in the Fe-containing solution originates from at least one of Fe(NO3)2, FeSO4, and FeCl2, preferably Fe(NO3)2; the Fe element content in the Fe-containing solution is 0.02-0.04 mol / L. When the Fe element content in the Fe-containing solution meets this range, it can improve the catalyst activity while effectively stabilizing the Ru element loading on the support and preventing the loss of the precious metal Ru.

[0074] According to the present invention, preferably, the second impregnation is saturated impregnation. Saturated impregnation involves immersing the primary catalyst precursor in an impregnation solution containing Fe, such that the volume of the impregnation solution is equal to the absorbable volume of the primary catalyst precursor, thereby coating the surface of the primary catalyst precursor with Fe. Since Fe itself has a relatively high loading and is coated on the outer layer, supersaturated impregnation would cause excessive Fe adsorption, thus affecting the activity of Ru. Saturated impregnation allows Fe to coat the surface of the primary catalyst precursor in an appropriate amount.

[0075] According to the present invention, preferably, the temperature of the second impregnation is 30-50°C and the time is 1-2 hours. When the conditions of the second impregnation meet this range, Fe element can be effectively dispersed in the solution and further react with slightly oxidized Ru element to generate more stable forms of Fe and Ru oxides.

[0076] According to the present invention, preferably, in step (4), the obtained solid is first subjected to a third drying and then to a third calcination; wherein the temperature of the third drying is 130-150°C and the time is 1.5-2.5 h; the most preferred time is 2 h. When the conditions of the third drying meet this range, the physical water contained in the secondary catalyst precursor can be better removed, and a material with a suitable moisture content can be obtained.

[0077] According to the present invention, preferably, the third calcination temperature is 400-500°C and the time is 2-4 hours. When the conditions of the third calcination meet this range, nitrate ions, sulfate ions, and chloride ions remaining on the surface of the primary catalyst precursor can be better decomposed, thereby avoiding damage to the specific surface area of ​​the catalyst precursor before the reduction reaction.

[0078] According to the present invention, preferably, the reduction reaction is carried out in a reducing atmosphere, for example, in a hydrogen atmosphere.

[0079] According to the present invention, preferably, the conditions for the reduction reaction include: a temperature of 210-230°C, a pressure of 0.3-0.8 MPa, and a time of 0.5-1.5 h.

[0080] According to the present invention, preferably, the catalyst has a specific surface area of ​​200-230 m². 2 / g, pore volume 0.2-0.3cm 3 / g, with an average pore size of 4.1-5.1nm.

[0081] The specific surface area of ​​the primary catalyst precursor before Fe coating was 215-240 m². 2 / g, pore volume is 0.26-0.35cm³ 3 / g, with an average pore size of 4.3-5.3 nm; while the catalyst product coated with Fe was crushed and the central part of the catalyst was analyzed, and the specific surface area inside the catalyst product was found to be 200-230 m². 2 / g, pore volume 0.2-0.3cm 3 / g, with an average pore size of 4.1-5.1nm. This indicates that Fe not only encapsulates Ru but also permeates to the surface of the unloaded support, thus binding with the support and acting as both an active component and a structure modulator.

[0082] In this invention, the specific surface area, pore volume, and average pore size of the primary modified support, primary catalyst precursor, and catalyst can be determined using a NOVA2200e physical adsorption instrument via a low-temperature N2 adsorption-desorption method.

[0083] A third aspect of the present invention provides a catalyst for the hydrogenation of phthalic acid esters prepared by the preparation method provided by the present invention.

[0084] The fourth aspect of the present invention provides the application of the catalyst for hydrogenation of phthalic acid esters provided by the present invention in the catalytic hydrogenation reaction of phthalic acid esters to prepare cyclohexane 1,2-dicarboxylate, wherein the phthalic acid ester is diisononyl phthalate (DINP) and the cyclohexane 1,2-dicarboxylate is diisononyl cyclohexane 1,2-dicarboxylate (DINCH).

[0085] The fifth aspect of the present invention provides a method for preparing diisononyl cyclohexane 1,2-dicarboxylate from diisononyl phthalate, the method comprising: hydrogenating diisononyl phthalate in a hydrogen atmosphere in the presence of a catalyst for hydrogenation of phthalic acid esters provided by the present invention.

[0086] The conditions for the hydrogenation reaction include: a molar ratio of diisononyl phthalate to H2 of 1:(40-160), a temperature of 145-155℃, a pressure of 5-7 MPa, a time of 80-600 h, and a liquid hourly space velocity (LISH) of diisononyl phthalate of 0.5-0.7 h⁻¹. -1 .

[0087] The present invention will be described in detail below through examples and comparative examples. Unless otherwise specified, all methods used in the following examples are conventional; the reagents and materials used are commercially available unless otherwise specified. The determination methods involved in each example and comparative example are as follows:

[0088] Specific surface area, pore volume and average pore size were determined using a NOVA2200e physical adsorption instrument via a low-temperature N2 adsorption-desorption method.

[0089] The content of γ-Al2O3 was determined by chemical titration.

[0090] The contents of Ru and Fe, Al and Ti, and modulated metal elements were determined using an AA6300F atomic absorption spectrometer.

[0091] The content of the primary modified carrier was determined using a thermoelectric iCAP6300 plasma atomic emission spectrometer;

[0092] The surface acidity of the carrier was determined by titration with n-butylamine as an adsorption indicator.

[0093] The loss rate of metallic Ru was determined by microwave digestion ICP-MS.

[0094] The following examples illustrate the preparation of catalysts for the hydrogenation of phthalic acid esters.

[0095] Example 1

[0096] Step (1): Under air atmosphere, 102g of boehmite and 10g of TiO2 (Al:Ti molar ratio = 16:1) were uniformly mixed and then heat-treated in a muffle furnace at 400℃ for 4h to obtain a specific surface area of ​​250m². 2 / g, pore volume is 0.41cm 3 / g, a primary modified support with an average pore size of 6.1nm;

[0097] Step (2): Dissolve 10g of copper nitrate trihydrate and 30g of magnesium nitrate hexahydrate in water to prepare a 0.1mol / L mixed metal salt solution. Then add the primary modified carrier to the mixed metal salt solution, and neutralize and precipitate with sodium hydroxide at 45℃. Control the final pH value to 8. The obtained material is then filtered, dried at 150℃ for 2h, calcined at 600℃ for 2h, and compressed into tablets to obtain a secondary modified carrier with a surface acidity of 0.26mmol / g.

[0098] Step (3): Dissolve RuCl3 in a 20wt% hydrazine hydrate solution to prepare a 3mmol / L solution rich in the active component Ru. 3+ The solution was prepared, and the stirring speed was controlled at 100 rpm and the temperature at 40℃. The secondary modified carrier was immersed in the solution for 1.5 h using the supersaturated impregnation method. Then, it was removed and dried at 110℃ for 2 h and calcined at 300℃ for 2 h to obtain a specific surface area of ​​240 m². 2 / g, pore volume 0.35cm 3 / g, a primary catalyst precursor containing the active component Ru with an average pore size of 5.3nm;

[0099] Step (4): Dissolve Fe(NO3)2 in water to prepare a 0.02 mol / L solution rich in the active component Fe. 2+ The solution was prepared at 30℃, and the primary catalyst precursor was impregnated in it for 1 hour using a saturated impregnation method. The precursor was then removed, dried at 150℃ for 2 hours, and calcined at 500℃ for 3 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​230 m². 2 / g, pore volume 0.3cm 3 The catalyst product S1, with an average pore size of 5.1 nm and containing 0.1 wt% Fe and 0.015 wt% Ru, is a dual-active metal component catalyst.

[0100] Based on the total weight of the catalyst product S1, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.44wt%, and the content of Cu and Mg elements is 2.64wt% and 2.81wt%, respectively.

[0101] The XRD pattern of catalyst product S1 is shown below. Figure 1 ,Depend on Figure 1 It can be seen that the diffraction peaks at 47.8° and 67.2° are typical γ-Al2O3 diffraction peaks. No diffraction peaks of active metals Fe and Ru are shown in the figure, indicating that active metals Fe and Ru are highly dispersed on the support surface.

[0102] Example 2

[0103] Step (1): Under air atmosphere, 102g of boehmite and 20g of TiO2 (Al:Ti molar ratio = 8:1) were uniformly mixed and then heat-treated in a muffle furnace at 600℃ for 2h to obtain a specific surface area of ​​228m². 2 / g, pore volume is 0.29cm 3 / g, a primary modified support with an average pore size of 5.3nm;

[0104] Step (2): Dissolve 10g potassium nitrate and 10g zirconium nitrate in water to prepare a 0.1mol / L mixed metal salt solution. Then add the primary modified carrier to the mixed metal salt solution and neutralize and precipitate with sodium hydroxide at 60℃. Control the final pH value to 9. The obtained material is then filtered, dried at 180℃ for 2h, calcined at 600℃ for 3h and compressed into tablets to obtain a secondary modified carrier with a surface acidity of 0.4mmol / g.

[0105] Step (3): Dissolve RuCl3 in a 20wt% hydrazine hydrate solution to prepare a 6.4 mmol / L solution rich in the active component Ru. 3+ The solution was prepared, and the stirring speed was controlled at 300 rpm and the temperature at 25℃. The secondary modified carrier was immersed in the solution for 2.5 h using the supersaturated impregnation method. Then, it was removed and dried at 130℃ for 2 h and calcined at 400℃ for 1 h to obtain a specific surface area of ​​215 m². 2 / g, pore volume is 0.26cm 3 / g, a primary catalyst precursor containing the active component Ru with an average pore size of 4.3nm;

[0106] Step (4): Dissolve Fe(NO3)2 in water to prepare a 0.02 mol / L solution rich in the active component Fe. 2+ The solution was prepared at 50℃, and the primary catalyst precursor was impregnated in it for 2 hours using a saturated impregnation method. The precursor was then removed, dried at 130℃ for 2 hours, and calcined at 400℃ for 4 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​200 m². 2 / g, pore volume 0.2cm 3 The finished product S2 is a dual-active metal component catalyst with an average pore size of 4.1 nm and containing 0.1 wt% Fe and 0.032 wt% Ru.

[0107] Based on the total weight of the finished catalyst S2, the content of γ-Al2O3 in the support is 80wt%, the content of Al and Ti in the primary modified support is 44.26wt% and 9.44wt%, respectively, the content of the primary modified support is 93.34wt%, and the content of K and Zr is 3.87wt% and 2.68wt%, respectively.

[0108] The XRD pattern of catalyst product S2 is shown below. Figure 1 Similar to the XRD pattern of the catalyst product S1, the diffraction peaks at 47.8° and 67.2° are typical γ-Al2O3 diffraction peaks. No diffraction peaks of active metals Fe and Ru are shown in the figure, indicating that active metals Fe and Ru are highly dispersed on the support surface.

[0109] Example 3

[0110] Step (1): Under air atmosphere, 102g of boehmite and 15g of TiO2 (Al:Ti molar ratio = 10.67:1) were uniformly mixed and then heat-treated in a muffle furnace at 500℃ for 3h to obtain a specific surface area of ​​239m². 2 / g, pore volume 0.32cm 3 / g, a primary modified support with an average pore size of 5.6nm;

[0111] Step (2): Dissolve 10g potassium nitrate and 10g calcium nitrate in water to prepare a 0.08mol / L mixed metal salt solution. Then add the primary modified carrier to the mixed metal salt solution and neutralize and precipitate with sodium hydroxide at 50℃. Control the final pH value to 9.5. The obtained material is then filtered, dried at 160℃ for 2h, calcined at 500℃ for 3h and compressed into tablets to obtain a secondary modified carrier with a surface acidity of 0.2mmol / g.

[0112] Step (3): Dissolve RuCl3 in a 20wt% hydrazine hydrate solution to prepare a 6mmol / L solution rich in the active component Ru. 3+ The solution was prepared by stirring at 200 rpm and maintaining a temperature of 30°C. The secondary modified carrier was immersed in the solution for 2 hours using a supersaturated impregnation method. The carrier was then removed, dried at 120°C for 2 hours, and calcined at 380°C for 1 hour to obtain a specific surface area of ​​227 m². 2 / g, pore volume is 0.31cm 3 / g, a primary catalyst precursor containing the active component Ru with an average pore size of 4.7nm;

[0113] Step (4): Dissolve Fe(NO3)2 in water to prepare a 0.04 mol / L solution rich in the active component Fe. 2+The solution was prepared at 40℃, and the primary catalyst precursor was impregnated in it for 2 hours using a saturated impregnation method. The precursor was then removed, dried at 140℃ for 2 hours, and calcined at 450℃ for 4 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​216 m². 2 / g, pore volume 0.25cm 3 The catalyst product S3, with an average pore size of 4.5 nm and containing 0.2 wt% Fe and 0.03 wt% Ru, is a dual-active metal component catalyst.

[0114] Based on the total weight of the finished catalyst S3, the content of γ-Al2O3 in the support is 84.5 wt%, the content of Al and Ti in the primary modified support is 46.15 wt% and 7.38 wt%, respectively, the content of the primary modified support is 93.47 wt%, and the content of K and Ca is 3.86 wt% and 2.44 wt%, respectively.

[0115] The XRD pattern of catalyst product S3 is shown below. Figure 1 Similar to the XRD pattern of the catalyst product S1, the diffraction peaks at 47.8° and 67.2° are typical γ-Al2O3 diffraction peaks. No diffraction peaks of active metals Fe and Ru are shown in the figure, indicating that active metals Fe and Ru are highly dispersed on the support surface.

[0116] Example 4

[0117] Step (1): Under air atmosphere, 102g of boehmite and 12.3g of TiO2 (Al:Ti molar ratio = 13:1) were uniformly mixed and then heat-treated in a muffle furnace at 500℃ for 3h to obtain a specific surface area of ​​245m². 2 / g, pore volume is 0.38cm 3 / g, a primary modified support with an average pore size of 5.9nm;

[0118] Step (2): Dissolve 5g magnesium nitrate hexahydrate, 10g zirconium nitrate and 10g sodium nitrate in water to prepare a 0.07mol / L mixed metal salt solution. Then add the primary modified carrier to the mixed metal salt solution, and neutralize and precipitate with sodium hydroxide at 55℃. Control the final pH value to 9. The obtained material is then filtered, dried at 180℃ for 2h, calcined at 550℃ for 2h and compressed into tablets to obtain the secondary modified carrier with a surface acidity of 0.29mmol / g.

[0119] Step (3): Dissolve RuCl3 in a 20wt% hydrazine hydrate solution to prepare a 4mmol / L solution rich in the active component Ru. 3+The solution was prepared by stirring at 150 rpm and at 30°C. The secondary modified carrier was immersed in the solution for 2 hours using a supersaturated impregnation method. The carrier was then removed, dried at 125°C for 2 hours, and calcined at 400°C for 1 hour to obtain a specific surface area of ​​238 m². 2 / g, pore volume 0.32cm 3 / g, a primary catalyst precursor containing the active component Ru with an average pore size of 5.1nm;

[0120] Step (4): Dissolve Fe(NO3)2 in water to prepare a 0.03 mol / L solution rich in the active component Fe. 2+ The solution was prepared at 30℃, and the primary catalyst precursor was impregnated in it for 1 hour using a saturated impregnation method. The precursor was then removed, dried at 150℃ for 2 hours, and calcined at 400℃ for 4 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​227 m². 2 / g, pore volume 0.28cm 3 The catalyst product S4, with an average pore size of 4.8 nm and containing 0.15 wt% Fe and 0.02 wt% Ru, is a dual-active metal component catalyst.

[0121] Based on the total weight of the finished catalyst S4, the content of γ-Al2O3 in the support is 86.9 wt%, the content of Al and Ti in the primary modified support is 47.24 wt% and 6.2 wt%, respectively, the content of the primary modified support is 93.86 wt%, and the contents of Mg, Zr and Na are 0.47 wt%, 2.68 wt% and 2.82 wt%, respectively.

[0122] The XRD pattern of catalyst product S4 is shown below. Figure 1 Similar to the XRD pattern of the catalyst product S1, the diffraction peaks at 47.8° and 67.2° are typical γ-Al2O3 diffraction peaks. No diffraction peaks of active metals Fe and Ru are shown in the figure, indicating that active metals Fe and Ru are highly dispersed on the support surface.

[0123] Example 5

[0124] The catalyst for phthalate hydrogenation was prepared according to the method of Example 1, except that the ratio of boehmite to TiO2 was different. Specifically, in step (1), when preparing the primary modified support, 102g of boehmite and 8.33g of TiO2 (Al:Ti molar ratio = 19.21:1) were uniformly mixed and then heat-treated to obtain a specific surface area of ​​278m². 2 / g, pore volume 0.51cm 3A primary modified support with an average pore size of 6.8 nm was obtained at a g / g. The secondary modified support had a surface acidity of 0.26 mmol / g, resulting in a specific surface area of ​​265 m² / g. 2 / g, pore volume 0.46cm 3 A primary catalyst precursor with an average pore size of 6.1 nm was obtained at a concentration of 257 m² / g. 2 / g, pore volume is 0.39cm 3 The finished product S5 is a dual-active metal component catalyst with an average pore size of 5.8 nm and containing 0.11 wt% Fe and 0.016 wt% Ru.

[0125] Based on the total weight of the finished catalyst S5, the content of γ-Al2O3 in the support is 90.7wt%, the content of Al and Ti in the primary modified support is 48.94wt% and 4.35wt%, respectively, the content of the primary modified support is 94.42wt%, and the content of Cu and Mg is 2.65wt% and 2.82wt%, respectively.

[0126] Example 6

[0127] The catalyst for hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that in step (1), the heat treatment temperature was 750°C and the time was 2 hours, resulting in a specific surface area of ​​320 m². 2 / g, pore volume 0.6cm 3 A primary modified support with an average pore size of 7.5 nm was obtained at a concentration of 0.26 mmol / g. A secondary modified support with a surface acidity of 0.26 mmol / g was then obtained, resulting in a specific surface area of ​​301 m². 2 / g, pore volume 0.55cm 3 A primary catalyst precursor with an average pore size of 6.9 nm was obtained per g. The final product had a specific surface area of ​​286 m². 2 / g, pore volume is 0.43cm 3 The finished product S6 is a dual-active metal component catalyst with an average pore size of 6.2 nm and containing 0.11 wt% Fe and 0.018 wt% Ru.

[0128] Based on the total weight of the finished catalyst S6, the content of γ-Al2O3 in the support is 53.8 wt%, the content of Al and Ti in the primary modified support is 48.21 wt% and 5.14 wt%, respectively, the content of the primary modified support is 94.42 wt%, and the content of Cu and Mg is 2.64 wt% and 2.81 wt%, respectively.

[0129] Example 7

[0130] The catalyst for the hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that the amount of modulating metal element was different. Specifically, in step (2), 20g of copper nitrate trihydrate and 60g of magnesium nitrate hexahydrate were dissolved in water to prepare a 0.2mol / L mixed metal salt solution. Then, the primary modified support was added to the mixed metal salt solution, and the surface acidity of the resulting secondary modified support was 0.16mmol / g, resulting in a specific surface area of ​​219m². 2 / g, pore volume 0.28cm 3 A primary catalyst precursor with an average pore size of 4.5 nm was obtained per g. The final product had a specific surface area of ​​208 m². 2 / g, pore volume 0.2cm 3 The finished product S7 is a dual-active metal component catalyst with an average pore size of 4 nm and containing 0.09 wt% Fe and 0.015 wt% Ru.

[0131] Based on the total weight of the finished catalyst S7, the content of γ-Al2O3 in the support is 89wt%, the content of Al and Ti in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 89.58wt%, and the content of Cu and Mg is 5.08wt% and 5.23wt%, respectively.

[0132] Example 8

[0133] The catalyst for the hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that the type of modulating metal element was different. Specifically, in step (2), 12g of lanthanum nitrate was dissolved in water to prepare a 0.1mol / L mixed metal salt solution. Then, the primary modified support was added to the mixed metal salt solution, and the surface acidity of the resulting secondary modified support was 0.42mmol / g, resulting in a specific surface area of ​​225m². 2 / g, pore volume is 0.26cm 3 A primary catalyst precursor with an average pore size of 4.5 nm was obtained at a concentration of 215 m² / g. 2 / g, pore volume 0.19cm 3 The finished product S8 is a dual-active metal component catalyst with an average pore size of 3.9 nm and containing 0.1 wt% Fe and 0.016 wt% Ru.

[0134] Based on the total weight of the finished catalyst S8, the content of γ-Al2O3 in the support is 89wt%, the content of Al and Ti in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 93.81wt%, and the content of lanthanum is 6.07wt%.

[0135] Example 9

[0136] The catalyst for phthalate hydrogenation was prepared according to the method of Example 1, except that the conditions for the first calcination were different. Specifically, in step (2), the obtained material was filtered, dried, calcined at 400°C for 5 hours, and pressed into tablets to obtain a secondary modified support with a surface acidity of 0.26 mmol / g. Then, a specific surface area of ​​230 m² was obtained. 2 / g, pore volume is 0.31cm 3 A primary catalyst precursor with an average pore size of 4.8 nm was obtained at a density of 219 m² / g. 2 / g, pore volume is 0.26cm 3 The finished product S9 is a bilayer active metal component catalyst with an average pore size of 4.3 nm and containing 0.1 wt% Fe and 0.015 wt% Ru.

[0137] Based on the total weight of the finished catalyst S9, the content of γ-Al2O3 in the support is 89wt%, the content of Al and Ti in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.51wt%, and the content of Cu and Mg is 2.61wt% and 2.76wt%, respectively.

[0138] Example 10

[0139] The catalyst for phthalate hydrogenation was prepared according to the method of Example 1, except that the sources of Ru and Fe were different. Specifically, in step (3), potassium ruthenium chloride was dissolved in a 20 wt% hydrazine hydrate solution to prepare a 3 mmol / L solution rich in the active component Ru. 3+ A solution with a specific surface area of ​​225 m² was obtained. 2 / g, pore volume 0.34cm 3 / g, a primary catalyst precursor with an average pore size of 5.1nm. In step (4), FeSO4 is dissolved in water to prepare a 0.02mol / L solution rich in the active component Fe. 2+ The solution was ultimately obtained with a specific surface area of ​​220 m². 2 / g, pore volume 0.28cm 3 The finished product S10 is a bilayer active metal component catalyst with an average pore size of 4.6 nm and containing 0.1 wt% Fe and 0.015 wt% Ru.

[0140] Based on the total weight of the finished catalyst S10, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.43wt%, and the content of Cu and Mg elements is 2.64wt% and 2.81wt%, respectively.

[0141] Example 11

[0142] The catalyst for the hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that in step (3), a 7 mmol / L catalyst rich in the active component Ru was prepared. 3+ A solution with a specific surface area of ​​235 m² was obtained. 2 / g, pore volume 0.32cm 3 A primary catalyst precursor with an average pore size of 5 nm was obtained at a concentration of 227 m² / g. 2 / g, pore volume 0.28cm 3 The finished product S11 is a bilayer active metal component catalyst with an average pore size of 4.7 nm and containing 0.1 wt% Fe and 0.035 wt% Ru.

[0143] Based on the total weight of the finished catalyst S11, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.41wt%, and the content of Cu and Mg elements is 2.64wt% and 2.81wt%, respectively.

[0144] Example 12

[0145] The catalyst for phthalate hydrogenation was prepared according to the method of Example 1, except that the conditions for the second calcination were different. Specifically, in step (3), the secondary modified support was impregnated with a Ru-containing solution using a supersaturated impregnation method. 3+ The solution was removed, dried, and then calcined at 500℃ for 2 hours to obtain a specific surface area of ​​215 m². 2 / g, pore volume 0.25cm 3 A primary catalyst precursor containing the active component Ru was obtained at a density of / g and an average pore size of 4.4nm. The final product had a specific surface area of ​​202m². 2 / g, pore volume 0.24cm 3 The finished product S12 is a bilayer active metal component catalyst with an average pore size of 4.3 nm and containing 0.1 wt% Fe and 0.015 wt% Ru.

[0146] Based on the total weight of the finished catalyst S12, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.47wt%, and the content of Cu and Mg elements is 2.64wt% and 2.81wt%, respectively.

[0147] Example 13

[0148] The catalyst for hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that in step (4), Fe(NO3)2 was dissolved in water to prepare a 0.05 mol / L solution rich in the active component Fe. 2+ The solution was ultimately obtained with a specific surface area of ​​219 m². 2 / g, pore volume is 0.26cm 3 The finished product S13 is a bilayer active metal component catalyst with an average pore size of 4.5 nm and containing 0.25 wt% Fe and 0.015 wt% Ru.

[0149] Based on the total weight of the finished catalyst S13, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.31wt%, and the content of Cu and Mg elements is 2.63wt% and 2.79wt%, respectively.

[0150] Example 14

[0151] The catalyst for the hydrogenation of phthalic acid esters was prepared according to the method of Example 1, except that the conditions for the third calcination were different. Specifically, in step (4), the primary catalyst precursor was impregnated with Fe-containing substrate using a saturated impregnation method. 2+ The solution was removed, dried, and then calcined at 600℃ for 2 hours to obtain a final specific surface area of ​​228 m². 2 / g, pore volume is 0.26cm 3 The finished product S14 is a bilayer active metal component catalyst with an average pore size of 4.6 nm and containing 0.1 wt% Fe and 0.015 wt% Ru.

[0152] Based on the total weight of the finished catalyst S14, the content of γ-Al2O3 crystal form in the support is 89wt%, the content of Al and Ti elements in the primary modified support is 48.21wt% and 5.14wt%, respectively, the content of the primary modified support is 94.43wt%, and the content of Cu and Mg elements is 2.64wt% and 2.81wt%, respectively.

[0153] Comparative Example 1

[0154] The catalyst support in this comparative example was γ-Al₂O₃ without modulation and heat treatment, and Ru 3+ The element dissolves in water, not in hydrazine hydrate. The specific preparation method of the catalyst is as follows:

[0155] RuCl3 was dissolved in water to obtain 3.6 mmol / L of Ru rich in the active component. 3+ The solution was prepared, and then 100g of γ-Al2O3 support powder was heat-treated at 60℃ for 2h and then compressed into tablets to obtain a specific surface area of ​​238m². 2 / g, pore volume is 0.41cm 3 A support with an average pore size of 5.7 nm was prepared by impregnating an equal volume of the support in the above Ru salt solution for 2 hours. The solution was then removed and dried at 130°C for 2 hours and calcined at 500°C for 2 hours to obtain a primary catalyst precursor containing the active component Ru. Fe(NO3)2 was dissolved in water to prepare a 0.02 mol / L solution rich in the active component Fe. 2+ The primary catalyst precursor was impregnated in a solution, then removed, dried at 130°C for 2 hours, and calcined at 550°C for 1 hour to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220°C and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​203 m². 2 / g, pore volume 0.22cm 3 Catalyst product D1 is a bimetallic active component containing 0.1 wt% Fe and 0.018 wt% Ru with an average pore size of 3.5 nm.

[0156] Comparative Example 2

[0157] The catalyst support in this comparative example is heat-treated activated carbon, without any modulating metal elements, and the only active metal component supported is Ru. The specific preparation method of the catalyst is as follows:

[0158] RuCl3 was dissolved in 20 wt% hydrazine hydrate to obtain 6 mmol / L RuCl3 rich in the active component. 3+ The solution; under air atmosphere, 100g of activated carbon was heat-treated in a muffle furnace at 550℃ for 3h; then the heat-treated activated carbon carrier (with a specific surface area of ​​950m²) was... 2 / g, pore volume 0.8cm 3 / g, with an average pore size of 9.5nm) added Ru 3+ The catalyst precursor was immersed in a solution for 3 hours, then removed and dried at 140℃ for 2 hours and calcined at 500℃ for 3 hours to obtain the catalyst precursor. The catalyst precursor was then reduced at 220℃ and 0.5 MPa hydrogen atmosphere for 1 hour to obtain a final product with a specific surface area of ​​582 m². 2 / g, pore volume is 0.68cm³ 3 The catalyst product D2 has an average pore size of 7.2 nm and contains 0.03 wt% Ru.

[0159] Comparative Example 3

[0160] The catalyst support in this comparative example was prepared by mixing heat-treated boehmite and cellulose, without loading any modulating metal elements, and the loaded active metal components were Ru and Ni. The specific preparation method of the catalyst is as follows:

[0161] 102g of boehmite was heat-treated in a muffle furnace at 550℃ for 3 hours in air atmosphere. The heat-treated material was then mixed with 3g of cellulose and pressed into tablets to obtain a specific surface area of ​​278m². 2 / g, pore volume 0.56m 3 / g, with an average pore size of 7.2nm; RuCl3 was dissolved in a 20wt% hydrazine hydrate solution to prepare a 3.6mmol / L solution rich in the active component Ru. 3+ A solution of Ni(NO3)2 was sprayed onto a support using an atomization spraying method, and then dried at 120℃ for 2 hours and calcined at 400℃ for 2 hours to obtain a primary catalyst precursor containing the active component Ru; Ni(NO3)2 was dissolved in water to prepare a 0.02 mol / L solution rich in the active component Ni. 2+ The solution was prepared at 40℃, and the primary catalyst precursor was impregnated in it for 1 hour using a saturated impregnation method. After removal, it was dried at 140℃ for 2 hours and calcined at 550℃ for 3 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour, ultimately yielding a catalyst with a specific surface area of ​​232 m². 2 / g, pore volume is 0.29cm 3 The finished product D3 is a bilayer active metal component catalyst with an average pore size of 4.9 nm and containing 0.1 wt% Ni and 0.018 wt% Ru.

[0162] Comparative Example 4

[0163] The catalyst support in this comparative example was prepared by mixing heat-treated TiO2 and cellulose, without loading any modulating metal elements, and the only active metal component loaded was Ru. The specific preparation method of the catalyst is as follows:

[0164] RuCl3 was dissolved in a 20 wt% hydrazine hydrate solution to prepare a 5 mmol / L solution rich in the active component Ru. 3+ A solution was prepared; 100g of TiO2 was heat-treated in a muffle furnace at 550℃ for 3h under air atmosphere, and then the heat-treated TiO2 support was kneaded and compressed with 3g of cellulose to obtain a tablet with a specific surface area of ​​201m². 2 / g, pore volume is 0.38cm 3 / g, a support with an average pore size of 5.2nm; the support was added to Ru 3+ The catalyst precursor was impregnated in a solution for 2 hours, then removed and dried at 130℃ for 3 hours and calcined at 400℃ for 4 hours to obtain the catalyst precursor. The catalyst precursor was then reduced at 220℃ and 0.5 MPa hydrogen atmosphere for 1 hour to obtain a final product with a specific surface area of ​​196 m². 2 / g, pore volume 0.32cm 3 The catalyst product D4 has an average pore size of 4.8 nm and contains 0.025 wt% Ru.

[0165] Comparative Example 5

[0166] The catalyst support in this comparative example was prepared by calcining a mixture of alumina and cellulose, without loading any modulating metal elements, and the only active metal component loaded was Ru. The specific preparation method of the catalyst is as follows:

[0167] 102g of alumina powder and 3g of cellulose were uniformly mixed and compressed into tablets, then dried at 130℃ for 3 hours, and then calcined at 550℃ for 4 hours to obtain a specific surface area of ​​235m². 2 / g, pore volume 0.53cm 3 / g, a support with an average pore size of 5.6nm; RuCl3 was dissolved in a 20wt% hydrazine hydrate solution to prepare a 3.6mmol / L solution rich in the active component Ru. 3+ The solution was sprayed onto the support using an atomization spraying method, then dried at 120℃ for 2 hours, and then calcined at 400℃ for 2 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour to obtain a catalyst with a specific surface area of ​​217 m². 2 / g, pore volume 0.42cm 3 The catalyst product D5 has an average pore size of 4.6 nm and contains 0.018 wt% Ru.

[0168] Comparative Example 6

[0169] The catalyst support in this comparative example was prepared by calcining a mixture of alumina and n-butylamine, without loading any modulating metal elements, and the only active metal component loaded was Ru. The specific preparation method of the catalyst is as follows:

[0170] 102g of alumina powder and 5g of n-butylamine were uniformly mixed and extruded into strips, then dried at 130℃ for 3 hours, and then calcined at 550℃ for 4 hours to obtain a specific surface area of ​​230m². 2 / g, pore volume 0.53cm 3 / g, a support with an average pore size of 5.2nm; RuCl3 was dissolved in water to prepare a 0.18mol / L solution rich in the active component Ru 3+ The solution was sprayed onto the support using an atomization spraying method, then dried at 120℃ for 2 hours, and then calcined at 400℃ for 2 hours to obtain the catalyst precursor. The catalyst precursor was then reduced in a hydrogen atmosphere at 220℃ and 0.5 MPa for 1 hour to obtain a catalyst with a specific surface area of ​​205 m². 2 / g, pore volume 0.35cm 3 The catalyst product D6 has an average pore size of 4.2 nm and contains 0.9 wt% Ru.

[0171] Test case

[0172] The catalysts prepared in each example and comparative example were respectively packed into a fixed trickle bed reactor for catalyzing the hydrogenation reaction of diisononyl phthalate to prepare diisononyl cyclohexane-1,2-dicarboxylate. In the presence of the catalyst, the hydrogenation reaction of diisononyl phthalate was carried out at an H2 / ester molar ratio of 150 and 50, a temperature of 150°C, a hydrogen pressure of 6 MPa, and a liquid hourly space velocity of 0.6 h⁻¹. -1 The hydrogenation reaction was carried out under the specified conditions, and samples were taken for analysis at 100 h and 500 h of hydrogenation reaction time, respectively. The results are shown in Table 1.

[0173] Table 1

[0174]

[0175] Table 1 (Continued from Table 1)

[0176]

[0177]

[0178] As can be seen from the examples, comparative examples, and the data in Table 1, in Examples 1-14, the primary catalyst precursors with modified metal oxides loaded on the surface and inside the pores showed varying degrees of reduction in specific surface area, pore volume, and average pore size compared to the primary modified support without modified metal oxides, indicating that the modified metal oxides played a role in structural modulation. Furthermore, the catalyst product coated with Fe also showed varying degrees of reduction in specific surface area, pore volume, and average pore size compared to the primary catalyst precursor without Fe coating, indicating that Fe not only served as an active component but also played a role in structural modulation.

[0179] Furthermore, catalysts S1-S4 prepared using this method, at a reaction temperature of 150℃, a reaction pressure of 6MPa, and a liquid space velocity of 0.6h⁻¹, showed good performance. -1Under the specified conditions, regardless of whether the H2 / ester molar ratio was 150 or 50, good DINP conversion and DINCH selectivity were observed at 100h and 500h, with good stability. Although catalysts S5-S14 were prepared using the method provided in this invention, their preparation method did not meet the preferred conditions. Therefore, the activity and stability of the catalysts were slightly lower than those of S1-S4. However, regardless of whether the H2 / ester molar ratio was 150 or 50, the DINP conversion and DINCH selectivity at 500h showed little fluctuation compared to 100h, and the stability was good. Catalyst D1 prepared in Comparative Example 1 showed only average conversion and selectivity in the initial and later stages of the reaction, possibly due to insufficient pre-reduction of Ru during preparation and insufficient reduction time in the later stages. Although catalysts D2-D6 prepared in Comparative Examples 2-6 showed good conversion and selectivity in the initial stage of the reaction, their conversion and selectivity decreased significantly after 500h, indicating poor stability and significant loss of metallic Ru. Therefore, after the reaction was completed, physicochemical analysis was performed on catalysts S1-S14 and catalysts D1-D6. The results showed that, except for S5, S6, S7 and S11 which showed slight loss of the noble metal Ru after use, the noble metal Ru in the catalysts S1-S14 prepared by the method of the present invention did not lose any, while the noble metal loss rate of catalysts D1-D6 was 0.2-0.8 ppm.

[0180] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst for the hydrogenation of phthalic acid esters, characterized in that, The catalyst comprises: a primary catalyst precursor and Fe coated on the surface of the primary catalyst precursor; wherein, the primary catalyst precursor comprises a support and Ru supported on the surface of the support; wherein, The support comprises a primary modified support and a modulated metal oxide supported on the primary modified support; the primary modified support is a mixed metal oxide of Al and Ti; Based on the total weight of the catalyst, the contents of Ru and Fe in the catalyst are 0.015-0.032 wt% and 0.1-0.2 wt%, respectively.

2. The catalyst according to claim 1, characterized in that, The modulated metal oxide is selected from at least one of Zr oxide, Cu oxide, Mg oxide, K oxide, Na oxide, and Ca oxide.

3. The catalyst according to claim 1 or 2, characterized in that, Based on the total weight of the catalyst, the content of the modulating metal element in the support is 5.45-6.55 wt%.

4. The catalyst according to claim 1, characterized in that, Based on the total weight of the catalyst, the content of γ-Al2O3 crystal form in the primary modified support is 80-89 wt%.

5. The catalyst according to claim 1, characterized in that, Based on the total weight of the catalyst, the contents of Al and Ti in the primary modified support are 44.26-48.21 wt% and 5.14-9.44 wt%, respectively.

6. The catalyst according to claim 1, characterized in that, Based on the total weight of the catalyst, the content of the primary modified support is 93.22-94.44 wt%.

7. The catalyst according to claim 1, characterized in that, The catalyst has a specific surface area of ​​200-230 m². 2 / g, pore volume 0.2-0.3cm 3 / g, with an average pore size of 4.1-5.1nm.

8. A method for preparing a catalyst for the hydrogenation of phthalic acid esters, characterized in that, The preparation method includes the following steps: (1) Boehmite and TiO2 are mixed and heat-treated to obtain a primary modified support; (2) The primary modified carrier is mixed with an aqueous solution containing a modulating metal element, and then neutralized and precipitated with an alkaline solution. The precipitate is then subjected to a first calcination to obtain a secondary modified carrier. (3) The secondary modified support is first impregnated with a hydrated hydrazine solution containing Ru, and the resulting solid is second-calcined to obtain the primary catalyst precursor; (4) The primary catalyst precursor is impregnated a second time with a solution containing Fe, the resulting solid is then calcined a third time and subjected to a reduction reaction to obtain the catalyst; Based on the total weight of the catalyst, the contents of Ru and Fe in the catalyst are 0.015-0.032 wt% and 0.1-0.2 wt%, respectively.

9. The preparation method according to claim 8, characterized in that, In step (1), the heat treatment temperature is 400-600℃ and the time is 2-4h.

10. The preparation method according to claim 8, characterized in that, In step (1), boehmite is calculated as Al and TiO2 is calculated as Ti, and the molar ratio of boehmite to TiO2 is (8-16):

1.

11. The preparation method according to claim 8, characterized in that, The heat treatment is carried out in an air atmosphere.

12. The preparation method according to claim 8, characterized in that, In step (2), the content of the modulating metal element in the aqueous solution is 0.02-0.1 mol / L.

13. The preparation method according to claim 12, characterized in that, The modulating metal element is selected from at least one of Zr, Cu, Mg, K, Na, and Ca.

14. The preparation method according to claim 8, characterized in that, The neutralization precipitation temperature is 45-60℃, and the pH value of the precipitate is 8-9.

5.

15. The preparation method according to claim 8, characterized in that, The first roasting temperature is 500-600℃, and the time is 2-4 hours.

16. The preparation method according to any one of claims 8-15, characterized in that, The Ru-containing hydrazine hydrate solution contains Ru at a concentration of 3-6.4 mmol / L.

17. The preparation method according to claim 8, characterized in that, The first impregnation is a supersaturated impregnation.

18. The preparation method according to claim 17, characterized in that, The temperature of the first impregnation is 25-40℃, and the time is 1.5-2.5h.

19. The preparation method according to claim 8, characterized in that, The second roasting temperature is 300-400℃, and the time is 1-2 hours.

20. The preparation method according to claim 8, characterized in that, In step (4), the Fe content in the Fe-containing solution is 0.02-0.04 mol / L.

21. The preparation method according to claim 8, characterized in that, The second impregnation is a saturated impregnation.

22. The preparation method according to claim 21, characterized in that, The second impregnation temperature is 30-50℃, and the time is 1-2 hours.

23. The preparation method according to claim 8, characterized in that, The third roasting temperature is 400-500℃, and the time is 2-4 hours.

24. The preparation method according to claim 8, characterized in that, The reduction reaction is carried out in a hydrogen atmosphere.

25. The preparation method according to claim 24, characterized in that, The conditions for the reduction reaction include: a temperature of 210-230℃, a pressure of 0.3-0.8MPa, and a time of 0.5-1.5h.

26. A catalyst for hydrogenation of phthalic acid esters prepared by any one of claims 8-25.

27. The use of a catalyst for hydrogenation of phthalic acid esters according to any one of claims 1-7 and 26 in the catalytic hydrogenation reaction of phthalic acid esters to prepare cyclohexane 1,2-dicarboxylate.

28. A method for preparing diisononyl cyclohexane-1,2-dicarboxylate from diisononyl phthalate, characterized in that, The method comprises: hydrogenating diisononyl phthalate in a hydrogen atmosphere in the presence of a catalyst for hydrogenation of phthalic acid esters as described in any one of claims 1-7 and 26; The conditions for the hydrogenation reaction include: a molar ratio of diisononyl phthalate to H2 of 1:(40-160), a temperature of 145-155℃, a pressure of 5-7 MPa, a time of 80-600 h, and a liquid hourly space velocity (LISH) of diisononyl phthalate of 0.5-0.7 h⁻¹. -1 .

Images