Catalyst carrier, porous catalyst as well as preparation method and application of porous catalyst

Abstract

The invention provides a catalyst carrier, a porous catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. According to the present invention, 1, 3, 5-tri (4-bromophenyl) benzene is adopted as a polymerization monomer, and a polymerization reaction is performed under the catalysis of bis (1, 5-cyclooctadiene) nickel (0) to obtain a carrier skeleton structure; the interior of the obtained carrier has various characteristics including nano-scale pore channels, large specific surface area, good thermal stability and chemical stability and the like. The porous catalyst with good catalytic performance, thermal stability and chemical stability is prepared by taking the carrier disclosed by the invention as a substrate and taking titanium as an active component.

Description

Technical Field

[0001] The present disclosure relates to the field of catalyst technology, and in particular to a catalyst carrier, a porous catalyst, and a preparation method and application thereof. Background Art

[0002] Catalyst supports have a significant impact on catalyst performance. They not only physically support the pore structure and expose active sites, but also interact with active components, thereby affecting catalytic performance. Porous materials are an important type of catalyst support.

[0003] Porous materials are categorized by their composition and structure into inorganic porous materials, inorganic-organic hybrid porous materials, and organic framework materials. Inorganic porous materials are formed by atoms connected by ionic bonds; inorganic-organic hybrid porous materials are formed by coordination bonds between organic ligands and metal atoms; and organic porous materials are formed by building blocks connected by covalent bonds. Their composition and bonding methods determine their respective advantages and disadvantages: Inorganic porous materials have a strong framework and good stability, but poor modifiability; inorganic-organic hybrid porous materials have a tunable structure and good modifiability, but poor stability; and organic porous materials have good stability but suffer from disadvantages such as a flexible framework, small specific surface area, low available density, and difficulty exposing functional groups. Summary of the Invention

[0004] The purpose of the present disclosure is to overcome the deficiencies of the prior art and to provide a catalyst carrier, a porous catalyst, and a preparation method and application thereof.

[0005] To achieve the above objectives, the technical solutions adopted by this disclosure are:

[0006] In a first aspect, a method for preparing a catalyst support is provided, comprising the following steps:

[0007] Mixing 1,3,5-tris(4-bromophenyl)benzene, a catalyst and a solvent, and reacting at 75-135° C. for 10-48 hours to obtain a catalyst support;

[0008] The catalyst is bis(1,5-cyclooctadiene)nickel(0) and 1,5-cyclooctadiene; and the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:2-5 mmol.

[0009] In one embodiment, the reaction temperature is 115-130° C., and the reaction time is 30-42 h.

[0010] In one embodiment, the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:3-4 mmol.

[0011] In the present disclosure, a polymerization reaction is carried out using 1,3,5-tris(4-bromophenyl)benzene as a monomer to prepare a catalyst support; the catalyst support uses 1,3,5-tris(4-bromophenyl)benzene containing a benzene ring as a monomer, so that the catalyst support has a rigid structure and improves the mechanical strength of the catalyst support; the monomers are connected by covalent bonds, thereby the catalyst support has good thermal stability and chemical stability; and the catalyst support of the present disclosure has nano-scale pores inside, thereby having a large specific surface area.

[0012] During the preparation of a catalyst support, the mass of the catalyst and the molar ratio of 1,3,5-tris(4-bromophenyl)benzene, as well as the reaction temperature and time, affect the specific surface area, thermal stability, and chemical stability of the catalyst support. If the molar ratio of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is too large, the reaction temperature is too low, or the reaction time is too short, the degree of polymerization of the monomer is low, resulting in a decrease in the specific surface area of the catalyst support and a reduction in the loading of the active component, thereby reducing the performance of the catalyst. If the molar ratio of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is too small, the reaction temperature is too high, or the reaction time is too long, the catalytic activity of bis(1,5-cyclooctadiene)nickel(0) and 1,5-cyclooctadiene decreases, thereby reducing the thermal stability of the catalyst support. The preferred reaction temperature of the present invention is 115-130°C, the reaction time is 30-42h, and the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9g:3-4mmol; the more preferred reaction temperature is 120°C, the reaction time is 40h, and the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9g:4mmol, so that the specific surface area, thermal stability and chemical stability of the catalyst support are maintained within an appropriate range.

[0013] The reaction equation of the catalyst support is as follows:

[0014]

[0015] In one embodiment, the product of the reaction needs to be post-treated; the post-treatment includes filtration, washing, and Soxhlet extraction.

[0016] The present disclosure does not particularly limit the specific operation method of the filtration, and a filtration method well known to those skilled in the art can be used.

[0017] The present disclosure does not specifically limit the washing solution, and washing can be performed using a washing solution well known in the art, such as deionized water, ethanol, ammonia solution, etc. The present disclosure preferably uses an ammonia solution with a molar concentration of 1-2 mol / L for washing; further preferably uses an ammonia solution with a molar concentration of 1.5 mol / L for washing.

[0018] The present disclosure has no special limitation on the solvent for Soxhlet extraction, and a solvent well known in the art for Soxhlet extraction is used for Soxhlet extraction; the present disclosure prefers dichloromethane, tetrahydrofuran and petroleum ether for Soxhlet extraction, and the specific steps are: the washed product is sequentially subjected to Soxhlet extraction with dichloromethane, tetrahydrofuran and petroleum ether.

[0019] The present disclosure does not have any particular limitation on the time of Soxhlet extraction. Those skilled in the art can select a suitable time according to actual needs. The present disclosure selects the time of Soxhlet extraction to be 48-72 h / time, preferably 60-70 h / time, and more preferably 70 h / time.

[0020] In one embodiment, the solvent is at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, ethylene dichloride, and carbon tetrachloride.

[0021] In a second aspect, the present disclosure provides a catalyst carrier, which is prepared by the above-mentioned catalyst carrier preparation method.

[0022] In a third aspect, the present disclosure provides a porous catalyst, which includes the above-mentioned catalyst carrier.

[0023] In a fourth aspect, the present disclosure provides a method for preparing a porous catalyst, comprising the following steps: immersing the porous catalyst in a titanium source aqueous solution with a concentration of 1-5 mol / L, and drying after the immersion to obtain a porous catalyst; wherein the mass ratio of the porous catalyst to the titanium source is (1:1)-(1:5).

[0024] The porous catalyst uses the catalyst carrier disclosed in the present invention as a carrier of the porous catalyst and titanium as an active component; the active component is loaded on the catalyst carrier by an impregnation method. On the one hand, the large specific surface area of the catalyst carrier provides multiple binding sites for the active component, and the active component interacts with the groups on the surface of the catalyst carrier and is connected to the surface of the catalyst carrier; on the other hand, the active component enters the nanopores of the catalyst carrier and combines with the catalyst carrier, thereby increasing the loading amount of the active component; the above two aspects work together to improve the catalytic performance of the porous catalyst.

[0025] The mass ratio of the catalyst support and the titanium source affects the catalytic performance and stability of the porous catalyst. If the mass ratio of the catalyst support and the titanium source is too small, the content of active components loaded on the porous catalyst is small, which leads to a decrease in the catalytic performance of the porous catalyst; if the mass ratio of the catalyst support and the titanium source is too large, the excessive active components clog the pores of the catalyst support, resulting in a decrease in the stability and catalytic performance of the porous catalyst; the present disclosure selects a mass ratio of the catalyst support and the titanium source of (1:2)-(1:4) to obtain a porous catalyst with better stability and catalytic performance.

[0026] The present disclosure does not specifically limit the specific operation method of the drying, and a filtration method well known to those skilled in the art can be used. The preferred drying method of the present disclosure is vacuum drying.

[0027] The present disclosure does not specifically limit the drying temperature and time. Those skilled in the art can select appropriate temperature and time according to actual needs. The present disclosure selects a drying temperature of 50-100°C and a drying time of 18-24 hours; preferably, a drying temperature of 75-95°C and a drying time of 21-23 hours; more preferably, a drying temperature of 80°C and a drying time of 22 hours.

[0028] In a fifth aspect, a method for producing diisononyl phthalate comprises reacting phthalic anhydride and isononyl alcohol in a reactor using the porous catalyst.

[0029] In one embodiment, the molar ratio of phthalic anhydride to isononanol is 5:1 to 1:5; and / or the reaction temperature is 150 to 220° C.; and / or the reaction time is 5 to 12 hours.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. In the present disclosure, 1,3,5-tris(4-bromophenyl)benzene is used as a monomer and a polymerization reaction is carried out under the catalysis of a catalyst to prepare a catalyst carrier; the obtained catalyst carrier has nano-scale pores inside, a large specific surface area, and good thermal stability and chemical stability.

[0032] 2. The porous catalyst provided by the present disclosure uses the catalyst carrier of the present disclosure as the carrier of the porous catalyst and titanium as the active component; the obtained porous catalyst has good catalytic performance and good thermal stability and chemical stability.

[0033] 3. The porous catalyst disclosed herein is used to catalyze the reaction of hexahydrophthalic anhydride and isononyl alcohol to produce diisononyl cyclohexane-1,2-dicarboxylate. The porous catalyst has high catalytic efficiency. DETAILED DESCRIPTION

[0034] In order to better illustrate the purpose, technical solutions and advantages of the present disclosure, the present disclosure will be further described below in conjunction with specific embodiments and comparative examples. Its purpose is to understand the content of the present disclosure in detail, rather than to limit the present disclosure. All other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present disclosure. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of the present disclosure are all commonly used ordinary reagents and instruments.

[0035] Example 1

[0036] The preparation method of the catalyst carrier of this embodiment is as follows:

[0037] 2 g of bis(1,5-cyclooctadiene)nickel(0) and 1 g of 1,5-cyclooctadiene as a catalyst were added to a round-bottom flask; the flask was evacuated, filled with nitrogen, and then tetrahydrofuran was injected, and then 1,3,5-tris(4-bromophenyl)benzene was added to the round-bottom flask, wherein the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene was 0.9 g:4 mmol, and the mixture was heated to 120° C. and reacted for 40 h. The reaction product was filtered, and the filtered product was treated with a 1.5 mol / L HCl solution. The treated product was sequentially Soxhlet extracted with dichloromethane, tetrahydrofuran and petroleum ether, and the Soxhlet extraction time was 70 h / time to obtain a catalyst support, and the average pore diameter of the obtained catalyst support was 1.1 nm, and the volume ratio of the nanopore diameter was 70%.

[0038] Example 2

[0039] The preparation method of the catalyst support of this embodiment differs from that of Example 1 only in that the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:3 mmol, the average pore diameter of the obtained catalyst support is 1.3 nm, and the volume ratio of the nanopore diameter is 60%.

[0040] Example 3

[0041] The preparation method of the catalyst support of this embodiment differs from that of Example 1 only in that the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:2 mmol, the average pore diameter of the obtained catalyst support is 1.5 nm, and the volume ratio of the nanopore diameter is 75%.

[0042] Example 4

[0043] The preparation method of the catalyst support of this embodiment differs from that of Example 1 only in that the molar ratio of the catalyst mass to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:5 mmol, the average pore diameter of the obtained catalyst support is 1.6 nm, and the volume ratio of the nanopore diameter is 78%.

[0044] Example 5

[0045] The preparation method of the catalyst support in this embodiment differs from that in Example 1 only in that the reaction temperature is 115° C., the average pore diameter of the obtained catalyst support is 1.9 nm, and the volume ratio of nanopores is 80%.

[0046] Example 6

[0047] The preparation method of the catalyst support in this embodiment differs from that in Example 1 only in that the reaction temperature is 130° C., the average pore size of the obtained catalyst support is 2 nm, and the volume ratio of nanopores is 86%.

[0048] Example 7

[0049] The preparation method of the catalyst support in this embodiment differs from that in Example 1 only in that the reaction temperature is 75° C., the average pore size of the obtained catalyst support is 1.4 nm, and the volume ratio of nanopores is 64%.

[0050] Example 8

[0051] The preparation method of the catalyst support in this embodiment differs from that in Example 1 only in that the reaction temperature is 135° C., the average pore diameter of the obtained catalyst support is 1.4 nm, and the volume ratio of nanopores is 77%.

[0052] Comparative Example 1

[0053] The preparation method of the catalyst support of this comparative example differs from that of Example 1 only in that the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:1 mmol, the average pore diameter of the obtained catalyst support is 1.6 nm, and the volume ratio of the nanopore diameter is 68%.

[0054] Comparative Example 2

[0055] The preparation method of the catalyst support of this comparative example differs from that of Example 1 only in that the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:6 mmol, the average pore diameter of the obtained catalyst support is 1.5 nm, and the volume ratio of the nanopore diameter is 66%.

[0056] Comparative Example 3

[0057] The preparation method of the catalyst support of this comparative example differs from that of Example 1 only in that the reaction temperature is 65° C., the average pore diameter of the obtained catalyst support is 1.2 nm, and the volume ratio of nanopores is 78%.

[0058] Comparative Example 4

[0059] The preparation method of the catalyst support of this comparative example differs from that of Example 1 only in that the reaction temperature is 145° C., the average pore diameter of the obtained catalyst support is 1.4 nm, and the volume ratio of nanopores is 71%.

[0060] Example 9

[0061] The preparation method of the porous catalyst of this embodiment is as follows:

[0062] The catalyst support obtained in Example 1 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 245 m 2 / g.

[0063] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0064] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 97%.

[0065] Example 10

[0066] The preparation method of the porous catalyst of this embodiment is as follows:

[0067] The catalyst support obtained in Example 1 was added to a 3 mol / L aqueous solution of tetraisopropyl titanate, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 231 m 2 / g.

[0068] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0069] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg based on 1 g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 96%.

[0070] Example 11

[0071] The preparation method of the porous catalyst of this embodiment is as follows:

[0072] The catalyst support obtained in Example 1 was added to a 3 mol / L barium titanate aqueous solution with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 267 m 2 / g.

[0073] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0074] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 98%.

[0075] Example 12

[0076] The preparation method of the porous catalyst of this embodiment is as follows:

[0077] The catalyst support obtained in Example 1 was added to a 3 mol / L lithium titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the mixture was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 263 m 2 / g.

[0078] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0079] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 98%.

[0080] Example 13

[0081] The preparation method of the porous catalyst of this embodiment is as follows:

[0082] The catalyst support obtained in Example 1 was added to a 3 mol / L tetrabutyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 273 m 2 / g.

[0083] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0084] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 98%.

[0085] Example 14

[0086] The preparation method of the porous catalyst of this embodiment is as follows:

[0087] The catalyst support obtained in Example 2 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 245 m 2 / g.

[0088] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0089] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 97%.

[0090] Example 15

[0091] The preparation method of the porous catalyst of this embodiment is as follows:

[0092] The catalyst support obtained in Example 3 was added to a 3 mol / L isopropyl titanate aqueous solution with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 216 m 2 / g.

[0093] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0094] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg per 1 g of phthalic anhydride, and the catalytic efficiency of the porous catalyst was 92%.

[0095] Example 16

[0096] The preparation method of the porous catalyst of this embodiment is as follows:

[0097] The catalyst support obtained in Example 4 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 205 m 2 / g.

[0098] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0099] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove water. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 91%.

[0100] Example 17

[0101] The preparation method of the porous catalyst of this embodiment is as follows:

[0102] The catalyst support obtained in Example 5 was added to a 3 mol / L isopropyl titanate aqueous solution with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 289 m 2 / g.

[0103] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0104] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 97%.

[0105] Example 18

[0106] The preparation method of the porous catalyst of this embodiment is as follows:

[0107] The catalyst support obtained in Example 6 was added to a 3 mol / L isopropyl titanate aqueous solution with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 288 m 2 / g.

[0108] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0109] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 97%.

[0110] Example 19

[0111] The preparation method of the porous catalyst of this embodiment is as follows:

[0112] The catalyst support obtained in Example 7 was added to a 3 mol / L isopropyl titanate aqueous solution with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 215 m 2 / g.

[0113] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0114] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove water. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 91%.

[0115] Example 20

[0116] The preparation method of the porous catalyst of this embodiment is as follows:

[0117] The catalyst support obtained in Example 8 was added to a 3 mol / L aqueous solution of isopropyl titanate, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 204 m 2 / g.

[0118] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0119] 20g of phthalic anhydride, 100g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170°C for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 94%.

[0120] Example 21

[0121] The preparation method of the porous catalyst of this embodiment is as follows:

[0122] The catalyst support obtained in Example 1 was added to a 3 mol / L tetraisopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:5. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 287 m 2 / g.

[0123] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0124] 100g of phthalic anhydride, 20g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 150°C for 12h to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 96%.

[0125] Example 22

[0126] The preparation method of the porous catalyst of this embodiment is as follows:

[0127] The catalyst support obtained in Example 1 was added to a 3 mol / L tetraisopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:3. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80° C. and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 257 m 2 / g.

[0128] The method for producing diisononyl phthalate using the porous catalyst of this embodiment comprises the following steps:

[0129] 20g of phthalic anhydride, 60g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 220°C for 5h to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20mg based on 1g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 97%.

[0130] Comparative Example 5

[0131] The preparation method of the porous catalyst of this comparative example is as follows:

[0132] The catalyst support obtained in Comparative Example 1 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 177 m 2 / g.

[0133] The method for producing diisononyl phthalate using the porous catalyst of this comparative example comprises the following steps:

[0134] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg per 1 g of phthalic anhydride, and the catalytic efficiency of the porous catalyst was 84%.

[0135] Comparative Example 6

[0136] The preparation method of the porous catalyst of this comparative example is as follows:

[0137] The catalyst support obtained in Comparative Example 2 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 151 m 2 / g.

[0138] The method for producing diisononyl phthalate using the porous catalyst of this comparative example comprises the following steps:

[0139] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg per 1 g of phthalic anhydride, and the catalytic efficiency of the porous catalyst was 84%.

[0140] Comparative Example 7

[0141] The preparation method of the porous catalyst of this comparative example is as follows:

[0142] The catalyst support obtained in Comparative Example 3 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 171 m 2 / g.

[0143] The method for producing diisononyl phthalate using the porous catalyst of this comparative example comprises the following steps:

[0144] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg per 1 g of phthalic anhydride, and the catalytic efficiency of the porous catalyst was 87%.

[0145] Comparative Example 8

[0146] The preparation method of the porous catalyst of this comparative example is as follows:

[0147] The catalyst support obtained in Comparative Example 4 was added to a 3 mol / L isopropyl titanate aqueous solution, with a mass ratio of the catalyst support to isopropyl titanate of 1:1. After impregnation and stirring for 10 h, the catalyst support was filtered. The filtered product was heated to 80°C and dried for 22 h under vacuum to obtain a porous catalyst. The specific surface area of the porous catalyst was 184 m 2 / g.

[0148] The method for producing diisononyl phthalate using the porous catalyst of this comparative example comprises the following steps:

[0149] 20 g of phthalic anhydride, 100 g of isononanol, and a porous catalyst were simultaneously added to a reactor and reacted at 170° C. for 10 hours to remove moisture. The mixture was then neutralized, washed with water, dealcoholized, filtered, and decolorized to obtain diisononyl phthalate. The amount of the porous catalyst used was 20 mg based on 1 g of phthalic anhydride. The catalytic efficiency of the porous catalyst was 88%.

[0150] Performance Testing

[0151] The catalyst supports obtained in Examples 1-8 and Comparative Examples 1-4 were tested using the following test methods:

[0152] (1) Specific surface area: The specific surface area of the sample was measured using the test standard GB / T 13390-2008;

[0153] (2) Acid stability: 1 g of the catalyst support was added to 10 ml of a 10% by mass sulfuric acid solution and soaked for 2 hours. The mixture was then filtered, washed with water, and dried. The specific surface area of the dried sample was measured using the test standard GB / T 13390-2008.

[0154] (3) Alkali stability: 1 g of the catalyst support was added to 10 ml of a 10% by mass sodium hydroxide solution and soaked for 2 hours. The mixture was then filtered, washed with water, and dried. The specific surface area of the dried sample was measured using the test standard GB / T13390-2008.

[0155] (3) Thermal stability: 1 g of the catalyst support was heated at 300°C for 5 min and then cooled to room temperature. The specific surface area of the heated sample was measured using the test standard GB / T 13390-2008.

[0156] The test results are shown in Table 1.

[0157] Table 1

[0158]

[0159] From the experimental data in Table 1, it can be seen that Example 1 has the largest specific surface area, and the specific surface areas of Examples 2-8 are slightly smaller than those of Example 1, indicating that the catalyst support prepared in Example 1 of the present invention has better overall performance; the specific surface areas of the catalyst supports of Comparative Examples 1-4 are small, and the reason is that the polymerization degree of the catalyst supports of Comparative Examples 1-4 is low, and there are a large number of incompletely polymerized raw materials in the structure. These fragment structures are interspersed and coated with each other, resulting in a lower specific surface area.

[0160] After acid washing or water washing, the specific surface area of the catalyst supports of Examples 1-8 decreases to a certain extent; while after acid washing or water washing, the specific surface area of the catalyst supports of Comparative Examples 1-4 decreases significantly. The reason may be that when the temperature and catalyst dosage are changed, the bulk density of the catalyst supports of Comparative Examples 1-4 decreases, resulting in a decrease in the π-π interaction between the layered materials in the catalyst supports, thereby resulting in a decrease in acid-base stability.

[0161] After the catalyst supports of Examples 1-8 were heat-treated at 300°C, the decrease in specific surface area was low, while after the catalyst supports of Comparative Examples 1-4 were heat-treated at 300°C, the decrease in specific surface area was high. The reason may be that when the temperature and catalyst dosage were changed, the degree of polymerization of the catalyst supports of Comparative Examples 1-4 decreased during the polymerization reaction, resulting in reduced thermal stability.

[0162] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present disclosure rather than to limit the scope of protection of the present disclosure. Although the present disclosure 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 disclosure may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present disclosure.

Claims

1. A method for preparing a catalyst carrier, characterized in that: The following steps are involved: Mixing 1,3,5-tris(4-bromophenyl)benzene, a catalyst and a solvent, and reacting at 75-135° C. for 10-48 hours to obtain a catalyst support; The catalyst is bis(1,5-cyclooctadiene)nickel(0) and 1,5-cyclooctadiene; and the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:2-5 mmol.

2. The preparation method according to claim 1, wherein The reaction temperature is 115-130°C, and the reaction time is 30-42h; And / or, the molar ratio of the mass of the catalyst to 1,3,5-tris(4-bromophenyl)benzene is 0.9 g:3-4 mmol.

3. The preparation method according to claim 1, wherein The product of the reaction needs to be post-processed; the post-processing includes filtration, washing, and Soxhlet extraction.

4. The preparation method according to claim 1, wherein The solvent is at least one of chloroform, ether, benzene, methyl acetate, tetrahydrofuran, acetone, methanol, petroleum, chlorophenol, ethylene dichloride, and carbon tetrachloride.

5. A catalyst carrier, characterized in that The catalyst carrier is prepared by the preparation method of the catalyst carrier according to any one of claims 1 to 4.

6. A porous catalyst, characterized in that The porous catalyst comprises the catalyst support according to claim 5.

7. The method for preparing a porous catalyst according to claim 6, wherein: The following steps are involved: The porous catalyst is immersed in a titanium source aqueous solution and dried after the immersion to obtain a porous catalyst; wherein the mass ratio of the catalyst support to the titanium source is (1:1)-(1:5).

8. The preparation method according to claim 7, wherein The mass ratio of the catalyst support to the titanium source is (1:2)-(1:4).

9. A method for producing diisononyl phthalate, comprising reacting phthalic anhydride and isononyl alcohol in a reactor using the porous catalyst according to claim 6.

10. The method according to claim 9, wherein The molar ratio of phthalic anhydride to isononanol is 5:1 to 1:5; and / or the reaction temperature is 150 to 220° C.; and / or the reaction time is 5 to 12 hours.

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