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CN110642718A - Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof - Google Patents

Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof Download PDF

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CN110642718A
CN110642718A CN201910843000.0A CN201910843000A CN110642718A CN 110642718 A CN110642718 A CN 110642718A CN 201910843000 A CN201910843000 A CN 201910843000A CN 110642718 A CN110642718 A CN 110642718A
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catalyst
acid
drying
carrier
titanium source
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CN110642718B (en
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魏天荣
孙苏红
於国伟
张小元
李善华
陈坤
徐保明
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Hubei Sanning Carbon-Phosphorus Based New Material Industry Technology Research Institute Co Ltd
Hubei Sanning Chemical Co Ltd
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Hubei Sanning Carbon-Phosphorus Based New Material Industry Technology Research Institute Co Ltd
Hubei Sanning Chemical Co Ltd
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    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B01J31/22—Organic complexes
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract

The invention discloses a heterogeneous catalyst for synthesizing diphenyl carbonate and a preparation method thereof, wherein the catalyst comprises a carrier, a titanium source and organic acid, the mass ratio of the titanium source to the carrier is 10-70:90-30, and the molar ratio of titanium to the organic acid is 0.05-5: 1. The titanium source is tetrabutyl titanate, tetraisopropyl titanate, titanyl sulfate, titanocene dichloride, tetraethyl titanate orBis-cyclopentadienyl titanium dimethyl. The carrier is ZSM molecular sieve, HZSM molecular sieve, TS-1 molecular sieve, MCM-41 molecular sieve or SiO2. The organic acid is acetic acid, succinic acid, adipic acid, sebacic acid, terephthalic acid, benzoic acid or chlorosulfonic acid. When the catalyst is specifically prepared, 1) dissolving a titanium source by adopting a solvent, then adding a carrier, carrying out hydrothermal synthesis reaction at 80-120 ℃ for 10-48h, filtering, and drying the carrier to obtain a catalyst intermediate; 2) dissolving the catalyst intermediate in a solvent, dropwise adding organic acid in an ice-water bath, stirring at normal temperature for 2-4 days, filtering, washing and drying to obtain the catalyst. The catalyst has the characteristics of high activity and high selectivity.

Description

Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof
Technical Field
The invention relates to the field of catalytic chemistry and organic chemistry, and relates to a heterogeneous catalyst for synthesizing diphenyl carbonate and a preparation method thereof.
Background
Diphenyl carbonate is an important carbonylation intermediate, is non-toxic and pollution-free, is an environment-friendly chemical product, is not only a raw material for synthesizing polycarbonate, but also can be widely used as a solvent, a plasticizer, a medical intermediate and the like. With the international popularization and application of the polycarbonate clean production technology and the successive production of large polycarbonate devices with the domestic introduction of technology and self development, the market demand of diphenyl carbonate will increase rapidly, so that the technology for cleanly producing diphenyl carbonate becomes a hotspot for research and development.
The catalyst for synthesizing diphenyl carbonate by reacting phenol and dimethyl carbonate mainly comprises an organic tin catalyst, a titanocene catalyst, a supported catalyst, a metal oxide catalyst, an ionic liquid catalyst and the like. Wherein the homogeneous catalyst has the highest catalytic activity, but after the ester exchange reaction is finished, the activity of part of the catalyst is reduced according to the characterization result of the catalyst. JP8188558, EP0780361 and JP10032361 introduce organic titanium and organic tin catalysts, such as tetrabutyl titanate, dibutyltin oxide and the like, which have high catalytic activity and yield of products of over 50 percent, but have the problems of difficult separation, recovery, environmental pollution and the like. In CN1803282A, Tongshen et al used vanadium-copper bimetallic oxide compounds as catalysts, and the yield and selectivity of the transesterification products were 40% and 96%, respectively. The transesterification reaction of dimethyl carbonate and phenol is a thermodynamically reversible reaction with a small equilibrium constant (3X 10-4 at 453K), which is detrimental to the formation of the target product, resulting in a low yield of diphenyl carbonate and a slow reaction rate. Therefore, it is very important to develop an environmentally friendly high-efficiency catalyst.
Disclosure of Invention
The invention provides a heterogeneous catalyst for synthesizing diphenyl carbonate and a preparation method thereof, which can solve the problems of difficult separation and difficult recycling of the existing catalyst and have the characteristics of high activity and high selectivity.
The invention adopts the technical scheme that the heterogeneous catalyst for synthesizing diphenyl carbonate comprises a carrier, a titanium source and organic acid, wherein the mass ratio of the titanium source to the carrier is 10-70:90-30, and the molar ratio of titanium to the organic acid is 0.05-5: 1.
Further, the titanium source is tetrabutyl titanate, tetraisopropyl titanate, titanyl sulfate, titanocene dichloride, tetraethyl titanate or dicyclopentadienyl dimethyl titanium.
Further, the carrier is ZSM-5 molecular sieve, HZSM-5 molecular sieve, TS-1 molecular sieve, MCM-41 molecular sieve or SiO2。
Further, the organic acid is acetic acid, succinic acid, adipic acid, sebacic acid, terephthalic acid, benzoic acid, or chlorosulfonic acid.
Further preferably, the mass ratio of the titanium source to the carrier is 30-50: 70-50, the molar ratio of the titanium source to the organic acid is 2-4: 1.
the invention also relates to a method for preparing said catalyst, comprising the following steps:
1) dissolving a titanium source by adopting a solvent, then adding a carrier, carrying out hydrothermal synthesis reaction at the temperature of 80-120 ℃ for 10-48h, filtering, and drying the carrier to obtain a catalyst intermediate;
2) dissolving the catalyst intermediate in a solvent, dropwise adding organic acid in an ice-water bath, stirring at normal temperature for 2-4 days, filtering, washing to neutrality, and drying the obtained solid to obtain the catalyst.
Further, when drying in the step 1), firstly, naturally drying for 1-5h, and then drying in an oven for 5-20h, wherein the drying temperature is 50-100 ℃.
Further, during the drying in the step 2), drying is carried out for 10-20h in an oven at 50-80 ℃.
The invention also relates to a method for synthesizing diphenyl carbonate by using the catalyst, which takes dimethyl carbonate and phenol as raw materials to react in a reaction kettle provided with a rectifying column, wherein the molar ratio of the dimethyl carbonate to the phenol is 0.5-2: 1, the dosage of the catalyst is 1-3wt% of the total mass of the dimethyl carbonate and the phenol, the reaction time is 10-20h, the reaction temperature is 130-200 ℃, after the reaction is finished, the catalyst is filtered and separated, and a sample is analyzed by adopting Agilent 7890B gas chromatography.
In the ester exchange process of dimethyl carbonate and phenol, the ester exchange reaction is a nucleophilic substitution reaction which can be catalyzed by acid and alkali, the phenol has stronger nucleophilicity due to the alkali catalyst, and the DMC has electron deficiency due to the acid catalyst, so that more phenol attacks the electron-deficient carbonyl carbon, and the selectivity of the product is improved. When the Lewis acid on the solid surface of the heterogeneous catalyst is used for activating the dimethyl carbonate, the generation of free phenol oxygen anions is avoided, so that the yield of the target product is improved.
The invention has the following beneficial effects:
1. since the transesterification of phenol and dimethyl carbonate to synthesize diphenyl carbonate is a reaction limited by thermodynamics, its equilibrium constant is small and is unfavorable for the main reaction. Aiming at the characteristics of the ester exchange reaction and the problems of the existing catalyst, the selected catalyst active substance and the carrier both have weak acid centers, can promote the reaction to be carried out, improve the product selectivity and have good activity on the dimethyl carbonate ester exchange reaction.
2. The organic titanium in the homogeneous catalyst has the highest activity, so that the organic titanium is selected as an active center, the porous molecular sieve is used as a carrier, the active component can be fully loaded on the carrier, and the porous molecular sieve can avoid the blockage of the carrier pore channel, avoid the loss of the active component and increase the activity of the catalyst. And active ingredients are loaded through the carrier, so that the problem that the catalyst and a product are difficult to separate is avoided. In addition, the active component is loaded on the catalyst, and the acid amount of the catalyst is increased by utilizing the weak acid center of the carrier, so that the activity of the catalyst is improved.
3. The organic acid is used as an auxiliary agent to increase the stability of the catalyst, and the addition of the organic acid requires an acidic catalyst, so that the acid content of the catalyst can be further ensured, and the loading amount of an active center on a carrier can be increased, so that the catalytic activity of the catalyst can be ensured.
4. The hydrothermal synthesis method is adopted for the active titanium source and the carrier, the hydrothermal reaction kettle has pressure, the connection between the titanium source and the carrier is increased through the pressure, so that the connection between the titanium source and the carrier is firmer and is not easy to break or fall off, the using amount of the titanium source loaded on the carrier is increased, the solvent and the moisture are removed, and the loss of components is reduced.
5. The catalyst directly loads the titanium source and the carrier, so that the titanium source and the carrier are closely connected, loss is avoided, the original catalytic activity of the titanium source can be ensured, the selectivity is good, and the method for preparing the catalyst is simple to operate, the materials are easy to obtain, the catalyst can be recycled, the economic cost is greatly reduced, and the industrialization is easy.
Detailed Description
The invention will be further elucidated with reference to the following examples.
Example 1:
dissolving 2.84g (0.01mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 6.63g of MCM-41 molecular sieve (mass ratio of 30:70), carrying out hydrothermal synthesis reaction at 105 ℃ for 24h, filtering, naturally drying the filtered mixture for 2h, and then drying in an oven for 8h at the drying temperature of 80 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding chlorosulfonic acid 0.005mol in an ice-water bath, stirring for 2 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 60 ℃ for 20 hours to obtain the catalyst 1.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 1: 1, the catalyst dosage is 1 wt%, the reaction time is 10h, and the reaction temperature is 170 ℃. The results obtained are shown in table 1.
Example 2:
dissolving 2.48g (0.01mol) of titanocene dichloride in absolute methanol, stirring and mixing uniformly, adding 5.79g of MCM-41 molecular sieve (mass ratio of 30:70), carrying out hydrothermal synthesis reaction at 105 ℃ for 24 hours, filtering, naturally drying the filtered mixture for 2 hours, and then drying in an oven for 8 hours at the drying temperature of 80 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding chlorosulfonic acid 0.005mol in an ice-water bath, stirring for 2 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 60 ℃ for 20 hours to obtain the catalyst 2.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 1: 1, the catalyst dosage is 1 wt%, the reaction time is 10h, and the reaction temperature is 170 ℃. The results obtained are shown in table 1.
Example 3
Dissolving 2.80g (0.01mol) of dicyclopentadienyl dimethyl titanium in absolute methanol, stirring and mixing uniformly, adding 6.53g of MCM-41 molecular sieve (mass ratio of 30:70), carrying out hydrothermal synthesis reaction at 105 ℃ for 24 hours, filtering, naturally air-drying the filtered mixture for 2 hours, and then drying in an oven for 8 hours at 80 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding chlorosulfonic acid 0.005mol in an ice-water bath, stirring for 2 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 60 ℃ for 20 hours to obtain the catalyst 3.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 1: 1, the catalyst dosage is 1 wt%, the reaction time is 10h, and the reaction temperature is 170 ℃. The results obtained are shown in table 1.
Example 4
Dissolving 3.40g (0.01mol) of tetrabutyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 7.93g of MCM-41 molecular sieve (mass ratio of 30:70), carrying out hydrothermal synthesis reaction at 105 ℃ for 24 hours, filtering, naturally drying the filtered mixture for 2 hours, and then drying in an oven for 8 hours at the drying temperature of 80 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding chlorosulfonic acid 0.005mol in an ice-water bath, stirring for 2 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 60 ℃ for 20 hours to obtain the catalyst 4.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 1: 1, the catalyst dosage is 1 wt%, the reaction time is 10h, and the reaction temperature is 170 ℃. The results obtained are shown in table 1.
Example 5
Dissolving 1.60g (0.01mol) of titanyl sulfate in anhydrous methanol, stirring and mixing uniformly, adding 3.73g of MCM-41 molecular sieve (mass ratio of 30:70), carrying out hydrothermal synthesis reaction at 105 ℃ for 24 hours, filtering, naturally drying the filtered mixture for 2 hours, and then drying in an oven for 8 hours at the drying temperature of 80 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding chlorosulfonic acid 0.005mol in an ice-water bath, stirring for 2 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 60 ℃ for 20 hours to obtain the catalyst 5.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 1: 1, the catalyst dosage is 1 wt%, the reaction time is 10h, and the reaction temperature is 170 ℃. The results obtained are shown in table 1.
TABLE 1
As can be seen from table 1, under the same catalyst preparation conditions and the same transesterification conditions, catalyst 1 has the highest conversion rate, the highest selectivity and the highest yield, which indicates that the catalyst 1 has the best activity of tetraisopropyl titanate.
Example 6
8.53g (0.03mol) of tetraisopropyl titanate was dissolved in anhydrous methanol, and after stirring and mixing, 12.80g of SiO were added2(mass ratio 40:60), carrying out hydrothermal synthesis reaction at 90 ℃ for 12h, filtering, naturally drying the filtered mixture for 5h, and then drying in an oven for 20h at the drying temperature of 60 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of succinic acid in an ice-water bath, stirring for 3 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 80 ℃ for 10 hours to obtain the catalyst 6.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 2: 1, the catalyst dosage is 2 wt%, the reaction time is 20h, and the reaction temperature is 140 ℃. The results obtained are shown in Table 2.
Example 7
Dissolving 8.53g (0.03mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 12.80g of ZSM-5 (mass ratio of 40:60), carrying out hydrothermal synthesis reaction at 90 ℃ for 12h, filtering, naturally drying the filtered mixture for 5h, and then drying in an oven for 20h at the drying temperature of 60 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of succinic acid in an ice-water bath, stirring for 3 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 80 ℃ for 10 hours to obtain the catalyst 7.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 2: 1, the catalyst dosage is 2 wt%, the reaction time is 20h, and the reaction temperature is 140 ℃. The results obtained are shown in Table 2.
Example 8
Dissolving 8.53g (0.03mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 12.80g of HZSM-5 (mass ratio 40:60), carrying out hydrothermal synthesis reaction at 90 ℃ for 12h, filtering, naturally drying the filtered mixture for 5h, and then drying in an oven for 20h at the drying temperature of 60 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of succinic acid in an ice-water bath, stirring for 3 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 80 ℃ for 10 hours to obtain the catalyst 8.
And (2) carrying out ester exchange reaction on phenol and dimethyl carbonate under the catalyst, wherein in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column, the molar ratio of the dimethyl carbonate to the phenol is 2: 1, the catalyst dosage is 2 wt%, the reaction time is 20h, and the reaction temperature is 140 ℃. The results obtained are shown in Table 2.
TABLE 2
Figure BDA0002194309320000061
As can be seen from Table 2, the conversion of phenol was over 50%, the transesterification selectivity was between 97.2 and 99.1%, and the yield was between 51.2 and 52.3%. Under the same active component, the effect of the carrier HZSM-5 is better than that of SiO2Is superior to ZSM-5 molecular sieve, which shows that the carrier has great influence on the activity of the catalyst.
Example 9
Dissolving 11.37g (0.04mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 11.37g of HZSM-5 (mass ratio of 50:50), carrying out hydrothermal synthesis reaction at 120 ℃ for 40h, filtering, naturally drying the filtered mixture for 3h, and then drying in an oven for 15h at the drying temperature of 100 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of acetic acid in an ice-water bath, stirring for 4 days at normal temperature, filtering, washing to neutrality, and drying the obtained solid in an oven at 70 ℃ for 15 hours to obtain the catalyst 9.
The ester exchange reaction of phenol and dimethyl carbonate is carried out under the catalyst, and the molar ratio of the dimethyl carbonate to the phenol in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column is 0.5: 1, the catalyst amount is 3wt%, the reaction time is 14h, and the reaction temperature is 190 ℃. The results obtained are shown in Table 3.
Example 10
Dissolving 11.37g (0.04mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 11.37g of HZSM-5 (mass ratio of 50:50), carrying out hydrothermal synthesis reaction at 120 ℃ for 40h, filtering, naturally drying the filtered mixture for 3h, and then drying in an oven for 15h at the drying temperature of 100 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of benzoic acid in an ice-water bath, stirring for 4 days at normal temperature, filtering, washing to be neutral, and drying the obtained solid in an oven at 70 ℃ for 15 hours to obtain the catalyst 10.
The ester exchange reaction of phenol and dimethyl carbonate is carried out under the catalyst, and the molar ratio of the dimethyl carbonate to the phenol in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column is 0.5: 1, the catalyst amount is 3wt%, the reaction time is 14h, and the reaction temperature is 190 ℃. The results obtained are shown in Table 3.
Example 11
Dissolving 11.37g (0.04mol) of tetraisopropyl titanate in anhydrous methanol, stirring and mixing uniformly, adding 11.37g of HZSM-5 (mass ratio of 50:50), carrying out hydrothermal synthesis reaction at 120 ℃ for 40h, filtering, naturally drying the filtered mixture for 3h, and then drying in an oven for 15h at the drying temperature of 100 ℃ to obtain a catalyst intermediate; and dissolving the catalyst intermediate in anhydrous methanol, stirring for about 2 hours, slowly dropwise adding 0.01mol of adipic acid in an ice-water bath, stirring for 4 days at normal temperature, filtering, washing to be neutral, and drying the obtained solid in an oven at 70 ℃ for 15 hours to obtain the catalyst 11.
The ester exchange reaction of phenol and dimethyl carbonate is carried out under the catalyst, and the molar ratio of the dimethyl carbonate to the phenol in a four-neck flask provided with a gas guide tube, a thermometer and a rectifying column is 0.5: 1, the catalyst amount is 3wt%, the reaction time is 14h, and the reaction temperature is 190 ℃. The results obtained are shown in Table 3.
TABLE 3
Figure BDA0002194309320000071
As can be seen from Table 3, the conversion of phenol was over 51.7-54.1%, the transesterification selectivity was between 97.8-99.4%, and the yield was between 50.6-53.8%. Under the same active component and carrier conditions, different organic acids also have a large influence on the activity of the catalyst, and as seen from table 3, the effect of benzoic acid is the best.
Example 12
The catalyst obtained in example 1 was separated, filtered, washed with DMC, and dried at 150 ℃ in an oven to obtain catalyst 12.
The reaction conditions were the same as in example 1, and the reaction results are shown in Table 4.
Example 13
The catalyst obtained in example 12 was separated, filtered, washed with DMC, and dried at 150 ℃ in an oven to obtain catalyst 13.
The reaction conditions were the same as in example 1, and the reaction results are shown in Table 4.
TABLE 4
Figure BDA0002194309320000081
As can be seen from Table 4, after catalyst 1 was reused 3 times, the conversion of phenol decreased by 0.8 percentage point, the transesterification selectivity did not decrease, and the yield decreased by 0.8 percentage point. From the data, the catalytic activity of the catalyst prepared by the method is relatively stable by adopting a mode of combining organic and catalysis, immobilizing organic titanium on a carrier and adding organic acid as an auxiliary agent.

Claims (9)

1. A heterogeneous catalyst for the synthesis of diphenyl carbonate, characterized in that: the catalyst comprises a carrier, a titanium source and organic acid, wherein the mass ratio of the titanium source to the carrier is 10-70:90-30, and the molar ratio of the titanium source to the organic acid is 0.05-5: 1.
2. The catalyst of claim 1, wherein: the titanium source is tetrabutyl titanate, tetraisopropyl titanate, titanyl sulfate, titanocene dichloride, tetraethyl titanate or dicyclopentadienyl dimethyl titanium.
3. The catalyst of claim 1, wherein: the carrier is ZSM-5 molecular sieve, HZSM-5 molecular sieve, TS-1 molecular sieve, MCM-41 molecular sieve or SiO2。
4. The catalyst of claim 1, wherein: the organic acid is acetic acid, succinic acid, adipic acid, sebacic acid, terephthalic acid, benzoic acid or chlorosulfonic acid.
5. The catalyst of claim 1, wherein: the mass ratio of the titanium source to the carrier is 30-50: 70-50, the molar ratio of the titanium source to the organic acid is 2-4: 1.
6. a process for preparing the catalyst according to any one of claims 1 to 5, characterized in that it comprises the following steps:
1) dissolving a titanium source by adopting a solvent, then adding a carrier, carrying out hydrothermal synthesis reaction at the temperature of 80-120 ℃ for 10-48h, filtering, and drying the carrier to obtain a catalyst intermediate;
2) dissolving the catalyst intermediate in a solvent, dropwise adding organic acid in an ice-water bath, stirring at normal temperature for 2-4 days, filtering, washing to neutrality, and drying the obtained solid to obtain the catalyst.
7. The method of claim 6, wherein: when drying in the step 1), firstly, naturally drying for 1-5h, and then drying in an oven for 5-20h, wherein the drying temperature is 50-100 ℃.
8. The method of claim 6, wherein: and (3) drying in an oven at 50-80 ℃ for 10-20h during drying in the step 2).
9. A method for synthesizing diphenyl carbonate using the catalyst according to any one of claims 1 to 5, characterized in that: dimethyl carbonate and phenol are used as raw materials and are reacted in a reaction kettle provided with a rectifying column, wherein the molar ratio of the dimethyl carbonate to the phenol is 0.5-2: 1, the dosage of the catalyst is 1-3wt% of the total mass of the dimethyl carbonate and the phenol, the reaction time is 10-20h, the reaction temperature is 130-.
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