CN107778178B - Method for preparing monophenyl maleate - Google Patents

Method for preparing monophenyl maleate Download PDF

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CN107778178B
CN107778178B CN201610791489.8A CN201610791489A CN107778178B CN 107778178 B CN107778178 B CN 107778178B CN 201610791489 A CN201610791489 A CN 201610791489A CN 107778178 B CN107778178 B CN 107778178B
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phenol
maleic anhydride
reaction
molecular sieve
catalyst
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CN107778178A (en
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吴国文
林民
史春风
朱斌
王宝荣
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification

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Abstract

The invention relates to a method for preparing monophenyl maleate, which comprises the steps of carrying out contact reaction on reaction materials including phenol and maleic anhydride in the presence of a catalyst, and recovering the obtained monophenyl maleate.

Description

Method for preparing monophenyl maleate
Technical Field
The invention relates to a method for preparing monophenyl maleate, in particular to a method for preparing monophenyl maleate under the catalysis of a molecular sieve.
Background
The product of the esterification reaction of phenol and maleic anhydride is monophenyl maleate which is an important raw material for preparing 4-chromanone-2-formic acid.
The following two general methods exist for the preparation of monophenyl maleate.
The first method is to put phenol and maleic anhydride into a reaction bottle, heat to melt, add dry pyridine under stirring, react for a certain time under heating, determine that the acid value in the system is reduced by about 50%, and end the reaction. And (4) obtaining a white product after column chromatography purification, wherein the yield can reach 70%. However, this method has a problem that the pyridine used as a catalyst is highly toxic and causes a great pollution to the environment. In addition, in the operation process, a certain amount of pyridine needs to be supplemented, the operation is complicated, the reaction process needs absolute absence of water, the conditions are harsh, and the used catalyst cannot be reused.
The second method is that phenol is dissolved in sodium hydroxide solution and then maleic anhydride is added, after the reaction is finished, hydrochloric acid and ice are used for processing, and the monophenyl maleate is prepared through the procedures of suction filtration, water washing, drying and the like. However, this method has a problem that the yield of the product is low.
In addition, solid bases, e.g. Na, can be used in the absence of solvents2CO3A method for preparing monophenyl maleate by direct catalysis. Although the method does not use any solvent, the yield of the product is not high and is only about 50 percent, and although solid alkali is used, the reaction process is a homogeneous reaction, so that the separation is difficult after the reaction is finished, and hydrochloric acid needs to be added after the reaction is finished to precipitate white crystals.
Disclosure of Invention
The inventor of the invention unexpectedly discovers that when a titanium silicalite molecular sieve containing an alkaline template is taken as an active component of a catalyst and is combined with a specific feeding sequence in the process of generating the product of monophenyl maleate by the esterification reaction of phenol and maleic anhydride, the yield of monophenyl maleate is high; particularly, the method combines a specific solvent to carry out a reaction process, so that the reaction efficiency is higher. Based on this, the present invention was made.
Therefore, the invention aims to provide an environment-friendly, high-conversion and high-selectivity method for preparing monophenyl maleate, aiming at the defects of the prior art.
The invention provides a method for preparing monophenyl maleate, which is characterized in that in the presence of a catalyst, reaction materials including phenol and maleic anhydride are subjected to contact reaction, and the monophenyl maleate is obtained by recovery, wherein the active component of the catalyst is a titanium silicalite molecular sieve with a pore channel containing an alkaline template, and the method is to pre-mix phenol and the catalyst and then add maleic anhydride, wherein the catalyst accounts for 0.01-20 wt% of the reaction materials, and the weight ratio of the phenol to the maleic anhydride is 0.05-12: 1.
The method for preparing monophenyl maleate has the advantages that the conversion rate of phenol is high, the selectivity of monophenyl maleate reaches 100%, and particularly, the method has higher reaction efficiency in the presence of benzene as a solvent.
Detailed Description
The invention provides a method for preparing monophenyl maleate, which is characterized in that in the presence of a catalyst, reaction materials including phenol and maleic anhydride are subjected to contact reaction, and the monophenyl maleate is obtained by recovery, wherein the active component of the catalyst is a titanium silicalite molecular sieve with a pore channel containing an alkaline template, and the method is to pre-mix phenol and the catalyst and then add maleic anhydride, wherein the catalyst accounts for 0.01-20 wt% of the reaction materials, and the weight ratio of the phenol to the maleic anhydride is 0.05-12: 1.
In the method provided by the invention, the active component of the catalyst is a titanium silicalite molecular sieve with a pore channel containing a basic template agent, preferably the titanium silicalite molecular sieve with the pore channel containing the basic template agent after hydrothermal crystallization synthesis.
The titanium silicalite is a generic term for zeolites in which a part of silicon atoms in the lattice framework is replaced by titanium atoms. The titanium silicalite molecular sieve can be common titanium silicalite molecular sieves with various topologies, such as: can be selected from titanium silicalite molecular sieves with MFI structure (such as TS-1), MEL structure (such as TS-2), BEA structure (such as Ti-Beta), MWW structure (such as Ti-MCM-22), MOR structure (such as Ti-MOR), TUN structure (such as Ti-TUN), two-dimensional hexagonal structure (such as Ti-MCM-41, Ti-SBA-15) and other structure (such as Ti-ZSM-48); preferably selected from a titanium silicalite molecular sieve of MFI structure, a titanium silicalite molecular sieve of MEL structure or a titanium silicalite molecular sieve of BEA structure, more preferably a titanium silicalite molecular sieve of MFI structure.
The organic template in the hydrothermal crystallization synthesis of the titanium silicalite molecular sieve can be various organic templates commonly used in the process of synthesizing the titanium silicalite molecular sieve, such as: the organic matterThe templating agent may be one or more of a quaternary ammonium base, an aliphatic amine, and an aliphatic alcohol amine. The quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH3In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (e.g., an alkyl group), which may be a variety of NH3Wherein at least one hydrogen is substituted with a hydroxyl-containing aliphatic group (e.g., an alkyl group).
Specifically, the basic template agent may be one or more selected from the group consisting of a quaternary ammonium base represented by formula I, an aliphatic amine represented by formula II, and an aliphatic alcohol amine represented by formula III.
Figure BDA0001104301260000031
In the formula I, R1、R2、R3And R4Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r1、R2、R3And R4Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R5(NH2)n(formula II)
In the formula II, n is an integer of 1 or 2. When n is 1, R5Is C1-C6Alkyl of (2) including C1-C6Straight chain alkyl of (2) and C3-C6Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R5Is C1-C6Alkylene of (2) including C1-C6Linear alkylene of (A) and (C)3-C6Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene.
(HOR6)mNH(3-m)(formula III)
In the formula III, m R6Are the same or different and are each C1-C4Alkylene of (2) including C1-C4Linear alkylene of (A) and (C)3-C4Branched alkylene groups of (a), such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3.
The organic template agent can be specifically but not limited to: one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide (including various isomers of tetrapropylammonium hydroxide, such as tetra-n-propylammonium hydroxide and tetraisopropylammonium hydroxide), tetrabutylammonium hydroxide (including various isomers of tetrabutylammonium hydroxide, such as tetra-n-butylammonium hydroxide and tetraisobutylammonium hydroxide), ethylamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, and triethanolamine. Preferably, the templating agent is tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. More preferred basic templating agents are tetrapropylammonium hydroxide or tetraethylammonium hydroxide, with tetrapropylammonium hydroxide being most preferred.
The alkaline template agent plays a role in structure guiding, is positioned in the pore channel to support and stabilize the framework of the whole molecular sieve, has very good stability, and cannot be removed through the steps of washing, extracting and the like. The molecular sieve containing basic organic substances is generally used in catalytic reactions after being calcined at high temperature, and the basic template is converted into nitrogen oxides during calcination. For example, the basic template used in the synthesis of TS-1 is typically tetrapropylammonium hydroxide or tetraethylammonium hydroxide, an expensive organic material, which is calcined to create significant waste.
The invention utilizes the titanium silicalite molecular sieve containing the alkaline template agent in the pore channel as an active component, can synthesize monophenyl maleate in an environment-friendly and efficient manner, is a novel method for saving cost, reducing waste and reducing pollution from an economic perspective, can expand the application range of the titanium silicalite molecular sieve, can reduce waste, and is more economic and environment-friendly. Therefore, in the method of the invention, the titanium silicalite molecular sieve containing the basic template agent is used as the active component of the catalyst. The active component is a titanium-silicon molecular sieve containing organic alkali obtained by crystallization and washing steps without roasting by a hydrothermal synthesis method, and an alkaline template agent is retained in a molecular sieve framework.
In the molecular sieve containing the organic template, the content of the organic template is not more than 30 percent by weight; preferably, the content of the organic template agent is 0.1-15 wt%; more preferably, the content of the organic template agent is 0.5-12.5 wt%. The content of the organic template can be determined by a thermogravimetric analysis method, and generally, the weight loss percentage between 200 and 800 ℃ in the thermogravimetric analysis can be used as the content of the organic template, namely the template.
The titanium silicalite molecular sieve of MFI structure is known as titanium silicalite molecular sieve TS-1, and can be referred to the description of patent GB2071071A or USP 4410501. The titanium silicalite TS-1 is not subjected to a process of roasting to remove the template agent after hydrothermal crystallization synthesis, or even if the titanium silicalite is subjected to the process of roasting to remove the template agent, the template agent is not completely removed. The content of titanium oxide in the molecular sieve is not more than 20 weight percent, and the content of the organic template is not more than 30 weight percent; preferably, the content of the titanium oxide is 0.01-10 wt%, and the content of the organic template is 0.1-15.0 wt%; more preferably, the content of titanium oxide is 0.02 to 5.0 wt%, and the content of the organic template is 0.5 to 12.5 wt%.
For example, the titanium silicalite TS-1 can specifically comprise the following steps:
(1) according to SiO2:TiO25-200: 1, OH-:SiO20.1-1: 1, H2O:SiO220-200: 1, alkali metal SiO20 to 0.5, organic base SiO2Preparing a titanium-silicon precursor containing a titanium source, a silicon source and an organic base in a ratio of 0.1-2.0; the SiO2:TiO2Preferably 35-65: 1, OH-:SiO2Preferably in the range of 0.3 to 0.6:1, H2O:SiO2Preferably 60 to 100:1, and the alkali metal SiO2Preferred range of (B) is 0:1, organic base SiO2The preferable range of (A) is 0.4 to 1.0; the silicon source is tetraalkyl n-silicone grease or silica solA gum, preferably tetraethyl orthosilicate; the titanium source is TiCl4、TiOCl2Or a tetraalkyl titanate, preferably tetraethyl titanate; the organic base is tetraalkylammonium hydroxide, preferably tetrapropylammonium hydroxide;
(2) placing the titanium-silicon precursor obtained in the step (1) in a high-pressure kettle at the temperature of 130-200 ℃ for hydrothermal crystallization for 6-30 days;
(3) and (3) recovering the product obtained in the step (2), and drying to obtain the titanium silicalite TS-1 containing the structure directing agent in the pore channel.
From the viewpoint of further improving the conversion rate of phenol and the yield of monophenyl maleate, the titanium silicalite molecular sieve is a hollow titanium silicalite molecular sieve with an MFI structure, and the synthesis of the hollow titanium silicalite molecular sieve (HTS) with the MFI structure is disclosed in patent CN 1132699C, but does not include a subsequent roasting step. The hollow titanium silicalite molecular sieve with MFI structure can be prepared by two methods. One of the methods specifically comprises the following steps:
(1) mixing TS-1, an acidic compound and water uniformly according to a certain proportion, and reacting for a certain time at a certain temperature to obtain TS-1-A; the ratio of the TS-1 to the acidic compound to the water is (TS-1) to (water: 100) (0.10-2.0) to (5-250), preferably (100) (0.080-0.8) to (10-100); the acid compound can be an organic fatty acid compound, an inorganic acid compound or an acid salt compound; the reaction temperature is 5-95 ℃, and preferably 15-60 ℃; the reaction time is 5-300 min, preferably 10-180 min;
(2) uniformly mixing the TS-1-A obtained in the step (1), organic alkali and water according to a certain proportion, putting the obtained mixture into a sealed reaction kettle, and reacting for a plurality of times at a certain temperature and under autogenous pressure; the proportion of the TS-1-A, the organic base and the water is that the ratio of the TS-1 to the organic base to the water is 100 (0.0050-0.50) to 5-200, preferably 100 (0.010-0.15) to 20-80; the organic base is a fatty amine compound, an alcohol amine compound or a quaternary ammonium base compound, preferably ethylamine, n-butylamine, butanediamine, hexamethylene diammonium, ethanolamine, diethanolamine, triethanolamine or tetrapropylammonium hydroxide; the reaction temperature is 120-200 ℃, and preferably 150-180 ℃; the reaction time is 1-192 h, preferably 3-72 h;
(3) and (3) recovering the product obtained in the step (2), and drying to obtain the titanium silicalite molecular sieve HTS with the hollow structure and the structure-directing agent in the pore channel.
The second method comprises the following steps:
(1) mixing TS-1, organic alkali and water in certain proportion; the proportion of the TS-1, the organic alkali and the water is that the TS-1, the organic alkali and the water are 100 (0.0050-0.50) to (5-200), preferably 100 (0.010-0.15) to (20-80); the organic base is a fatty amine compound, an alcamine compound, a quaternary ammonium base compound or a mixture containing the organic bases, preferably ethylamine, n-butylamine, butanediamine, hexamethylene diammonium, ethanolamine, diethanolamine, triethanolamine or tetrapropylammonium hydroxide;
(2) putting the uniform mixture obtained in the step (1) into a sealed reaction kettle, and reacting for a plurality of times at a certain temperature and autogenous pressure; the reaction temperature is 120-200 ℃, and preferably 150-180 ℃; the reaction time is 1-192 h, preferably 2-120 h;
(3) and (3) recovering the product obtained in the step (2), and drying to obtain the titanium silicalite molecular sieve HTS with the pore channel containing the structure directing agent and the hollow structure.
In the method provided by the invention, the mass of the added catalyst in the reaction process is 0.01-20% of the total mass of the reactants, and the mass of the added catalyst is preferably 1-6% of the total mass of the reactants.
According to the method provided by the invention, the weight ratio of phenol to maleic anhydride is 0.05-12:1, and the preferred weight ratio of phenol to maleic anhydride is 0.1-2: 1.
In the method provided by the invention, the reaction temperature in the reaction process is room temperature-140 ℃, the stirring speed is 100-600r/min, the reaction time is 1min-500min, and the preferable reaction conditions are as follows: the reaction temperature is 30-100 ℃, the stirring speed is 200-500r/min, and the reaction time is 5-200 min.
According to the method provided by the invention, no solvent is added in the reaction process, or a certain amount of common solvent including ketones, alcohols, esters, aromatic hydrocarbon, halogen-containing solvent and the like can be added, wherein the mass of the added solvent is 10-50% of the total mass of reactants. After analyzing the technical effects of the technical scheme of adding the solvent, the inventors surprisingly found that when benzene is used as the reaction solvent under the condition of basically the same reaction conditions, the reaction rate is greatly improved under the condition of obtaining the same high yield of monophenyl maleate. For example, in the case of a 1:1 weight ratio of phenol to maleic anhydride in the reaction mass and a 0.5 wt% catalyst in the reaction mass, if a 90% yield is also obtained, a scheme using benzene as the solvent and maleic anhydride pre-mixed with benzene uniformly can achieve a 90% yield in 30min, whereas a scheme without solvent or with solvent but with solvent other than benzene requires at least 100 min. (see examples and comparative examples)
Therefore, the most preferable scheme of the invention is that the titanium silicalite molecular sieve is a titanium silicalite molecular sieve HTS with a hollow structure, the alkaline template agent is tetraethylammonium hydroxide, the molar ratio of phenol to maleic anhydride is 1-1.2:1, the solvent is benzene, the benzene and the maleic anhydride are premixed, the benzene accounts for 20-30 wt% of the maleic anhydride, and the reaction condition is normal pressure and 80-95 ℃.
In the method provided by the invention, the monophenyl maleate crystal product obtained by the post-reaction treatment can be recovered by common methods of filtration, washing, drying and the like in the prior art, and the method has no special requirements. All washing can be carried out by using distilled water or deionized water; the drying conditions can be carried out at room temperature to 120 ℃.
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
In the examples, TiO in the TS-1 molecular sieves2The mass percentage of the titanium dioxide is 2.1 percent, and TiO in the HTS molecular sieve2The mass percentage of (B) is 2.1%.
The reagents used were commercially available, chemically pure reagents. The reaction vessel used was a three-necked flask with a condenser tube and the product was subjected to phenol conversion on a 6890N chromatograph using an HP-5 capillary column.
Phenol conversion ═ mole of phenol added-mole of unreacted phenol)/mole of phenol added
The selectivity of monophenyl maleate is equal to the mole number of monophenyl maleate/(mole number of added phenol-mole number of unreacted phenol)
Yield of monophenyl maleate ═ phenol conversion × monophenyl maleate selectivity
Comparative example 1
This comparative example illustrates the catalyst-free process and results.
Adding a mixture consisting of 3.9g of phenol and 4.5g of maleic anhydride into a reaction bottle, stirring the mixture uniformly without using any solvent, slowly heating the mixture, controlling the reaction temperature to be about 80 ℃, and stirring the mixture at 350 r/min. Samples were taken every 30min after the reaction and the product composition was analyzed by gas chromatography.
Comparative example 2
This comparative example illustrates the course of the reaction and the results in the presence of a catalyst.
The difference from comparative example 1 is that 0.5g of TS-1 molecular sieve containing 12.5 wt% tetrapropylammonium hydroxide was added simultaneously with phenol and maleic anhydride.
Comparative example 3
The same as in comparative example 2, but with the difference in the order of addition, the mixture of phenol and maleic anhydride was charged to the reaction flask and 0.5g of TS-1 molecular sieve containing 12.5 wt% tetrapropylammonium hydroxide was added.
Example 1
This example illustrates the process of the present invention.
The difference from comparative example 2 is that the addition sequence is that phenol and catalyst are mixed in advance and then maleic anhydride is added.
Example 2
This example illustrates the process of the present invention.
The same as example 1, except that a solvent was added, the solvent being 1g of acetone.
Example 3
This example illustrates the process of the present invention.
The same as example 1, except that a solvent was added, the solvent was 1g of ethanol.
Example 4
This example illustrates the process of the present invention.
The same as in example 1, except that a solvent was added, the solvent was 1g of ethyl acetate.
Example 5
This example illustrates the process of the present invention.
The same as example 1, except that a solvent was added, the solvent being 1g of carbon tetrachloride.
Example 6
This example illustrates the process of the present invention.
The same as in example 1, except that a solvent was added, the solvent was 1g of benzene.
Example 7
This example illustrates the process of the present invention.
The same as example 1, except that a solvent was added, the solvent was 1g of benzene, and the benzene was premixed with maleic anhydride.
Example 8
The difference is that TS-1 is replaced by a titanium silicalite HTS with a hollow structure with a uniform tetrapropylammonium hydroxide content of 4.5% by weight, as in example 1.
Example 9
The difference is that TS-1 is replaced by a titanium silicalite HTS with a hollow structure with a uniform tetrapropylammonium hydroxide content of 4.5% by weight, as in example 6.
Example 10
The difference is that TS-1 is replaced by a titanium silicalite HTS with a hollow structure with a uniform tetrapropylammonium hydroxide content of 4.5% by weight, as in example 7.
Figure BDA0001104301260000101
Example 11
Adding a mixture consisting of 3.2g of phenol and 0.9g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 7g of maleic anhydride and 2g of benzene, then adding the mixture, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 80 ℃, stirring the mixture at 350r/min, reacting for 30min, then sampling, analyzing the composition of a product by using a gas chromatography, and obtaining the result: the phenol conversion was 89% and the monophenyl maleate selectivity was 100%.
Example 12
Adding a mixture consisting of 6.4g of phenol and 0.3g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 5.5g of maleic anhydride and 1.2g of benzene, adding the mixture into the reaction bottle, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 85 ℃, stirring the mixture at 350r/min, sampling after reacting for 30min, analyzing the composition of a product by using gas chromatography, and obtaining a result: the phenol conversion was 44% and the monophenyl maleate selectivity was 100%.
Example 13
Adding a mixture consisting of 5.6g of phenol and 0.2g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 5.0g of maleic anhydride and 1.7g of benzene, then adding the mixture into the reaction bottle, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 90 ℃, stirring the mixture at 350r/min, sampling after reacting for 30min, analyzing the composition of a product by using gas chromatography, and obtaining a result: the conversion of phenol was 47% and the selectivity to monophenyl maleate was 100%.
Example 14
Adding a mixture consisting of 7.5g of phenol and 0.8g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 7.8g of maleic anhydride and 2.2g of benzene, adding the mixture into the reaction bottle, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 100 ℃, stirring the mixture at 350r/min, sampling after reacting for 30min, analyzing the composition of a product by using a gas chromatography, and obtaining a result: the conversion of phenol was 51% and the selectivity to monophenyl maleate was 100%.
Example 15
Adding a mixture consisting of 4.5g of phenol and 0.2g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 5.0g of maleic anhydride and 1.2g of benzene, then adding the mixture into the reaction bottle, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 70 ℃, stirring the mixture at 350r/min, sampling after reacting for 30min, analyzing the composition of a product by using gas chromatography, and obtaining a result: the conversion of phenol was 66% and the selectivity to monophenyl maleate was 100%.
Example 16
Adding a mixture consisting of 9g of phenol and 0.6g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 5g of maleic anhydride and 1.2g of benzene, adding the mixture into the reaction bottle, stirring the mixture uniformly, slowly heating the mixture, controlling the temperature to be about 80 ℃, stirring the mixture at 350r/min, reacting the mixture for 30min, sampling, analyzing the composition of a product by using a gas chromatography, and obtaining a result: the conversion of phenol was 37% and the selectivity to monophenyl maleate was 100%.
Example 17
Adding a mixture consisting of 1g of phenol and 0.65g of TS-1 molecular sieve containing 12.5 weight percent of tetrapropylammonium hydroxide into a reaction bottle, then premixing 12g of maleic anhydride and 3g of benzene, uniformly stirring the mixture, slowly heating, controlling the temperature to be about 75 ℃, stirring at 350r/min, reacting for 30min, sampling, analyzing the composition of a product by using gas chromatography, and obtaining a result: the conversion of phenol was 94% and the selectivity to monophenyl maleate was 100%.
Example 18
The same as example 17 except that TS-1 molecular sieve containing 12.5 wt% tetrapropylammonium hydroxide was replaced with HTS molecular sieve containing 8.5 wt% tetrapropylammonium hydroxide.
After reacting for 30min, sampling, and analyzing the composition of the product by using gas chromatography to obtain the following results: the conversion of phenol was 99% and the selectivity to monophenyl maleate was 100%.

Claims (6)

1. A method for preparing monophenyl maleate is characterized in that in the presence of a catalyst, a reaction material comprising phenol and maleic anhydride is subjected to contact reaction in the presence of benzene as a solvent, and the monophenyl maleate is recovered, wherein the active component of the catalyst is a titanium silicalite molecular sieve with channels containing an alkaline template agent, and the method comprises the steps of premixing phenol and the catalyst, and then adding maleic anhydride, wherein the catalyst accounts for 0.01-20 wt% of the reaction material, and the weight ratio of the phenol to the maleic anhydride is 0.05-12: 1; the titanium silicalite molecular sieve is selected from TS-1 or hollow titanium silicalite molecular sieve HTS with MFI structure; the alkaline template is selected from tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
2. The process of claim 1 wherein the basic template-containing titanium silicalite molecular sieve comprises no more than 30 wt.% basic template.
3. The process of claim 1 wherein said catalyst comprises from 1 to 6 weight percent of said reaction mass.
4. The method of claim 1, wherein the weight ratio of phenol to maleic anhydride is 0.1-2: 1.
5. A process according to claim 1, characterized in that it is carried out at atmospheric pressure, at room temperature to 140 ℃.
6. The method of claim 1, wherein the catalyst is titanium silicalite HTS, the alkaline template is tetrapropylammonium hydroxide, the molar ratio of phenol to maleic anhydride is 1-1.2:1, the solvent benzene is premixed with maleic anhydride, the solvent benzene accounts for 20-30 wt% of the maleic anhydride, and the reaction condition is normal pressure and 80-95 ℃.
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