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CN110183308B - A kind of non-metallic catalyst for preparing phenol by direct oxidation of benzene, preparation method and application - Google Patents

A kind of non-metallic catalyst for preparing phenol by direct oxidation of benzene, preparation method and application Download PDF

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CN110183308B
CN110183308B CN201910462783.8A CN201910462783A CN110183308B CN 110183308 B CN110183308 B CN 110183308B CN 201910462783 A CN201910462783 A CN 201910462783A CN 110183308 B CN110183308 B CN 110183308B
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王伟涛
魏遥遥
唐皓
姜旭禄
马养民
杨秀芳
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Shaanxi University of Science and Technology
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Abstract

一种用于苯直接氧化制备苯酚的非金属催化剂制备其应用方法，该方法将对苯醌和二胺分别溶于甲醇中；接着将二者溶液混合均匀后，向所述混合溶液中滴加双氧水；并将其转移至高压反应釜中，在120℃～160℃下反应4～12h，过滤后得到的非金属催化剂；该非金属催化剂在乙酸水溶液为溶剂、醋酸盐为添加剂的条件下，在120℃～150℃，可以催化氧气氧化苯制备苯酚，获得较好的苯酚产率。本方法制备的非金属催化可以催化氧气氧化苯制备苯酚，从而避免了含有重金属催化剂的使用。An application method for preparing a non-metallic catalyst for preparing phenol by direct oxidation of benzene, wherein p-benzoquinone and diamine are dissolved in methanol respectively; Hydrogen peroxide; and transfer it to a high-pressure reactor, react at 120°C to 160°C for 4 to 12 hours, and filter the obtained non-metallic catalyst; the non-metallic catalyst is obtained under the condition that the aqueous acetic acid solution is the solvent and the acetate is the additive. , at 120℃～150℃, it can catalyze oxygen oxidation of benzene to prepare phenol, and obtain better phenol yield. The non-metal catalyst prepared by the method can catalyze the oxidation of benzene with oxygen to prepare phenol, thereby avoiding the use of catalysts containing heavy metals.

Description

Nonmetal catalyst for preparing phenol by directly oxidizing benzene, preparation method and application
Technical Field
The invention belongs to the technical field of novel catalyst preparation and energy chemical industry, and particularly relates to a preparation method and application of a nonmetal catalyst for preparing phenol by directly oxidizing benzene.
Background
Phenol is an important chemical intermediate and bulk basic raw material for petrochemical industry. At present, the industrial production method of phenol is mainly an isopropyl benzene method, and has the defects of long reaction process, low atom utilization rate and low total yield (< 5%). Therefore, in recent years, various countries around the world have been devoted to research on a green process for producing phenol, in which direct oxidation of benzene to produce phenol is receiving wide attention as a new economical green process for producing phenol. The oxygen as a green oxidant has the advantages of wide source, low price and the like, and the oxidation product is water, so that a byproduct polluting the environment is not generated. Therefore, the method for preparing phenol by directly oxidizing benzene by using oxygen as an oxidant has important theoretical and practical application significance.
Catalysts generally used in the reaction of benzene oxidation to produce phenol are transition metal-containing catalysts. In patent CN102921419A, supported catalyst containing copper is used for catalyzing benzene oxidation to prepare phenol; in patent CN102228833A, a porous material containing cobalt is used as a catalyst to catalyze benzene oxidation to prepare phenol; in patent CN104926614A, a metal organic framework compound HKUST-1 containing copper is used as a catalyst to catalyze benzene for oxidation to prepare phenol; the literature reports that catalysts containing transition metals such as vanadium, iron, palladium and the like catalyze the oxygen oxidation of benzene to produce phenol [ (a) Wang WT, Li N, Tang H, et al Molecular catalysis, 2018,453,113-120; (b) Qin Q, Liu YQ, Shann WJ, et al Industrial & Engineering Chemistry Research, 2017, 56 (43), 12289-12296; Shang SS, Yang H, Li J, et al Chemplus 2014, 79 (5), 680-683 ]. The reaction for oxidizing benzene with oxygen to produce phenol is generally carried out in an acidic reaction solvent. The metal catalyst is easy to have active center loss in an acid solvent, so that the problems of reduction of catalytic activity, pollution caused by heavy metal ions and the like are caused, the stability of the catalyst is difficult to ensure, the production cost of phenol is increased, and people pay attention to the economy and environmental protection. Therefore, the nonmetal catalyst is promoted to be developed and applied to the research of green phenol preparation. So far, no literature is reported on the preparation of a nonmetal catalyst by using p-benzoquinone and diamine and the preparation of phenol by using the nonmetal catalyst as a catalyst to catalyze the oxygen oxidation of benzene.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and an application method of a nonmetal catalyst for preparing phenol by directly oxidizing benzene, so that the use of a metal-containing catalyst in the reaction of preparing phenol by directly oxidizing benzene is avoided, the problem of metal loss is avoided, the stability of the catalyst is improved, and the prepared catalyst shows better phenol yield in the reaction of preparing phenol by catalyzing oxygen to oxidize benzene.
In order to achieve the purpose, the invention adopts the technical scheme that:
the catalyst is a nonmetal catalyst prepared by taking p-benzoquinone and diamine as raw materials, and the active centers of the catalyst are benzoquinone and hydroquinone, so that nonmetal catalysis of preparing phenol by directly oxidizing benzene with oxygen is realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nonmetal catalyst for preparing phenol by directly oxidizing benzene comprises the following steps:
the method comprises the following steps: respectively dissolving p-benzoquinone and diamine in a methanol solution according to a molar ratio of 6: 1-1.5: 1 to obtain a methanol solution A of the p-benzoquinone and a methanol solution B of the diamine;
step two: adding the solution A obtained in the step one into the solution B, and uniformly stirring to obtain a solution C;
step three: dropwise adding 1-3 mL of hydrogen peroxide into the solution C obtained in the step two, uniformly stirring, and transferring the solution into a high-pressure reaction kettle;
step four: and adding the high-pressure autoclave at 120-160 ℃ for 4-12 h, filtering the obtained solid product, washing the solid product with methanol and distilled water until the filtrate is colorless and transparent, and drying to obtain the non-metal catalyst.
Further, the molar ratio of the p-benzoquinone to the diamine is 6: 1-1.5: 1.
Further, the diamine comprises ethylenediamine, propylenediamine, hexamethylenediamine, o-phenylenediamine and melamine.
Furthermore, the hydrogen peroxide is 10-30% in mass concentration and 1-3 mL in dosage.
Further, the four heating steps are carried out at the temperature of 120-160 ℃ for 4-12 hours.
A non-metal catalyst for preparing phenol by directly oxidizing benzene is prepared by the preparation method of the solid acid catalyst.
A catalytic application method based on the nonmetal catalyst comprises the following steps:
the method comprises the following steps: adding 0.025-0.2 g of the nonmetal catalyst, 0.5-1.0 mL of benzene, 0.2-0.8 g of acetate and 3.0mL of acetic acid water solution with the volume fraction of 50% -100% into a high-pressure reaction kettle;
step two: filling oxygen pressure of 1.0-4.0 MPa into the reaction kettle;
step three: and stirring the reaction kettle at the temperature of between 120 and 150 ℃ for reaction for 12 to 24 hours to obtain the product phenol.
Further, the acetate in the first step is lithium acetate and sodium acetate, and the using amount of the acetate is 0.2-0.8 g.
Further, the reaction solvent in the step one is an acetic acid aqueous solution with the volume concentration of 50-100%.
Further, the oxygen pressure in the second step is 1.0-4.0 MPa.
Further, the reaction temperature in the third step is 120-150 ℃.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention uses benzoquinone and diamine as simple raw materials, and can prepare the nonmetal catalyst through simple polymerization reaction, and the active center of the nonmetal catalyst is mainly the contained quinone-hydroquinone functional group. The nonmetal catalyst can be directly used as a catalyst for catalyzing oxygen to oxidize benzene to prepare phenol, so that the pollution of the use of the metal catalyst and the loss of heavy metals to the environment is avoided; the yield of the phenol prepared by catalyzing oxygen to oxidize benzene can reach the same level as that of the phenol prepared by catalyzing benzene by using a metal catalyst, and the catalyst has better catalytic activity; in addition, the preparation method of the catalyst is simple, efficient and convenient, and has the advantages of high catalytic activity, high yield and the like.
Drawings
FIG. 1 is a FT-IR plot of quinone amine polymers prepared from different amine sources. In the figure, (a) ethylenediamine, (b) propylenediamine, (c) hexamethylenediamine, (d) o-phenylenediamine, and (e) melamine.
FIG. 2 is an SEM spectrum of the non-metal catalyst obtained by the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of ethylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 3 MPa of O at room temperature2Reaction at 120 deg.c for 24 hr to obtain phenol in 13.1% yield.
Example 2
Respectively dissolving 20mmol of p-benzoquinone and 10mmol of ethylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 3 MPa of O at room temperature2Reaction at 120 deg.c for 12 hr gave phenol in 5.4% yield.
Example 3
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of propylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 3 MPa of O at room temperature2Reaction at 120 deg.c for 12 hr gave phenol in 15.9% yield.
Example 4
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of hexamethylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 2 MPa of O at room temperature2Reaction at 120 deg.c for 12 hr to obtain phenol in 15% yield.
Example 5
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of o-phenylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 2 MPa of O at room temperature2Reaction at 120 deg.c for 12 hr gave phenol in 5.1% yield.
Example 6
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of ethylenediamine in methanol, and adding the p-benzoquinone solution to the ethyleneAfter stirring the diamine solution uniformly, slowly adding 2 mL of 20% (wt.) H dropwise2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 130 ℃ for 7 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 3 MPa of O at room temperature2Reaction at 120 deg.c for 12 hr gave phenol in 5.2% yield.
Example 7
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of ethylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.2g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 3 MPa of O at room temperature2Reaction at 120 deg.c for 24 hr to obtain phenol in 6.4% yield.
Example 8
Respectively dissolving 30mmol of p-benzoquinone and 10mmol of ethylenediamine in methanol, adding the p-benzoquinone solution into the ethylenediamine solution, stirring uniformly, and slowly dropwise adding 1 mL of 30% (wt.) H2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of lithium acetate into 70% by volume of acetic acid solution, and charging 2 MPa of O at room temperature2Reaction at 140 deg.c for 24 hr to obtain phenol in 12.9% yield.
Example 9
30mmol of p-benzeneDissolving quinone and 10mmol ethylenediamine in methanol respectively, adding p-benzoquinone solution into ethylenediamine solution, stirring, and slowly adding 1 mL of 30% (wt.) H dropwise2O2. The solution was stirred to mix thoroughly and transferred to a high pressure autoclave equipped with a teflon liner and heated at 120 ℃ for 5 h. The resulting product was filtered, washed with 30 mL of methanol, and dried overnight at 80 ℃ to give a non-metallic catalyst.
Adding 0.1 g of catalyst, 0.5mL of benzene and 0.4 g of sodium acetate into 70% by volume of acetic acid solution, and charging 2 MPa O at room temperature2Reaction at 120 deg.c for 12 hr gave 14.3% yield of phenol.

Claims (6)

1.一种非金属催化剂在制备苯酚的应用，其特征在于，包括以下步骤：1. the application of a non-metallic catalyst in the preparation of phenol, is characterized in that, comprises the following steps: 将含有苯、醋酸盐、体积浓度为50%～100%的乙酸水溶液以及非金属催化剂的分散体置于高压容器中；向高压容器充入1.0MPa以上压力的氧气；令反应体系在120℃～150℃充分反应，即得到苯酚；Place the dispersion containing benzene, acetate, an aqueous acetic acid solution with a volume concentration of 50% to 100%, and a non-metallic catalyst in a high-pressure vessel; fill the high-pressure vessel with oxygen with a pressure of more than 1.0 MPa; make the reaction system at 120 ° C Fully reacted at ~150°C to obtain phenol; 所述的醋酸盐为醋酸锂、醋酸钠中的一种或多种；Described acetate is one or more in lithium acetate, sodium acetate; 所述的非金属催化剂由对苯醌、二胺类有机物及双氧水分散于足量的有机溶剂中，120℃～160℃进行溶剂热反应得到；The non-metallic catalyst is obtained by dispersing p-benzoquinone, diamine organic compounds and hydrogen peroxide in a sufficient amount of organic solvent, and performing solvothermal reaction at 120°C to 160°C; 所述的二胺类有机物为乙二胺、丙二胺、己二胺、邻苯二胺中的一种或多种。The diamine organic compounds are one or more of ethylene diamine, propylene diamine, hexamethylene diamine and o-phenylenediamine. 2.根据权利要求1所述的应用，其特征在于，制备非金属催化剂时，对苯醌与二胺类有机物的摩尔比为（6~1.5）:1。2 . The application according to claim 1 , wherein when preparing the non-metallic catalyst, the molar ratio of p-benzoquinone to diamine organics is (6～1.5):1. 3 . 3.根据权利要求1所述的应用，其特征在于，制备非金属催化剂时，所述的双氧水的质量浓度为10%～30%。3 . The application according to claim 1 , wherein when preparing the non-metallic catalyst, the mass concentration of the hydrogen peroxide is 10% to 30%. 4 . 4.根据权利要求1所述的应用，其特征在于，制备非金属催化剂时，溶剂热反应所采用的溶剂为甲醇，反应温度为120℃～160℃，反应时间为4～12小时。4 . The application according to claim 1 , wherein when preparing the non-metallic catalyst, the solvent used in the solvothermal reaction is methanol, the reaction temperature is 120° C. to 160° C., and the reaction time is 4 to 12 hours. 5 . 5.根据权利要求1~4任一项所述的应用，其特征在于，制备非金属催化剂时，具体步骤包括：5. application according to any one of claim 1～4, is characterized in that, when preparing non-metallic catalyst, concrete steps comprise: 步骤一：将对苯醌与二胺类有机物按照6:1～1.5:1的摩尔比，分别溶于甲醇溶液中，得到对苯醌的甲醇溶液A和二胺类有机物的甲醇溶液B；Step 1: dissolving p-benzoquinone and diamine organics in methanol solution according to the molar ratio of 6:1 to 1.5:1, respectively, to obtain methanol solution A of p-benzoquinone and methanol solution B of diamine organics; 步骤二：将步骤一得到的溶液A加入到溶液B中，并搅拌均匀，得到溶液C；Step 2: add solution A obtained in step 1 to solution B, and stir evenly to obtain solution C; 步骤三：向步骤二得到的溶液C中，滴加质量浓度为10%～30%双氧水1～3mL，搅拌均匀后，将溶液转移到高压反应釜中；Step 3: To the solution C obtained in step 2, add dropwise 1-3 mL of hydrogen peroxide with a mass concentration of 10% to 30%, and after stirring evenly, transfer the solution to the autoclave; 步骤四：将高压釜在120℃～160℃下反应4～12h，过滤后得到的固体产物，用甲醇和蒸馏水洗至滤液为无色透明后烘干，即得非金属催化剂。Step 4: The autoclave is reacted at 120°C to 160°C for 4 to 12 hours, and the solid product obtained after filtration is washed with methanol and distilled water until the filtrate is colorless and transparent, and then dried to obtain a non-metallic catalyst. 6.根据权利要求1所述的应用，其特征在于，具体步骤包括：6. application according to claim 1, is characterized in that, concrete steps comprise: 步骤一：在高压反应釜中加入0.025～0.2g所述非金属催化剂，0.5～1.0mL的苯，0.2～0.8g的醋酸盐，3.0mL 的体积浓度为50%～100%的乙酸水溶液；Step 1: add 0.025-0.2 g of the non-metallic catalyst, 0.5-1.0 mL of benzene, 0.2-0.8 g of acetate, and 3.0 mL of an aqueous acetic acid solution with a volume concentration of 50-100% in the autoclave; 步骤二：向反应釜中充入1.0～4.0MPa的氧气压力；Step 2: Fill the reaction kettle with an oxygen pressure of 1.0～4.0MPa; 步骤三：将所述反应釜在120℃～150℃下，搅拌反应12～24小时，即可到产物苯酚。Step 3: The reaction kettle is stirred and reacted at 120°C to 150°C for 12 to 24 hours to obtain the product phenol.
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