阅读说明：本技术 一种配位型邻苯三酚锆的合成及其在制备环己醇中的应用 (Synthesis of coordination type zirconium o-benzenetrisol and application of coordination type zirconium o-benzenetrisol in preparation of cyclohexanol ) 是由 王海军 徐广志 刘晨 于 2020-06-12 设计创作，主要内容包括：本发明公开一种配位型邻苯三酚锆的合成及其在制备环己醇中的应用,属于催化氢化应用领域。本发明以邻苯三酚(PA)和四氯化锆(ZrCl<Sub>4</Sub>)为原料合成,通过水热法合成配位型邻苯三酚锆催化剂。本发明制备出的催化剂配位型邻苯三酚锆不仅对环己酮转化为环己醇具有良好的催化效果,而且反应条件温和,大大减少了现有技术所需的能耗。此外,本发明中的配位型邻苯三酚锆(Zr-PA)催化剂为非均相型催化剂,反应结束后通过简单的过滤可将催化剂回收并用于下一次反应中,而且多次循环后仍具有良好的催化效果。(The invention discloses a synthesis method of coordination type zirconium pyrogallol and application of the coordination type zirconium pyrogallol in preparation of cyclohexanol, belonging to the field of catalytic hydrogenation application. The invention uses Pyrogallol (PA) and zirconium tetrachloride (ZrCl) 4 ) Synthesizing a coordination type zirconium pyrogallol catalyst by a hydrothermal method. The catalyst coordination type zirconium o-benzenetriol prepared by the invention has a good catalytic effect on the conversion of cyclohexanone into cyclohexanol, and has mild reaction conditions, so that the energy consumption required by the prior art is greatly reduced. In addition, the coordination type zirconium pyrogallol (Zr-PA) catalyst in the present invention is non-coordinatedThe homogeneous catalyst can be recovered and used in the next reaction through simple filtration after the reaction is finished, and still has good catalytic effect after multiple cycles.)

1. A method for synthesizing a coordination type zirconium pyrogallol catalyst is characterized by comprising the following steps: with Pyrogallol (PA) and zirconium tetrachloride (ZrCl)₄) The coordination type zirconium pyrogallol catalyst is synthesized by taking the raw materials as raw materials, wherein the molar ratio of pyrogallol to zirconium tetrachloride is 1: (1-3).

2. The method according to claim 1, wherein the zirconium pyrogallol catalyst is obtained by mixing pyrogallol and zirconium tetrachloride in a solution form, adding a glacial acetic acid solution into the mixed solution, reacting for 14-18 h at 140-160 ℃, and after the reaction is finished, performing solid-liquid separation and washing.

3. The process according to claim 1 or 2, wherein the process for the synthesis of zirconium pyrogallol catalyst is carried out by the following steps:

taking pyrogallol and zirconium tetrachlorideDissolving in DMF, ultrasonic dispersing, and adding dropwise pyrogallol solution after ultrasonic treatment to ZrCl after ultrasonic treatment₄And (2) after the solutions are uniformly mixed, dropwise adding a glacial acetic acid solution into the mixed solution, then reacting for 16 hours at 140 ℃, naturally cooling the reactor to room temperature after the reaction is finished, carrying out suction filtration, washing the obtained solid product for 2-3 times by using DMF (dimethyl formamide) and absolute ethyl alcohol respectively, drying the washed solid product for 8-15 hours at 70-100 ℃ in a vacuum drying oven, and grinding to obtain the Zr-PA catalyst.

4. A process according to any one of claims 1 to 3, wherein the molar ratio of pyrogallol to zirconium tetrachloride is from 1: 2.

5. the coordination type zirconium pyrogallol catalyst prepared by the method according to any one of claims 1 to 4.

6. A method for preparing cyclohexanol by catalytic hydrogenation of cyclohexanone, characterized in that the coordination type zirconium o-phthalate in claim 5 is used as a catalyst, cyclohexanone is used as a substrate, the addition amount of the catalyst is 0.1-0.3 g zirconium o-phthalate/mmol cyclohexanone, and the reaction lasts for 8-11 h at 110-150 ℃.

7. The process for the catalytic hydrogenation of cyclohexanone to cyclohexanol in claim 6, wherein isopropanol is used as hydrogen source.

8. The process for the catalytic hydrogenation of cyclohexanone to cyclohexanol in claim 6, wherein the catalyst is used in an amount of 0.02g/mmol of cyclohexanone.

9. The process for the catalytic hydrogenation of cyclohexanone to cyclohexanol as recited in claim 6, wherein the reaction is: the reaction was carried out at 140 ℃ for 10 h.

10. Use of the zirconium pyrogallol catalyst of claim 5 in the fields of paints, cosmetics, perfumes, foods, and medicines.

Technical Field

The invention relates to a synthesis method of coordination type zirconium pyrogallol and application thereof in preparation of cyclohexanol, belonging to the field of catalytic hydrogenation application.

Background

With the rapid development of society, the problems of energy and environment are more and more prominent, and the traditional production process can cause the problems of energy waste, environmental pollution and the like. In order to solve the contradiction between energy and environment, the search for novel, green and renewable energy has received extensive attention. Biomass is not only a renewable resource, but also an energy source which is distributed most widely, in the largest number and variety, on earth, and thus has attracted great attention from many researchers. At present, the basic material platform of biomass is utilized, more and more technologies are provided for producing high value-added compounds by taking the basic materials as raw materials, and the development of new production technologies, production routes and the production of high value-added compounds have profound influence on the actual production and the development of modern industries.

Cyclohexanol is an important organic intermediate and has been widely used in the fields of coating, cosmetics, perfume, food, medicine, and the like. The main method for preparing cyclohexanol by the traditional process is a cyclohexane oxidation method, but the preparation process of the method is complex, and various byproducts appear in the produced cyclohexanol, so that the application of the cyclohexanol in the fields of medicines, foods and cosmetics is limited. Therefore, the development of a green synthesis process is a problem to be solved urgently at present for preparing cyclohexanol.

Pyrogallol is a green novel catalyst and is widely used for organic reagents, biological reagents, chromatographic analysis reagents and the like, but the field of the catalytic hydrogenation reaction by using the pyrogallol as a raw material for synthesizing zirconium pyrogallol is not reported.

Disclosure of Invention

[ problem ] to

The main method for preparing cyclohexanol by the traditional process is a cyclohexane oxidation method, but the preparation process of the method is complex, and various byproducts appear in the produced cyclohexanol, so that the application of the cyclohexanol in the fields of medicines, foods and cosmetics is limited. Therefore, the development of a green synthesis process is a problem to be solved urgently at present for preparing cyclohexanol.

[ solution ]

Aiming at the problems, the invention provides a synthesis method of coordination type zirconium o-benzenetriol and an application of the coordination type zirconium o-benzenetriol in preparation of cyclohexanol. Meanwhile, the catalyst has the advantages of high reaction activity, greenness, no pollution, recycling and the like, and can realize the high-efficiency conversion of cyclohexanone to cyclohexanol under mild conditions.

The invention provides a method for synthesizing a coordination type zirconium pyrogallol catalyst, which comprises the following steps: with Pyrogallol (PA) and zirconium tetrachloride (ZrCl)₄) The coordination type zirconium pyrogallol catalyst is synthesized by taking the raw materials as raw materials, wherein the molar ratio of pyrogallol to zirconium tetrachloride is 1: (1-3).

In one embodiment of the invention, the zirconium pyrogallol catalyst is prepared by mixing pyrogallol and zirconium tetrachloride in a solution form, adding a glacial acetic acid solution into the mixed solution, reacting at 140-160 ℃ for 14-18 h, and after the reaction is finished, performing solid-liquid separation and washing.

In one embodiment of the present invention, the method for synthesizing the zirconium pyrogallol catalyst is performed by the following steps:

taking Pyrogallol (PA) and zirconium tetrachloride (ZrCl)₄) Respectively dissolving in DMF, ultrasonically dispersing, and dripping the treated pyrogallol solution into the treated ZrCl₄And (2) after the solutions are uniformly mixed, dropwise adding a glacial acetic acid solution into the mixed solution, then reacting for 16 hours at 140 ℃, naturally cooling the reactor to room temperature after the reaction is finished, carrying out suction filtration, washing the obtained solid product for 2-3 times by using DMF (dimethyl formamide) and absolute ethyl alcohol respectively, drying the washed solid product for 8-15 hours at 70-100 ℃ in a vacuum drying oven, and grinding to obtain the Zr-PA catalyst.

In one embodiment of the invention, the molar ratio of pyrogallol to zirconium tetrachloride is 1: 2.

in one embodiment of the invention, the concentration of the DMF of the pyrogallol is 0.1-0.25 mol/L.

In one embodiment of the present invention, the concentration of DMF in the zirconium tetrachloride is 0.1 to 0.25 mmol/L.

In one embodiment of the invention, the concentration of the glacial acetic acid solution is 0.078-0.158 mmol/L.

In one embodiment of the present invention, the method of ultrasonic dispersion is: and (4) carrying out ultrasonic treatment for 5-20 min by using an ultrasonic cleaning machine.

The invention provides a coordination type zirconium pyrogallol catalyst prepared by the method.

The invention provides a method for preparing cyclohexanol by catalytic hydrogenation of cyclohexanone by using the catalyst, wherein the reaction takes zirconium o-phthalate as the catalyst, cyclohexanone as a substrate, and the addition amount of the zirconium o-phthalate is as follows: 0.1 to 0.3g of zirconium pyrogallol/mmol of cyclohexanone, and reacting for 8 to 11 hours at a temperature of between 110 and 150 ℃.

In one embodiment of the present invention, isopropanol is used as a hydrogen source in the catalytic hydrogenation reaction.

In one embodiment of the invention, the amount of isopropanol added in the catalytic hydrogenation reaction is 5-10 mL/mmol of cyclohexanone.

In one embodiment of the present invention, the amount of zirconium pyrogallol used as the catalyst in the catalytic hydrogenation reaction is 0.02g/mmol of cyclohexanone.

In one embodiment of the present invention, the reaction temperature of the catalytic hydrogenation reaction is 140 ℃.

In one embodiment of the present invention, the reaction time of the catalytic hydrogenation reaction is 10 hours.

The invention provides application of the coordination type zirconium pyrogallol catalyst in the fields of paint, cosmetics, spice, food and medicine.

[ advantageous effects ]

(1) The catalyst prepared by the invention is coordination type zirconium pyrogallol, the pyrogallol used as the raw material of the catalyst has a special structure, and a good microenvironment can be provided for the reaction, so that the yield and the selectivity of cyclohexanol are improved. The catalyst coordination type zirconium o-benzenetriol provided by the invention has a good catalytic effect on the conversion of cyclohexanone into cyclohexanol, and is mild in reaction conditions, so that the energy consumption required by the prior art is greatly reduced.

(2) The coordination type zirconium pyrogallol (Zr-PA) catalyst is a heterogeneous catalyst, can be recycled and used in the next reaction through simple filtration after the reaction is finished, and still has good catalytic effect after multiple cycles.

Drawings

FIG. 1 is a graph showing yields of catalytic hydrogenation of cyclohexanone by a zirconium pyrogallol catalyst in coordination form at different temperatures in example 4.

FIG. 2 is a graph showing the yields of catalytic hydrogenation of cyclohexanone by the zirconium pyrogallol catalyst in coordination form at different times in example 5.

FIG. 3 is a graph showing the yields of the catalytic hydrogenation of cyclohexanone by the coordination type zirconium pyrogallol catalyst in example 6 at different catalyst dosages.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.

Method for determining cyclohexanol by Gas Chromatography (GC):

quantitative analysis of the reactants and products was carried out by gas chromatography using model GC 9790 from Agilent technologies, Inc. The parameters of the gas chromatograph were set as follows, column: SE-54(60 m); a detector: a flame ionization detector; mobile phase: 0.1mL/min hydrogen, 0.1mL/min nitrogen, 0.2mL/min air; sample introduction amount: 0.30 mu L; column temperature: 100 ℃; a detector: 300 ℃; a sample inlet: at 300 ℃. Naphthalene is selected as an internal standard substance, and the product is quantitatively analyzed by adopting an internal standard method.

Conversion refers to the percentage of conversion of a certain reactant; yield is the percentage of the total amount of reactants produced by the desired product. The specific calculation method is as follows:

[ example 1 ] preparation of zirconium Phthalic Triphenoxide catalyst

0.127g of Pyrogallol (PA) and 0.466g of zirconium tetrachloride (ZrCl)₄) Respectively dissolving in 20mL DMF solution, and ultrasonic treating for 10min with ultrasonic cleaning machine. Firstly, the ultrasonic-treated ZrCl₄The solution was poured into a 100mL PTFE reactor, and then pyrogallol solution was added dropwise thereto, and after the above solutions were mixed uniformly, 3mL of glacial acetic acid with a concentration of 0.1mmol/L was added dropwise thereto. The reactor was then moved to a thermostatted drying oven at 140 ℃ and the reaction was continued for 16 h. After the reaction is finished, the reactor is naturally cooled to room temperature, and is respectively washed 3 times by DMF and absolute ethyl alcohol, and is dried for 12 hours under the vacuum condition of 100 ℃, and the Zr-PA catalyst is obtained by grinding.

[ example 2 ] preparation of zirconium Phthalic Triphenoxide catalyst

0.127g of Pyrogallol (PA) and 0.233g of zirconium tetrachloride (ZrCl)₄) Respectively dissolving in 20mL DMF solution, and ultrasonic treating for 10min with ultrasonic cleaning machine. Firstly, the ultrasonic-treated ZrCl₄The solution was poured into a 100mL PTFE reactor, and then pyrogallol solution was added dropwise thereto, and after the above solutions were mixed uniformly, 3mL of glacial acetic acid with a concentration of 0.1mmol/L was added dropwise thereto. The reactor was then moved to a thermostatted drying oven at 140 ℃ and the reaction was continued for 16 h. After the reaction is finished, the reactor is naturally cooled to room temperature, and is respectively washed 3 times by DMF and absolute ethyl alcohol, and is dried for 12 hours under the vacuum condition of 100 ℃, and the Zr-PA catalyst is obtained by grinding.

[ example 3 ] preparation of zirconium Phthalic Triphenoxide catalyst

0.127g of Pyrogallol (PA) and 0.466g of zirconium tetrachloride (ZrCl)₄) Respectively dissolving in 20mL DMF solution, and ultrasonic treating for 10min with ultrasonic cleaning machine. Firstly, the ultrasonic-treated ZrCl₄Pouring the solution into a 100mL PTFE reactor, dropwise adding pyrogallol solution, and after the solution is uniformly mixed, dropwise adding 3mL of glacial acetic acid with the concentration of 0.1mmol/L. The reactor was then moved to a constant temperature dry box at 160 ℃ and the reaction was continued for 16 h. After the reaction is finished, the reactor is naturally cooled to room temperature, and is respectively washed 3 times by DMF and absolute ethyl alcohol, and is dried for 12 hours under the vacuum condition of 100 ℃, and the Zr-PA catalyst is obtained by grinding.

[ example 4 ] catalytic hydrogenation

(1) 0.2g of the coordination-type zirconium pyrogallol catalyst prepared in example 1 was weighed, placed in a 20mL polytetrafluoroethylene liner, and 5mL of isopropanol was added;

(2) weighing 1mmol of cyclohexanone, adding the cyclohexanone into the reaction system in the step (1), putting a polytetrafluoroethylene lining into a stainless steel reaction kettle, respectively putting the reaction kettle into oil bath pots at 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃, reacting for 10 hours under magnetic stirring, after the reaction is finished, cooling the reaction kettle to room temperature, separating solid from liquid by using a centrifugal machine, and taking the reaction liquid of a liquid phase as a sample to be detected;

(3) and (3) using a pipette to pipette 50. mu.L of the reaction solution obtained in the step (2), and measuring the yield of cyclohexanol by using a liquid chromatograph.

As a result, as shown in FIG. 1, when the reaction temperature was 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 150 ℃, the yields of cyclohexanol were 84.5%, 86.7%, 89.2%, 92.8% and 86.5%, respectively.

[ example 5 ] catalytic hydrogenation

(1) 0.2g of the coordination-type zirconium pyrogallol catalyst prepared in example 1 was weighed, placed in a 20mL polytetrafluoroethylene liner, and 5mL of isopropanol was added;

(2) weighing 1mmol of cyclohexanone, adding the cyclohexanone into the reaction system in the step (1), placing a polytetrafluoroethylene lining into a stainless steel reaction kettle, respectively placing the reaction kettles into oil bath kettles at 140 ℃, respectively reacting for 8h, 9h, 10h and 11h under magnetic stirring, after the reaction kettles are cooled to room temperature, separating solid from liquid by using a centrifugal machine, and taking liquid-phase reaction liquid as a sample to be detected;

(3) and (3) removing 50 mu L of the reaction liquid in the step (2) by using a liquid removing gun, and measuring the yield of the cyclohexanol by using a gas chromatograph.

According to the measurement, as shown in FIG. 2, when the reaction time is 8h, 9h, 10h and 11h, respectively, the yield of cyclohexanol is 85.6%, 82.8%, 92.8% and 82.3%, respectively.

[ example 6 ] catalytic hydrogenation

(1) 0.05g, 0.1g, 0.15g, 0.2g and 0.25g of the coordination type zirconium pyrogallol catalyst prepared in example 1 are weighed and placed in a polytetrafluoroethylene inner liner with 20mL, and 5mL of isopropanol is added;

(2) weighing 1mmol of cyclohexanone, respectively adding the cyclohexanone into the reaction system in the step (1), placing a polytetrafluoroethylene lining into a stainless steel reaction kettle, respectively placing the reaction kettles into oil bath kettles at 140 ℃, reacting for 10 hours under magnetic stirring, after the reaction is finished and the reaction kettles are cooled to room temperature, separating solid from liquid by using a centrifugal machine, and taking the reaction liquid of the liquid phase as a sample to be detected;

(3) and (3) using a liquid transfer gun to transfer 50 mu L of the reaction liquid in the step (2), and using a gas chromatograph to determine the yield of cyclohexanol.

As a result, as shown in FIG. 3, when the amounts of the catalysts were 0.05g, 0.1g, 0.15g, 0.2g and 0.25g, respectively, the yields of cyclohexanol were 55%, 72.8%, 76.4%, 92.8% and 84.4%, respectively.

[ example 7 ] catalytic hydrogenation

(1) Weighing 0.2g of coordination type zirconium pyrogallol catalyst prepared in example 1, placing the coordination type zirconium pyrogallol catalyst in a polytetrafluoroethylene lining with 20mL, and respectively adding solvents of methanol, ethanol, cyclohexanol, n-butanol, isobutanol and tert-butanol with the addition amount of 5 mL;

(2) respectively weighing 0.1mmol of cyclohexanone, adding the cyclohexanone into the reaction system in the step (1), placing a polytetrafluoroethylene lining into a stainless steel reaction kettle, placing the reaction kettle into an oil bath kettle at 140 ℃, reacting for 10 hours under magnetic stirring, after the reaction is finished, cooling the reaction kettle to room temperature, separating solid from liquid by using a centrifugal machine, and taking the reaction liquid of a liquid phase as a sample to be detected;

(3) and (3) using a liquid transfer gun to transfer 50 mu L of the reaction liquid in the step (2), and using a gas chromatograph to determine the yield of cyclohexanol.

As a result, as shown in Table 1, when the reaction solvent was methanol, ethanol, n-pentanol, 2-butanol, n-butanol, isobutanol, t-butanol, and isopropanol, the yields of cyclohexanol were 2.4%, 8.2%, 13.5%, 60.2%, 41.1%, 9.8%, 0.08%, and 92.8%, respectively.

TABLE 1 yield of cyclohexanol under different solvents

[ example 8 ] catalytic hydrogenation

(1) 0.2g of the coordination-type zirconium pyrogallol catalyst prepared in example 1, 2 or 3 was weighed, placed in a 20mL polytetrafluoroethylene liner, and 5mL of isopropanol was added;

(2) respectively weighing 1mmol of cyclohexanone, adding the cyclohexanone into the reaction system in the step (1), placing a polytetrafluoroethylene lining into a stainless steel reaction kettle, placing the reaction kettle into an oil bath kettle at 140 ℃, reacting for 10 hours under magnetic stirring, separating solid from liquid by using a centrifugal machine after the reaction kettle is cooled to room temperature, and taking the reaction liquid of the liquid phase as a sample to be detected;

(3) and (3) using a pipette to pipette 50. mu.L of the reaction solution obtained in the step (2), and measuring the yield of cyclohexanol by using a liquid chromatograph.

As a result, as shown in fig. 1, when the catalysts prepared in examples 1, 2 and 3 were used to catalyze the reaction, the yields of cyclohexanol were 92.8%, 80.4% and 83.6%, respectively.

[ example 9 ] catalytic hydrogenation