阅读说明：本技术 固体超强酸及制备方法、甘油环己酮缩酮物及制备方法 (Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof ) 是由 李万伟 张再兴 胡扬剑 于 2019-11-11 设计创作，主要内容包括：本发明涉及一种固体超强酸及制备方法、甘油环己酮缩酮物及制备方法。其中,固体超强酸催化剂的制备方法包括如下步骤：将氢氧化锆浸渍于0.4mol/L-0.6mol/L的过硫酸铵水溶液中,过滤得到滤饼；对所述滤饼进行干燥、焙烧处理即得固体超强酸催化剂,其中,所述氢氧化锆与所述过硫酸铵水溶液的质量体积比为(0.114-16.6):1g/mL。上述固体超强酸催化剂制备方法简单,只需将氢氧化锆与过硫酸铵水溶液按上述比例混合、过滤得到滤饼,再对所述滤饼干燥、焙烧处理使催化剂活化,最终制得含S<Sub>2</Sub>O<Sub>8</Sub><Sup>2-</Sup>/ZrO<Sub>2</Sub>的固体超强酸催化剂的催化活性好且产物选择性高。(The invention relates to a solid super acid and a preparation method thereof, and a glycerol cyclohexanone ketal and a preparation method thereof. The preparation method of the solid super acidic catalyst comprises the following steps: soaking zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution, and filtering to obtain a filter cake; and drying and roasting the filter cake to obtain the solid super acidic catalyst, wherein the mass-volume ratio of the zirconium hydroxide to the ammonium persulfate aqueous solution is (0.114-16.6):1 g/mL. The preparation method of the solid super acidic catalyst is simple, and only the zirconium hydroxide and the ammonium persulfate aqueous solution are mixed according to the proportion and filtered to obtain a filter cake, and then the filter cake is dried and roasted to activate the catalyst, so that the S-containing catalyst is finally prepared 2 O 8 2‑ /ZrO 2 The solid super acidic catalyst has good catalytic activity and high product selectivity.)

1. The preparation method of the solid super acidic catalyst is characterized by comprising the following steps:

soaking zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution, and filtering to obtain a filter cake; and drying and roasting the filter cake to obtain the solid super acidic catalyst, wherein the mass-volume ratio of the zirconium hydroxide to the ammonium persulfate aqueous solution is (0.114-16.6):1 g/mL.

2. The method for preparing a solid super acidic catalyst according to claim 1, wherein the zirconium hydroxide is prepared by the steps of: adding alkali liquor into a zirconium salt aqueous solution until the pH value is 9-11 to obtain a precipitate containing zirconium oxide, aging and filtering the precipitate containing zirconium oxide, and washing and drying collected solid components to obtain zirconium hydroxide.

3. The method for preparing a solid superacid catalyst according to claim 2, wherein the aqueous solution of a zirconium salt is an aqueous solution of zirconium oxychloride having a mass fraction of 5% to 15%.

4. The method for preparing a solid super acidic catalyst according to claim 2, wherein the washing is stopped when the collected solid component is washed until there is no residual chloride ion in the washing solution in the steps of washing and drying the collected solid component.

5. The method for preparing a solid superacid catalyst according to any one of claims 1 to 4, wherein in the step of immersing zirconium hydroxide in 0.4mol/L to 0.6mol/L aqueous ammonium persulfate solution, zirconium hydroxide is immersed in 0.4mol/L to 0.6mol/L aqueous ammonium persulfate solution for 12h to 36h, and a filter cake is obtained by suction filtration.

6. The method for preparing a solid super acidic catalyst according to any one of claims 1 to 4, wherein in the step of drying and calcining the filter cake, the calcining temperature is 580 ℃ to 700 ℃ and the calcining time is 3h to 5 h.

7. A solid super acidic catalyst obtained by the method for preparing a solid super acidic catalyst according to any one of claims 1 to 6.

8. The preparation method of the glycerol cyclohexanone ketal is characterized by comprising the following steps:

mixing cyclohexanone, glycerol, cyclohexane and the solid super acidic catalyst of claim 7, and reacting under ketal reaction conditions to obtain glycerol cyclohexanone ketal.

9. The method for preparing the glycerol cyclohexanone ketal as described in claim 8, wherein the mass-to-volume ratio of the solid super acid catalyst to the mixed solution of cyclohexanone, glycerol and cyclohexane is (10-20):1 g/mL.

10. A glycerol cyclohexanone ketal as obtained by the method for preparing a glycerol cyclohexanone ketal as described in claim 8 or 9.

Technical Field

The invention relates to the field of solid acid catalysts, in particular to a solid super acid and a preparation method thereof, a glycerol cyclohexanone ketal and a preparation method thereof.

Background

At present, effective catalysts commonly used in industrial production are mainly concentrated sulfuric acid, phosphoric acid and hydrochloric acid, and the catalysts have the defects of more side reactions such as sulfonation, oxidation and the like, strong corrosivity, serious environmental pollution, generation of 'three wastes' which are difficult to treat in the production process and the like in the catalytic reaction process, so that the application of the catalysts is limited.

The solid super acid is a strongly acidic solid acid prepared by loading an active component with acidity on a metal oxide, and the surface acid strength of the solid super acid is greater than 100 percent of sulfuric acid. In the acid catalysis, the solid super acid overcomes the defects of poor catalytic activity, more side reactions, strong corrosivity and serious environmental pollution of a liquid acid catalyst, has high catalytic activity for isomerization, alkylation, dehydration, esterification and other reactions, and is generally regarded by people.

In the preparation process of the traditional solid acid catalyst, nitric acid, phosphoric acid, sulfuric acid and the like are mostly adopted as precipitating agents, but the prepared solid super acid catalyst has the defects of poor catalytic activity, low equilibrium conversion rate of reaction, poor product selectivity and the like.

Disclosure of Invention

Therefore, it is necessary to provide a solid super acidic catalyst capable of improving catalytic activity, a preparation method thereof, a glycerol cyclohexanone ketal compound and a preparation method thereof, aiming at the problem that the catalytic activity of the solid super acidic catalyst prepared by the conventional process is poor.

A preparation method of a solid super acidic catalyst comprises the following steps:

soaking zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution, and filtering to obtain a filter cake; and drying and roasting the filter cake to obtain the solid super acidic catalyst, wherein the mass-volume ratio of the zirconium hydroxide to the ammonium persulfate aqueous solution is (0.114-16.6):1 g/mL.

The preparation method of the solid super acidic catalyst is simple, and only zirconium hydroxide is needed to be dipped into the ammonium persulfate aqueous solution and filtered to obtain a filter cake, wherein the filter cake contains the zirconium hydroxide adsorbing the ammonium persulfate, and then the filter cake is dried and roasted to activate the catalyst, so that the S-containing catalyst is finally prepared₂O₈ ^2-/ZrO₂The solid super acidic catalyst of (1). Wherein the addition of ammonium persulfate brings S to the solid super acidic catalyst₂O₈ ^2-，S₂O₈ ^2-The catalyst has more super-strong acid sites and high crystallization degree, and compared with a solid super-strong acid catalyst prepared by mixing zirconium hydroxide and nitric acid or zirconium hydroxide and sulfuric acid, the solid super-strong acid catalyst has good catalytic activity and high product selectivity.

In one embodiment, the preparation steps of the zirconium hydroxide are as follows: adding alkali liquor into a zirconium salt aqueous solution until the pH value is 9-11 to obtain a precipitate containing zirconium oxide, aging and filtering the precipitate containing zirconium oxide, and washing and drying collected solid components to obtain zirconium hydroxide.

In one embodiment, the aqueous solution of zirconium salt is 5-15% by mass of an aqueous solution of zirconium oxychloride.

In one embodiment, in the step of washing and drying the collected solid component, the washing is stopped until there is no residual chloride ion in the washing liquid.

In one embodiment, in the step of immersing zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution, zirconium hydroxide is immersed in 0.4-0.6 mol/L ammonium persulfate aqueous solution for 12-36h, and the filter cake is obtained by suction filtration.

In one embodiment, in the step of drying and roasting the filter cake, the roasting temperature is 580-700 ℃, and the roasting time is 3-5 h.

The invention also provides a solid super acidic catalyst prepared by the preparation method of the solid super acidic catalyst in any embodiment of the invention.

The invention also provides a preparation method of the glycerol cyclohexanone ketal, which comprises the following steps:

cyclohexanone, glycerol, cyclohexane and the solid super acidic catalyst described in this example were mixed and reacted under ketal reaction conditions to obtain glycerol cyclohexanone ketal.

In one embodiment, the mass-to-volume ratio of the solid super acid catalyst to the mixed solution of cyclohexanone, glycerol and cyclohexane is (10-20):1 g/mL.

The invention also provides a glycerol cyclohexanone ketal material which is prepared by adopting the preparation method of the glycerol cyclohexanone ketal material in any embodiment of the invention.

Drawings

FIG. 1 shows S in embodiment 1 of the present invention₂O₈ ^2-/ZrO₂SEM image of solid super acidic catalyst.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The embodiment of the invention provides a preparation method of a solid super acidic catalyst, which comprises the following steps:

soaking zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution, and filtering to obtain a filter cake; and drying and roasting the filter cake to obtain the solid super acidic catalyst, wherein the mass-volume ratio of the zirconium hydroxide to the ammonium persulfate aqueous solution is (0.114-16.6):1 g/mL.

Specifically, in the step of dipping zirconium hydroxide in 0.4-0.6 mol/L ammonium persulfate aqueous solution and filtering to obtain filter cake, the zirconium hydroxide is dipped in 0.4-0.6 mol/L ammonium persulfate aqueous solution for 12-36h and filtered to obtain the filter cake. The suction filtration has the advantage of removing free water so as to avoid the formation of vapor pressure of water in the drying and roasting processes, which is unfavorable for preparing the catalyst. In addition, inactive components may be removed.

In one embodiment, the zirconium hydroxide can be prepared by the following steps: adding alkali liquor into a zirconium salt aqueous solution until the pH value is 9-11 to obtain white precipitate containing zirconium hydroxide, aging and filtering the precipitate containing zirconium hydroxide, collecting solid components, and then washing and drying to obtain the zirconium hydroxide. Further, the zirconium salt aqueous solution is a zirconium oxychloride aqueous solution with the mass fraction of 5% -15%. Furthermore, ammonia water is added dropwise, so that the obtained zirconium hydroxide is uniformly precipitated, the inner part of the zirconium hydroxide is in a hollow structure form of the zirconium oxychloride aqueous solution instead of the outer layer which forms the precipitate, and the subsequent drying and roasting processes are facilitated.

In this example, washing was stopped until no chloride ion remained in the washing solution. The purpose of removing the residual chloride ions is to reduce the adverse effect of chloride ions on the activity of the catalyst. Further, whether chloride ions remain or not is verified by adding silver nitrate into the washing solution.

In this embodiment, after the step of aging, filtering, washing, and drying the precipitate containing zirconium hydroxide to obtain zirconium hydroxide, grinding and sieving are further included to obtain zirconium hydroxide powder with a particle size of 8um to 20 um.

In one embodiment, the step of drying and roasting the filter cake to obtain the solid super acidic catalyst comprises the following steps: the drying temperature is 80-120 ℃, and the drying time is 10-14 h.

In one embodiment, the step of drying and roasting the filter cake to obtain the solid super acidic catalyst comprises the following steps: the roasting temperature is 550-700 ℃, and the roasting time is 3-5 h.

The invention also provides the solid super acidic catalyst prepared by any one of the preparation methods of the solid super acidic catalyst.

The above-mentioned fixingThe preparation method of the bulk super acidic catalyst is simple, and only zirconium hydroxide is needed to be dipped into the ammonium persulfate aqueous solution and filtered to obtain a filter cake, wherein the filter cake contains the zirconium hydroxide adsorbing the ammonium persulfate, and then the filter cake is dried and roasted to activate the catalyst, so that the S-containing catalyst is finally prepared₂O₈ ^2-/ZrO₂The solid super acidic catalyst of (1). Wherein the addition of ammonium persulfate brings S to the solid super acidic catalyst₂O₈ ^2-，S₂O₈ ^2-The catalyst has more super-strong acid sites and high crystallization degree, and compared with a solid super-strong acid catalyst prepared by mixing zirconium hydroxide and nitric acid or zirconium hydroxide and sulfuric acid, the solid super-strong acid catalyst has good catalytic activity and high product selectivity.

The invention also provides a preparation method of the glycerol cyclohexanone ketal, which comprises the following steps:

cyclohexanone, glycerol, cyclohexane and the solid super acidic catalyst according to an embodiment of the present invention are mixed and reacted under a ketal reaction condition to obtain a glycerol cyclohexanone ketal.

The specific reaction formula is as follows:

in one embodiment, the mass-to-volume ratio of the solid super acid catalyst to the mixed solution of cyclohexanone, glycerol and cyclohexane is (10-20):1 g/mL.

In one embodiment, cyclohexanone, glycerol and cyclohexane are uniformly mixed, heated, condensed and refluxed, then the solid super acidic catalyst provided by the invention is added to react to obtain a reaction solution, the solid super acidic catalyst in the reaction solution is removed, and a colorless and transparent product glycerol cyclohexanone ketal is obtained by distillation.

The catalyst is added after the temperature is raised from the view point of reaction kinetics in order to better utilize the activity of the catalyst and reduce the generation of byproducts.

In one embodiment, the solid super acidic catalyst is added for reaction when the condensation reflux is carried out to the reflux temperature of 90-95 ℃. Further, the condensing reflux is carried out in a spherical condensing tube.

In one embodiment, the volume ratio of the cyclohexanone to the glycerol to the cyclohexane is (8-12): (8-12).

In one embodiment, the step of distilling to obtain the glycerol cyclohexanone ketal is performed by vacuum distillation.

The invention also provides a glycerol cyclohexanone ketal material which is prepared by adopting the preparation method of the glycerol cyclohexanone ketal material in any embodiment of the invention.

The preparation of the glycerol cyclohexanone ketal is to adopt the solid super acid of the invention as a catalyst, and the obtained product has higher selectivity and yield.

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.