CN110787811B - Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof - Google Patents
Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof Download PDFInfo
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Abstract
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 prepared2O8 2‑/ZrO2The solid super acidic catalyst has good catalytic activity and high product selectivity.
Description
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 superacid 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 acid is more 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 superacid catalyst.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying 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, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
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 preparation method of the solid super acidic catalyst is simple, and the solid super acidic catalyst containing S is prepared by only dipping zirconium hydroxide into the ammonium persulfate aqueous solution and filtering to obtain a filter cake, wherein the filter cake contains the zirconium hydroxide adsorbing the ammonium persulfate, drying and roasting the filter cake to activate the catalyst, and finally obtaining the S-containing catalyst2O8 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 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 compound which is prepared by the preparation method of the glycerol cyclohexanone ketal compound 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.
Example 1
A preparation method of a solid super acidic catalyst comprises the following steps:
weighing 24g of ZrOCl2·8H2ZrOCl with the mass fraction of 10% is prepared by dissolving O in 240mL of distilled water2And (3) slowly dripping ammonia water into the solution under the condition of uniform stirring, adjusting the pH value to 10, stopping adding the ammonia water to obtain a white precipitate, standing and aging the precipitate at room temperature for 24 hours, carrying out suction filtration, washing the precipitate with deionized water until no chloride ions exist (no white precipitate is detected by using 0.1mol/L silver nitrate), drying the precipitate in a forced air drying oven at 120 ℃, taking out and grinding the precipitate to obtain the zirconium hydroxide.
6g of zirconium hydroxide was immersed in 0.5 mol/L100 mL (NH4)2S2O8The solution is put for 24 hours, then the solution is filtered to obtain a filter cake, the filter cake is dried for 12 hours at the temperature of 100 ℃, and then the filter cake is roasted for 4 hours at the temperature of 600 ℃ in a muffle furnace to obtain S2O8 2-/ZrO2Solid super acidic catalyst.
A preparation method of a glycerol cyclohexanone ketal material comprises the following steps:
10mL of cyclohexanone, 10mL of glycerol and 10mL of cyclohexane were added to a 100mL three-necked flask equipped with a thermometer, a reflux condenser and a water separator, and 0.2g of the S prepared above was added thereto after heating to a reflux temperature of 92 ℃2O8 2-/ZrO2And reacting for 1h, pouring out reaction liquid, carrying out suction filtration to remove the catalyst, and then carrying out reduced pressure distillation to obtain a colorless transparent product glycerol cyclohexanone ketal.
Example 2
A method for preparing a solid super acidic catalyst was substantially the same as in example 1, except that 16g of zirconium hydroxide was impregnated with 0.5mol/L (NH4)2S2O850mL of solution for 24 h.
Example 3
A method for preparing a solid super acidic catalyst is substantially the same as in example 1, except that 1.0mol/L (NH4) is selected as the catalyst2S2O8And (3) solution.
Comparative example 1
A method of preparing a solid superacid catalyst substantially the same as in example 1, except that 6g of zirconium hydroxide was immersed in 1 mol/L50 mL of sulfuric acid solution for 24 hours.
Comparative example 2
A method of preparing a solid super acidic catalyst was substantially the same as in example 1 except that 6g of zirconium hydroxide was immersed in 1mol/L of 50mL of nitric acid solution for 24 hours.
Comparative example 3
A method for preparing a solid super acidic catalyst was substantially the same as in example 1 except that 6g of zirconium hydroxide was immersed in 1mol/L of 50mL of phosphoric acid solution for 24 hours.
Comparative example 4
A method for preparing a solid super acidic catalyst was substantially the same as in example 1 except that the calcination temperature was 550 ℃ in the steps of drying and calcining the cake.
Comparative example 5
A method for preparing a solid super acidic catalyst was substantially the same as in example 1 except that the calcination temperature was 700 ℃ in the steps of drying and calcining the cake.
Results of the experiment
Index measurement
SP-6890 type gas chromatograph, data acquisition and processing system: an N2000 chromatography workstation; a FID detector; the temperature of the sample injector and the detector is 280 ℃; the sample injection amount is 0.2 mu L; SGHK-500 type hydrogen, air generators; carrier gas N2The flow rate of (2) is 20 mL/min; temperature programming: the initial temperature was 60 ℃ and the temperature was raised to 240 ℃ at a rate of 20 ℃/min.
Dissolving 1mL of reaction solution by absolute ethyl alcohol to a constant volume of 10mL, taking 1mL of the ethanol solution, fixing the volume by cyclohexane to 10mL, and carrying out quantitative analysis by adopting GC (GC startup sequence, namely firstly starting nitrogen, then starting a GC power supply, waiting for temperature rise, starting hydrogen and air for ignition, finally starting software, checking a base line, preparing a sample to be measured, and vice versa). The selectivity of the product a is characterized by the percentage of the gas chromatogram peak area of the 2-hydroxymethyl-1, 4-dioxaspiro [4,5] decane (product a) to the total gas chromatogram peak area of the product, and the conversion rate of cyclohexanone and the yield of the product are calculated.
The conversion of cyclohexanone is calculated as:
x ═ a-a 1/a × 100% formula (1.1)
Wherein: X-Cyclohexanone conversion;
a-the peak area of cyclohexanone in a gas chromatogram before reaction;
a1-peak area of cyclohexanone in gas chromatogram after reaction;
the selectivity of the target product is:
s ═ a2/(a2+ A3) × 100% formula (1.2)
In formula (1.2): s-selectivity of the desired product, 2-hydroxymethyl-1, 4-dioxaspiro [4,5] decane;
a2-chromatographic peak area of product a 2-hydroxymethyl-1, 4-dioxaspiro [4,5] decane;
a3-chromatographic peak area of product b 3-hydroxy-1, 5-dioxaspiro [5,5] undecane;
yield of the target product:
y is X S type (1.3)
The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the conversion of cyclohexanone, the selectivity of product and the yield of product were better in each example group than in the comparative example group. Among them, the effect in example 1 is the best. Further, with respect to S obtained in example 12O8 2-/ZrO2The surface of the solid super acidic catalyst was scanned by an electron microscope, and S is shown in FIG. 12O8 2-/ZrO2The surface of the solid super acidic catalyst is a stable tetragonal phase, and the morphology regularity is good.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the glycerol cyclohexanone ketal is characterized by comprising the following steps:
mixing cyclohexanone, glycerol, cyclohexane and a solid superacid catalyst, and reacting under ketal reaction conditions to obtain a glycerol cyclohexanone ketal compound;
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.
2. The preparation method according to claim 1, 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.
3. The method according to claim 1, wherein the volume ratio of cyclohexanone to glycerol to cyclohexane is (8-12) to (8-12).
4. The method according to any one of claims 1 to 3, wherein the zirconium hydroxide is prepared by: 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.
5. The method according to claim 4, wherein the aqueous solution of a zirconium salt is an aqueous solution of zirconium oxychloride having a mass fraction of 5% to 15%.
6. The method according to claim 4, wherein 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.
7. The preparation method according to any one of claims 1 to 3 and 5 to 6, 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 the filter cake is obtained by suction filtration.
8. The preparation method according to any one of claims 1 to 3 and 5 to 6, wherein in the step of drying and roasting the filter cake, the roasting temperature is 580 ℃ to 700 ℃, and the roasting time is 3h to 5 h.
9. The preparation method according to any one of claims 1 to 3 and 5 to 6, wherein in the step of drying and roasting the filter cake to obtain the solid super acidic catalyst, the drying temperature is 80 ℃ to 120 ℃ and the drying time is 10h to 14 h.
10. The production method according to any one of claims 1 to 3 and 5 to 6, wherein the particle diameter of the zirconium hydroxide is 8 μm to 20 μm.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105817228A (en) * | 2016-04-15 | 2016-08-03 | 黄山学院 | Method for preparing cyclohexanone glycol ketal compounds by directly using fly ash as catalyst |
CN106000463A (en) * | 2016-05-30 | 2016-10-12 | 河南工业大学 | Preparation method and application of immobilized cesium phosphotungstate catalyst |
CN106540753A (en) * | 2016-10-25 | 2017-03-29 | 济南大学 | A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction |
CN106669838A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Supported heteropolyacid salt catalyst and application thereof to preparation of acetals(ketals) perfumes |
-
2019
- 2019-11-11 CN CN201911096533.3A patent/CN110787811B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105817228A (en) * | 2016-04-15 | 2016-08-03 | 黄山学院 | Method for preparing cyclohexanone glycol ketal compounds by directly using fly ash as catalyst |
CN106000463A (en) * | 2016-05-30 | 2016-10-12 | 河南工业大学 | Preparation method and application of immobilized cesium phosphotungstate catalyst |
CN106540753A (en) * | 2016-10-25 | 2017-03-29 | 济南大学 | A kind of modified solid catalyst containing phosphotungstic acid for Ketohexamethylene condensation reaction |
CN106669838A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Supported heteropolyacid salt catalyst and application thereof to preparation of acetals(ketals) perfumes |
Non-Patent Citations (2)
Title |
---|
"固体超强酸S2O82-/ZrO2催化合成硬脂酸月桂酯";张荷丽等;《精细石油化工进展》;20011231;第4-6页 * |
"固体超强酸SO42-/ZrO2催化合成环己酮甘油缩酮";尚倩倩等;《东南大学学报》;20111231;第140-144页 * |
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