A kind of aromatic alcohol and catalytic hydrogenation preparation method and application

Abstract

The present application belongs to the field of disinfection technology, and in particular, relates to a flavor alcohol and a catalytic hydrogenation preparation method and application; the flavor alcohol catalytic hydrogenation preparation method provided by the present application adopts a Pd / Fe2O3 single-atom catalyst to catalytically hydrogenate a flavor substrate, so that the product flavor alcohol has a fresh aroma. At the same time, due to the good catalytic performance of the Pd / Fe2O3 single-atom catalyst, the conversion rate of the flavor substrate is high, the selectivity of the product flavor is high, and the flavor alcohol prepared by catalytic hydrogenation is of high quality. It can be further configured into daily chemicals such as antipyretic patches, air fresheners, and hand sanitizers, thereby solving the technical problem of low quality of flavor alcohol prepared by catalytic hydrogenation in the prior art.

Description

Technical Field

[0001] The present application belongs to the field of disinfection technology, and in particular relates to a method for preparing flavored alcohol and catalytic hydrogenation and its application. Background Art

[0002] With the improvement of living standards, people have begun to use daily disinfectant chemicals to disinfect items they come into contact with. Disinfectant alcohol has a good bactericidal effect and is easy to clean. It is a widely used daily disinfectant chemical. Disinfectant alcohol contains a high content of ethanol, and the volatile odor of ethanol is relatively pungent, which will cause discomfort to most people and affect its use in daily disinfection.

[0003] Adding fragrance ingredients to disinfectant alcohol to give it a fragrance to cover up its pungent smell has become a solution. There are many scented disinfectant alcohols on the market. They usually add corresponding fragrances to ordinary disinfectant alcohol to make the disinfectant alcohol have a floral or fruity aroma; leaf alcohol, scientifically known as cis-3-hexen-1-ol, is a colorless liquid with a strong fragrance of green tender leaves. The aroma is fresh, rich and natural. It is an indispensable flavoring substance in the production of flavors and is easily soluble in alcohol solvents such as ethanol. Just add a small amount of leaf alcohol to ethanol to get a disinfectant alcohol with a significant grass aroma.

[0004] The method of adding flavor ingredients to disinfectant alcohol is to react the flavor substrate with disinfectant alcohol, and use a catalyst to catalyze hydrogenation to prepare the flavor disinfectant alcohol; however, the Lindlar catalyst that is more commonly used in the industry at this stage has the problem of Pb loss, and the catalytic performance and stability of the catalyst are not high, resulting in a large amount of lead ion residues in the flavor disinfectant alcohol product, which is not conducive to the purification of subsequent products, and the quality of the flavor alcohol is low; while the Pd / C, Pt / C and other catalysts on the market have the defects of insufficient selectivity and slow reaction rate. The catalytic hydrogenation of flavor disinfectant alcohol using Pd / C, Pt / C and other catalysts is slow, the conversion rate is low, and there are many by-products, which reduces the quality of the flavor disinfectant alcohol and makes it difficult to meet the current national standard requirements for alcohol disinfectants. Summary of the invention

[0005] In view of this, the present application provides a flavor alcohol and a catalytic hydrogenation preparation method and application, which are used to solve the technical problem of low quality of flavor alcohol prepared by catalytic hydrogenation in the prior art.

[0006] The first aspect of the present application provides a method for preparing aromatic alcohol by catalytic hydrogenation, comprising the steps of:

[0007] Step S1, mixing an alcohol aqueous solution, a fragrance substrate and a Pd / Fe2O3 single-atom catalyst to obtain a solution to be reacted;

[0008] Step S2: in a hydrogen atmosphere, subjecting the solution to be reacted to a catalytic hydrogenation reaction to obtain aromatic alcohol.

[0009] Preferably, in step S1, the volume ratio of the alcohol aqueous solution to the fragrance substrate is 100:0.01-20.

[0010] Preferably, in step S1, the volume mass ratio of the fragrance substrate and the Pd / Fe2O3 single atom catalyst is 1 mL: 0.1-100 mg.

[0011] Preferably, in step S1, the alcohol aqueous solution is selected from ethanol aqueous solution and / or isopropanol aqueous solution.

[0012] Preferably, the volume ratio of alcohol to water in the alcohol-water solution is 1 to 20:1.

[0013] It should be noted that the flavor alcohol provided in the present application can be configured with components of different contents as needed. For example, to enhance the flavor, the amount of the flavor substrate can be increased. To increase the rate of the catalytic hydrogenation reaction, the addition of the Pd / Fe2O3 single-atom catalyst can be considered. To configure different disinfection daily necessities, the use of alcohol solutions and changing the ratio of alcohol to water can be considered.

[0014] Preferably, in step S1, the fragrance substrate is selected from 3-hexyn-1-ol and / or 3,7-dimethyl-6-octen-1-ynyl-3-ol.

[0015] It should be noted that the flavored alcohol provided in the present application can be prepared using different flavor substrates as needed, giving the flavored alcohol product different flavors.

[0016] Preferably, in step S1, the preparation method of the Pd / Fe2O3 single-atom catalyst comprises: immersing the Fe2O3 carrier in an aqueous solution of a Pd metal salt, and sequentially evaporating, drying, and calcining to obtain the Pd / Fe2O3 single-atom catalyst.

[0017] Preferably, in step S2, the reaction temperature is 20-100°C, the reaction time is 1-360 min, and the pressure is 0.1-10 MPa.

[0018] Preferably, after step S2, the method further includes step S3, filtering.

[0019] The second aspect of the present application provides a flavored alcohol prepared by the above-mentioned catalytic hydrogenation preparation method.

[0020] The third aspect of the present application provides the use of the flavor alcohol prepared by the above-mentioned catalytic hydrogenation preparation method in daily chemical products.

[0021] Preferably, the daily chemicals include at least one of a fever-reducing patch, an air freshener, and a hand sanitizer.

[0022] In summary, a flavor alcohol and a catalytic hydrogenation preparation method and application are disclosed. The flavor alcohol catalytic hydrogenation preparation method provided in the present application is to first mix an alcohol aqueous solution, a flavor substrate and a Pd / Fe2O3 single-atom catalyst and then carry out a catalytic hydrogenation reaction. During the reaction, the Pd / Fe2O3 single-atom catalyst catalytically hydrogenates the alkynyl groups in the flavor substrate to form olefin bonds to obtain a flavor with a fresh fragrance, which masks the pungent smell of alcohol aqueous solutions such as ethanol and forms flavor alcohol; and the Pd / Fe2O3 single-atom catalyst has good catalytic performance for the flavor substrate, the conversion rate of the flavor substrate is high, the product flavor selectivity is good, and the quality of the flavor alcohol is significantly improved, thereby solving the technical problem of low quality of flavor alcohol prepared by catalytic hydrogenation in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 This is a schematic diagram of the process of preparing aromatic alcohol by catalytic hydrogenation of Pd / Fe2O3 single atom catalyst and traditional Lindlar catalyst in the embodiment of the present application;

[0025] Figure 2 This is a reaction principle diagram of preparing 3-hexene-1-ol by catalytic hydrogenation of Pd / Fe2O3 single atom catalyst in an embodiment of the present application;

[0026] Figure 3 A diagram of the preparation method and equipment provided in Example 2 of the present application, a diagram of the preparation product, the aroma alcohol, and a schematic diagram of daily use; Figure 3 a is the preparation instrument, Figure 3 b is the aroma alcohol diagram, Figure 3 c is a daily use diagram;

[0027] Figure 4 This is the chromatogram of 3-hexen-1-ol in anhydrous ethanol in Example 3 of the present application;

[0028] Figure 5 This is a chromatogram of the fragrance product prepared by the preparation method provided in Example 2 of the present application. DETAILED DESCRIPTION

[0029] The present application provides a flavor alcohol and a catalytic hydrogenation preparation method and application, which are used to solve the technical problem of low quality of flavor alcohol prepared by catalytic hydrogenation in the prior art.

[0030] The technical solution of the present application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0031] Example 1

[0032] In view of the defects of the current catalytic hydrogenation for preparing flavor alcohol, Example 1 of the present application provides a method for preparing flavor alcohol by catalytic hydrogenation, which comprises the steps of preparing a solution to be reacted and the steps of catalytic hydrogenation reaction.

[0033] The step of preparing the reaction solution includes: weighing 100 mg of Pd / Fe2O3 single atom catalyst, measuring 1 mL of 3-hexyn-1-ol flavor substrate, 75 mL of ethanol and 25 mL of water in an alcohol aqueous solution in a 300 mL high pressure reactor to obtain the reaction solution.

[0034] The steps of the catalytic hydrogenation reaction include: charging hydrogen into a reactor five times to exclude air, then introducing hydrogen to make the pressure of the reactor reach 1MPa, controlling the reaction temperature to 50°C, and reacting for 120 minutes to prepare aromatic alcohol containing cis-3-hexene-1-ol.

[0035] In the method for preparing aromatic alcohol by catalytic hydrogenation, the aromatic alcohol can be filtered after the reaction is completed in order to reuse the Pd / Fe2O3 single-atom catalyst.

[0036] In the preparation method of aromatic alcohol catalytic hydrogenation, the preparation method of the Pd / Fe2O3 single-atom catalyst used is an existing preparation method, and the preparation method includes: using a ready-made Fe2O3 carrier for impregnation loading, loading Pd onto Fe2O3 by impregnation, drying and grinding the impregnated solid, and then calcining to obtain the Fe2O3 single-atom catalyst. Specifically, the Fe2O3 carrier is added to a beaker, an appropriate amount of deionized water is added, and an aqueous solution of a metal salt of Pd is transferred into the beaker as an impregnation liquid, and the beaker is placed in a water bath to evaporate the solvent water. After the solvent is evaporated, the catalyst is transferred to a porcelain boat for drying, and then placed in a muffle furnace for calcination, and the Fe2O3 single-atom catalyst is obtained after calcination.

[0037] Example 2

[0038] The embodiment of the present application provides another method for preparing aromatic alcohol by catalytic hydrogenation. The difference between the preparation method and Example 1 is that the reaction kettle is replaced, the Pd / Fe2O3 single atom catalyst, 3-hexyn-1-ol and alcohol aqueous solution are placed in a crimp bottle for reaction, and a hydrogen balloon is used as a hydrogen source for reaction. During the reaction, the reaction temperature is 50°C, the reaction time is 120 min, and stirring is carried out at the same time, and the stirring speed is 500 r / min.

[0039] Example 3

[0040] The embodiment of the present application provides another method for preparing flavor alcohol by catalytic hydrogenation. The difference between the preparation method and the embodiment 1 is that the ratio of water to alcohol solution in the alcohol aqueous solution is adjusted, and the alcohol aqueous solution includes 60 mL of ethanol and 40 mL of water. It should be noted that flavor substrates such as 3-hexyn-1-ol are easily soluble in alcohol solutions. The present application can adjust the amount of alcohol in the flavor alcohol as needed, thereby configuring flavor alcohols with different alcohol concentrations.

[0041] Example 4

[0042] The embodiment of the present application provides another method for preparing flavor alcohol by catalytic hydrogenation. The difference between the preparation method and the embodiment 1 is that the flavor substrate is replaced, and the flavor substrate is 3,7-dimethyl-6-octen-1-alkynyl-3-ol. It should be noted that the flavor product 3,7-dimethyl-6-octen-1-alkynyl-3-ol prepared by catalytic hydrogenation of 3,7-dimethyl-6-octen-1-alkynyl-3-ol has the aroma of lily of the valley, which is different from 3-hexen-1-ol. The present application can adjust the type of flavor in the flavor alcohol as needed, so as to configure flavor alcohols with different aromas.

[0043] Example 5

[0044] The embodiment of the present application provides a daily chemical product, which is prepared by the fragrance alcohol described in Example 1; since the volatility of the fragrance in the prepared daily chemical product is lower than that of the alcohol solvent, the fragrance can be used as an indicator. When the fragrance is not volatile, it can be determined that the alcohol solvent has evaporated and new daily chemical products need to be replenished. The daily chemical product preparation process includes preparing a fever-reducing patch, an air freshener, and a hand sanitizer.

[0045] The process of preparing the antipyretic patch includes: preparing the antipyretic patch with scented alcohol and water. The antipyretic patch provided in the present application uses scented alcohol, so that in addition to the conventional physical cooling effect, the antipyretic patch also has the fragrance of leaves due to the addition of 3-hexen-1-ol, which can soothe the body and mind and give people a relaxed and pleasant feeling.

[0046] The process of preparing an air freshener includes: preparing an air freshener by mixing scented alcohol and water, solvents such as ethylene glycol, propylene glycol, and other fragrance extracts; the air freshener provided by the present application has the effect of disinfecting the air with conventional ethanol, and also has the fragrance of leaves in the air due to the addition of scented alcohol.

[0047] The process of preparing hand sanitizer includes: preparing hand sanitizer by mixing scented alcohol and water, solvents such as ethylene glycol, propylene glycol, and glycerin and other fragrance extracts; the hand sanitizer provided in the present application has the function of conventional ethanol disinfection and cleaning of hands, and also has the fragrance of leaves in the hands after disinfection and cleaning because of the addition of scented alcohol.

[0048] Experimental Example 1

[0049] Experimental Example 1 of the present application performs gas chromatography analysis on the flavor alcohol prepared in Example 2 to qualitatively and quantitatively analyze the flavor alcohol.

[0050] The chromatogram of the flavor alcohol prepared in Example 2 of the present application is as follows: Figure 5 As shown, and Figure 4 It can be seen from the chromatogram of 3-hexen-1-ol in anhydrous ethanol that the flavor alcohol prepared in Example 2 of the present application includes 3-hexen-1-ol. At the same time, since an alcohol aqueous solution is used as a solvent, the flavor alcohol also includes water and ethanol, and the conversion rate of the flavor substrate 3-hexyn-1-ol is greater than 99%, and the selectivity of leaf alcohol is greater than 98%; this shows that the reaction of catalytic hydrogenation of 3-hexyn-1-ol to prepare leaf alcohol in the present application has good catalytic performance, high catalytic reaction yield and good selectivity, and at the same time the catalyst is a single atom catalyst, which has the advantages of avoiding lead ion residues, high selectivity and fast reaction rate compared to the commonly used Lindlar catalyst and commercial Pd / C catalyst on the market.

[0051] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing aromatic alcohol by catalytic hydrogenation, characterized in that: Includes steps: Step S1, mixing an alcohol aqueous solution, a fragrance substrate and a Pd / Fe2O3 single-atom catalyst to obtain a solution to be reacted; Step S2, in a hydrogen atmosphere, subjecting the solution to be reacted to a catalytic hydrogenation reaction to obtain aromatic alcohol; In step S1, the fragrance substrate is selected from 3-hexyn-1-ol and / or 3,7-dimethyl-6-octen-1-ynyl-3-ol.

2. A method for preparing aromatic alcohol by catalytic hydrogenation according to claim 1, characterized in that: In step S1, the volume ratio of the alcohol aqueous solution to the fragrance substrate is 100:0.01-20.

3. A method for preparing aromatic alcohol by catalytic hydrogenation according to claim 1, characterized in that: In step S1, the volume mass ratio of the fragrance substrate and the Pd / Fe2O3 single atom catalyst is 1 mL: 0.1-100 mg.

4. A method for preparing aromatic alcohol by catalytic hydrogenation according to claim 1, characterized in that: In step S1, the alcohol aqueous solution is selected from ethanol aqueous solution and / or isopropanol aqueous solution.

5. A method for preparing aromatic alcohol by catalytic hydrogenation according to claim 1, characterized in that: In step S2, the reaction temperature is 20-100°C, the reaction time is 1-360 min, and the pressure is 0.1-10 MPa.

6. A method for preparing aromatic alcohol by catalytic hydrogenation according to claim 1, characterized in that: After step S2, the method further includes step S3: filtering.

7. A flavor alcohol, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the aromatic alcohol according to claim 7 in the preparation of daily chemicals.

9. The use according to claim 8, characterized in that: The daily chemicals are selected from air fresheners or hand sanitizers.

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