CN111777497A - Method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone - Google Patents
Method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone Download PDFInfo
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Abstract
The invention discloses a method for preparing 4-oxoisophorone by catalytic oxidation of β -isophorone, which adopts walnut shell based activated carbon (W-AC) loaded yttrium oxide-zirconium oxide-metal halide (M)mXn‑Y2O3‑ZrO2β -isophorone is oxidized with hydrogen peroxide in the presence of solvent, catalyst and cocatalyst to prepare 4-oxo-isophorone, the method has mild reaction conditions, simple process, high conversion rate of β -isophorone and product selectivity, and little environmental pollution, and can solve the problem that the catalyst is not recyclable.
Description
Technical Field
The invention belongs to the field of synthesis of organic intermediates, and particularly relates to a method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone.
Background
4-oxo-isophorone (KIP for short) is an important organic intermediate, can be used for preparing food flavoring agents and perfumes, and can also be used for synthesizing cosmetics. Furthermore, 4-oxoisophorone is also an important intermediate for the synthesis of vitamins and carotenoids.
There have been many known processes for the oxidation of beta-isophorone to 4-oxoisophorone for a long time.
In US4046813A a process for the preparation of 4-oxoisophorone by catalytic oxygen oxidation of beta-isophorone in the presence of pyridine using an acetylacetone complex of lead, vanadium, iron, cobalt, manganese, etc. as catalyst is described. Although the method has about 100 percent of conversion rate, the reaction process has conversion from beta-IP to alpha-IP and high polymerization byproducts, so the reaction selectivity is low.
The porphyrin or phthalocyanine complex of the transition metal can also be used as a catalyst to catalyze the reaction of preparing 4-oxo-isophorone by oxidizing beta-isophorone. For example, patent US4898985A discloses a process for preparing 4-oxoisophorone by oxidizing beta-isophorone with porphyrin or phthalocyanine complexes of iron, copper, manganese, cobalt as catalyst, triethylamine as organic base, and ethylene glycol dimethyl ether as solvent. Although the method has high yield, the preparation cost of the porphyrin or phthalocyanine complex catalyst is high, and the catalyst can be always easily damaged in the reaction. In addition, ethylene glycol dimethyl ether and triethylamine are dangerous under operating conditions, and thus are difficult to apply on a large scale.
In US6297404 and US6300521 a process for the preparation of 4-oxoisophorone by catalytic oxidation of beta-isophorone in the presence of tripropylamine and acetate salt with schiff base complex as catalyst and DMF or DMA as solvent is described. The greatest disadvantage of this method is that the reaction readily produces o-KIP as a vicinal oxidation by-product, which has similar physical properties to KIP and is therefore quite difficult to separate from the product. Patent CN1865210 discloses a method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with schiff base complex with arginine as main structure as catalyst, which has the problems of complex catalyst structure and difficult preparation, although the conversion rate and selectivity are high.
In addition, the transition metal complex is homogeneous as a catalyst in the reaction process, so that the catalyst is difficult to recycle after the reaction is finished, and difficulty is brought to the post-treatment process.
In conclusion, in the technology for preparing 4-oxoisophorone by oxidizing beta-isophorone in the prior patent publications, the defects of poor reaction selectivity, harsh process conditions, complex catalyst preparation, incapability of recycling and the like still exist.
Disclosure of Invention
The invention provides a method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone. The method has the advantages of mild reaction process, high conversion rate of beta-isophorone, high product selectivity and small environmental pollution, and the catalyst has the advantage of being recyclable, and the catalytic activity can be kept stable after repeated application.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone comprises the following steps: beta-isophorone reacts with hydrogen peroxide in the presence of solvent, catalyst and cocatalyst to obtain 4-oxo-isophorone.
The reaction equation is as follows:
the catalyst is walnut shell-based activated carbon (W-AC) loaded yttrium oxide-zirconium oxide-metal halide (M)mXn-Y2O3-ZrO2/W-AC)。
The walnut shell-based activated carbon is prepared from walnut shells serving as raw materials through activation, thermal cracking and the like. The prepared walnut shell-based activated carbon has the common characteristics of high specific surface area, complex pore structure and the like of the activated carbon, so that the walnut shell-based activated carbon is used as a catalyst carrier and is beneficial to the dispersion of active components, thereby promoting the contact of the active components of the catalyst and a substrate and avoiding the agglomeration of the active components. The loaded catalyst has good catalytic effect, high conversion rate and good selectivity. In addition, the walnut shells are used as raw materials to prepare the activated carbon, and the raw materials are environment-friendly and renewable and are more environment-friendly.
Walnut, also known as walnut and walnut, is a plant of the family juglandaceae. The Chinese herbs are mainly produced in North China, northwest China, southwest China, south China and east China, and in south China and west China. The walnut shell can be walnut shell without pulp.
The metal halide M of the inventionmXnIs one or more of transition metal chloride or bromide, such as one or more of lithium chloride, beryllium chloride, sodium chloride, magnesium chloride, potassium chloride, calcium chloride, rubidium chloride, strontium chloride, cesium chloride, barium chloride, lithium bromide, beryllium bromide, sodium bromide, magnesium bromide, potassium bromide, calcium bromide, rubidium bromide, strontium bromide, cesium bromide, and barium bromide, preferably one or more of magnesium chloride, magnesium bromide, calcium chloride, and calcium bromide, and more preferably magnesium chloride.
The catalyst comprises the following components: based on the mass portion, the weight percentage of the raw materials,
preferably, Y is2O3And ZrO2Is 0.5 to 2, preferably 1 to 1.5.
The cocatalyst is a phenolic compound, and comprises phenol with or without substituent or benzenediol with or without substituent, and specific examples include but are not limited to one or more of phenol, o-cresol, m-cresol, p-methylphenol, catechol, resorcinol, hydroquinone and the like; hydroquinone is preferred.
The phenolic compound is added to play a role in stabilizing free radicals. The method avoids the inactivation of a large amount of free radicals generated by the decomposition of the hydrogen peroxide, thereby improving the utilization rate of the hydrogen peroxide. Therefore, under the same reaction conditions, the addition of the cocatalyst further increases the reaction conversion rate. The hydroquinone is more beneficial to the stability of free radicals from the aspects of steric hindrance and electronic effect, so the conversion rate is improved more obviously.
In the invention, the mass ratio of the beta-isophorone to the catalyst is 1:0.01-0.05, preferably 1: 0.02-0.025.
In the invention, the mass ratio of the beta-isophorone to the cocatalyst is 1:0.02-0.1, preferably 1: 0.03-0.05.
In the present invention, the solvent is selected from one or more of acetone, acetonitrile, butanone, tetrahydrofuran and dichloromethane, preferably acetonitrile. The mass ratio of the beta-isophorone to the solvent is 1:0.5-2, preferably 1: 1-1.5.
In the invention, the molar weight ratio of the beta-isophorone to hydrogen peroxide is 1:2-3, preferably 1: 2.2-2.5.
In the invention, the concentration of the hydrogen peroxide is selected from 30-50 wt%, preferably 35-40 wt%.
In the invention, the temperature of the oxidation reaction is 10-50 ℃, preferably 20-30 ℃, and the time of the oxidation reaction is 5-20h, preferably 10-15 h.
Preparation of walnut shell-based activated carbon (W-AC) loaded yttrium oxide-zirconium oxide-metal halide (M)mXn-Y2O3-ZrO2/W-AC) process comprising the following steps:
(1) drying walnut shells, crushing, sieving with a sieve of 120-mesh and 160-mesh, adding an activating agent into the walnut shell powder, mixing and standing for 1-30h, preferably 10-20h, drying, pyrolyzing at high temperature, cooling to room temperature, washing to neutrality, drying, crushing, sieving with a sieve of 180-mesh and 200-mesh to obtain a carrier W-AC;
(2) nano Y2O3、ZrO2Adding carrier W-AC into water, stirring and mixing for 0.5-3 hr, preferably 1-2 hr, ultrasonic oscillating at frequency of 80-100Hz, 10-40 deg.C, preferably 20-30 deg.C for 1-5 hr, preferably 2-3 hr, drying, and grinding to obtain Y2O3-ZrO2/W-AC；
(3) Dispersing the product obtained in the step (2) in a metal halide water solution, stirring for 5-20h, preferably 10-15h at 40-80 ℃, preferably 50-60 ℃, and drying to obtain the catalyst.
In step (1) of the present invention, the activating agent is 10 to 60 wt% of H3PO4Aqueous solution, preferably 30-50 wt% of H3PO4An aqueous solution. The activating agent has the effects of enabling walnut shells to form more pore structures in the subsequent thermal cracking process, improving the number of surface active groups and facilitating the loading of active components of the catalyst.
In the step (1) of the invention, walnut shell powder and an activating agent (H) are used3PO4Mass of the aqueous solution) is 1:3-10, preferably 1: 5-8.
In the step (1) of the present invention, the high temperature pyrolysis temperature is 400-. Preferably, the high-temperature pyrolysis is carried out under the protection of an inert gas such as nitrogen.
In the step (2) of the present invention, Y2O3The mass ratio of the carrier W-AC is (1-20): 100, preferably (5-10): 100, respectively; ZrO (ZrO)2The mass ratio of the carrier W-AC is (1-20): 100, preferably (5-10): 100, respectively; preferably, Y is2O3And ZrO2Is 0.5 to 2, preferably 1 to 1.5.
In the step (3) of the present invention, the mass ratio of the metal halide to the carrier is (0.5-5): 100, preferably (1-3): 100.
the catalyst provided by the invention has the following beneficial effects:
(1) the W-AC carrier has a porous structure, and the metal oxide is loaded on the carrier, so that the dispersion area is increased, the agglomeration of the catalyst is effectively avoided, and the probability of contact and effective collision of catalyst molecules and a substrate is improved, thereby improving the utilization rate and catalytic activity of the catalyst. In addition, the carrier is prepared from walnut shells which are waste of agricultural products, namely walnuts, so that resources are effectively utilized, the cost is low, and the carrier is green and environment-friendly;
(2)Y2O3and ZrO2The combination of the two has the mutual promotion effect, and the effect is better than that of using any single oxide as the active component of the catalyst. The existence of the cocatalyst further activates the hydrogen peroxide, and improves the utilization rate of the oxidant, thereby improving the conversion rate of the substrate;
(3) the addition of the metal halide effectively inhibits the conversion of the beta-isophorone to the alpha-isophorone and the generation of polymers in the reaction process, and improves the product selectivity. Basic conditions are generally required for the conversion of beta-isophorone to alpha-isophorone and for the formation of multimers. The metal halide is used as Lewis acid, and can effectively inhibit the process.
Compared with the prior art, the method has the following outstanding effects: the hydrogen peroxide is used as an oxidant, so that the process is simple and the route is environment-friendly. The reaction condition is mild; the conversion rate of the raw material beta-isophorone can reach more than 99.5%, and the yield of 4-oxoisophorone can reach more than 92%; the catalyst is cheap and easy to obtain, the preparation process is simple, the catalyst can be recycled, and the catalytic activity can be kept stable after repeated application.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
Gas chromatography conditions: the chromatographic type is as follows: agilent WAX 1701.42249; carrier gas: high-purity nitrogen; nitrogen flow rate: 64.5 mL/min; vaporization chamber temperature: 280 ℃; split-flow sample introduction, split-flow ratio: 1: 40; sample introduction amount: 0.2 mu L; the column flow rate was 1.5 mL/min; column temperature: the temperature is programmed to 100 ℃ at the initial temperature and kept for 2 min. Then raising the temperature to 230 ℃ at the speed of 15 ℃/min, and keeping the temperature for 15 min; detector temperature: 300 ℃; and (4) selecting an external standard method for quantification.
XPS test instrument: escalab 250Xi photoelectron spectrometer.
The walnut shells used in the invention are purchased from Shijiazhuang Yuanjinghe products Co.
Example 1
Drying walnut shell at 120 deg.C to constant weight, pulverizing, and sieving with 160 mesh sieve. The activator adopts H with the mass fraction of 40%3PO4Adding 300g of activating agent into 50g of walnut shell powder, mixing and standing for 20h, drying the mixture at 120 ℃, and then putting the mixture into a tube furnace for pyrolysis at 550 ℃ for 1h (under the protection of nitrogen). After cooling to room temperature, the activated carbon is taken out and washed to be neutral. Drying the activated carbon, cooling, crushing, sieving with a 200-mesh sieve, and storing in a dryer for later use.
Weighing 4g of nano-Y2O34g of nano ZrO2And 50g of carrier W-AC are ground in an agate mortar for 30min, transferred into a beaker, added with 300g of pure water and stirred for 1h, so that the active component and the carrier are fully mixed. And (3) carrying out ultrasonic oscillation on the stirred mixed sample for 2 hours at the frequency of 100Hz and the temperature of 25 ℃ so as to further and fully mix the sample. And (5) putting the sample into a constant temperature box for drying. Taking out and grinding to obtain Y2O3-ZrO2/W-AC。
MmXn-Y2O3-ZrO2Preparation of/W-AC: all of the obtained Y2O3-ZrO2the/W-AC is dispersed in 100g of water and dissolved in 1.2g of magnesium chloride aqueous solution, and ultrasonic treatment is carried out for 1 h. Followed by vigorous stirring at 60 ℃ for 10 h. Stopping stirring, standing, discarding supernatant, centrifuging, and drying precipitate to obtain MgCl2-Y2O3-ZrO2The catalyst was a/W-AC catalyst (denoted as catalyst a). According to XPS test of the content of Y, Zr and Mg elements, the catalyst a is prepared from the following components: y is2O3：ZrO2：MgCl2100.0:8.0:8.0:2.1 (mass ratio)
Example 2
Adjusting W-AC Carrier, Y2O3、ZrO2、MgCl2Catalyst b was prepared in the amounts of 50g, 10g and 0.32g, respectively, except that the same conditions as in example 1 were applied. XPS analysis of its composition as a W-AC vector：Y2O3：ZrO2：MgCl2100.20.0:20.0:0.5 (mass ratio).
Example 3
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1382g of beta-isophorone, 1658g of acetonitrile, 34.55g of catalyst a and 41.46g of hydroquinone are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 30 ℃, dropwise adding 2429g of 35% hydrogen peroxide solution for 8 hours, and continuing to perform heat preservation reaction for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.57%, the alpha-IP selectivity is 0.51%, the o-KIP selectivity is 2.68%, the polymer selectivity is 1.75%, the KIP selectivity is 94.95% and the KIP yield is 94.54%.
The reaction solution was filtered, and the catalyst was washed with acetonitrile, dried and used indiscriminately according to the conditions of example 3. The results are shown in Table 1.
Table 1 catalyst application data
Example 4
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1382g of beta-isophorone, 1658g of acetonitrile, 34.55g of catalyst a and 41.46g of hydroquinone are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 50 ℃, dropwise adding 2429g of 35% hydrogen peroxide solution for 8 hours, and continuing to perform heat preservation reaction for 4 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.55%, the alpha-IP selectivity is 0.61%, the o-KIP selectivity is 2.86%, the polymer selectivity is 1.97%, the KIP selectivity is 94.44% and the KIP yield is 94.02%.
Example 5
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1382g of beta-isophorone, 1658g of acetonitrile, 34.55g of catalyst a and 41.46g of hydroquinone are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 30 ℃, dropwise adding 1700g of 50% hydrogen peroxide solution for 6 hours, and continuously reacting for 4 hours under heat preservation. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.43%, the selectivity of alpha-IP is 0.62%, the selectivity of o-KIP is 2.92%, the selectivity of polymer is 2.01%, the selectivity of KIP is 94.34%, and the yield of KIP is 93.80%.
Example 6
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1382g of beta-isophorone, 1658g of acetonitrile, 34.55g of catalyst b and 41.46g of hydroquinone are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 30 ℃, dropwise adding 2429g of 35% hydrogen peroxide solution for 8 hours, and continuing to perform heat preservation reaction for 2 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 99.52%, the alpha-IP selectivity is 0.88%, the o-KIP selectivity is 3.00%, the polymer selectivity is 2.28%, the KIP selectivity is 93.71% and the KIP yield is 93.26%.
Example 7
A reaction kettle provided with a six-blade turbine high-speed stirring paddle is used as a reactor. 1382g of beta-isophorone, 1658g of acetonitrile, 34.55g of catalyst b and 41.46g of phenol are sequentially added into a reaction kettle; starting electric heating and mechanical stirring, heating the temperature of the reaction solution to 40 ℃, dropwise adding 2429g of 35% hydrogen peroxide solution for 7 hours, and continuing to perform heat preservation reaction for 3 hours. After the reaction, gas chromatography analysis shows that the conversion rate of the raw material beta-isophorone is 98.70%, the alpha-IP selectivity is 0.55%, the o-KIP selectivity is 2.73%, the polymer selectivity is 1.80%, the KIP selectivity is 94.80%, and the KIP yield is 93.57%.
Comparative example 1
Except that no ZrO is used2MgCl was obtained in the same manner as in example 1 except that2-Y2O3The catalyst was a comparative catalyst a-1. According to the element content of XPS test Y, Mg, the composition of the comparative catalyst a-1 is W-AC carrier: y is2O3：MgCl2100.0:8.0:2.1 (mass ratio).
Except that Y is not used2O3MgCl was obtained in the same manner as in example 1 except that2-ZrO2The catalyst was a/W-AC catalyst (designated as comparative catalyst a-2). Testing the content of Zr and Mg elements according to XPS to obtain a comparative catalysta-2 is composed of a W-AC carrier: ZrO (ZrO)2：MgCl2100.0:8.0:2.1 (mass ratio).
The catalytic action of the comparative catalysts a-1, a-2 was examined with reference to the procedure of example 3.
The conversion rate of the raw material beta-isophorone of the comparative catalyst a-1 is 95.21%, the alpha-IP selectivity is 0.53%, the o-KIP selectivity is 2.72%, the polymer selectivity is 1.78%, the KIP selectivity is 94.84%, and the KIP yield is 90.30%.
The conversion rate of the raw material beta-isophorone of the comparative catalyst a-2 is 94.89%, the alpha-IP selectivity is 0.53%, the o-KIP selectivity is 2.74%, the polymer selectivity is 1.76%, the KIP selectivity is 94.83%, and the KIP yield is 89.98%.
Comparative example 2
With reference to the method of example 3, examine Y obtained in example 12O3-ZrO2The conversion rate of raw material β -isophorone is 99.00%, the selectivity of α -IP is 1.05%, the selectivity of o-KIP is 3.26%, the selectivity of polymer is 2.55%, the selectivity of KIP is 92.85%, and the yield of KIP is 91.92%.
Comparative example 3
Except that 2g of nano-Y is used2O36g of nano ZrO2And 50g of W-AC as a support, under the same conditions as in example 1, to obtain MgCl2-Y2O3-ZrO2a/W-AC catalyst. According to XPS test of the content of Y, Zr and Mg elements, the catalyst is prepared from the following components: y is2O3：ZrO2：MgCl2100.0:4.0:12.0:2.1 (mass ratio).
With reference to the method of example 3, MgCl was examined2-Y2O3-ZrO2The conversion rate of raw material β -isophorone was 95.50%, α -IP selectivity was 0.55%, o-KIP selectivity was 2.96%, multimer selectivity was 2.40%, KIP selectivity was 93.93%, and KIP yield was 89.70%.
Comparative example 4
MgCl was prepared as in example 1 using coconut shell activated carbon (available from Luoyang Bay environmental protection technologies, Ltd.) in place of W-AC under the same conditions as in example 12-Y2O3-ZrO2catalyst/C.
The resulting catalyst was examined by referring to the method of example 3. The conversion rate of the raw material beta-isophorone is 90.89%, the selectivity of alpha-IP is 0.85%, the selectivity of o-KIP is 3.00%, the selectivity of polymer is 2.20%, the selectivity of KIP is 93.82%, and the yield of KIP is 85.27%.
Comparative example 5
The procedure is as in example 3 except that hydroquinone is not used. The conversion rate of the raw material beta-isophorone is 97.32%, the alpha-IP selectivity is 0.60%, the o-KIP selectivity is 2.78%, the polymer selectivity is 1.95%, the KIP selectivity is 94.46%, and the KIP yield is 91.93%.
The above embodiments are not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (10)
1. A method for preparing 4-oxo-isophorone by catalytic oxidation of beta-isophorone comprises the following steps: carrying out oxidation reaction on the beta-isophorone and hydrogen peroxide in the presence of a solvent, a catalyst and a cocatalyst to obtain 4-oxo-isophorone; the catalyst is walnut shell-based activated carbon loaded yttrium oxide-zirconium oxide-metal halide.
2. The method according to claim 1, wherein the metal halide is one or more of a chloride or bromide of a transition metal, preferably one or more of lithium chloride, beryllium chloride, sodium chloride, magnesium chloride, potassium chloride, calcium chloride, rubidium chloride, strontium chloride, cesium chloride, barium chloride, lithium bromide, beryllium bromide, sodium bromide, magnesium bromide, potassium bromide, calcium bromide, rubidium bromide, strontium bromide, cesium bromide, barium bromide, more preferably one or more of magnesium chloride, magnesium bromide, calcium chloride, calcium bromide, and further preferably magnesium chloride.
3. The process according to claim 1 or 2, characterized in that the catalyst comprises the following composition: based on the mass portion, the weight percentage of the raw materials,
4. a method according to any one of claims 1 to 3, wherein the mass ratio of yttria to zirconia is in the range of 0.5 to 2, preferably 1 to 1.5.
5. A process according to any one of claims 1 to 4, wherein the co-catalyst is a phenolic compound, including phenol with or without substituents or benzenediol with or without substituents, preferably one or more of phenol, o-cresol, m-cresol, p-methylphenol, catechol, resorcinol, hydroquinone, preferably hydroquinone.
6. The process according to any one of claims 1 to 5, characterized in that the mass ratio of the beta-isophorone to catalyst is 1:0.01-0.05, preferably 1: 0.02-0.025; and/or the mass ratio of the beta-isophorone to the cocatalyst is 1:0.02-0.1, preferably 1: 0.03-0.05.
7. The process according to any one of claims 1 to 6, characterized in that the preparation process of the catalyst comprises the following steps:
(1) drying walnut shells, crushing, sieving with a sieve of 120-mesh and 160-mesh, adding an activating agent into the walnut shell powder, mixing and standing for 1-30h, preferably 10-20h, drying, pyrolyzing at high temperature, cooling to room temperature, washing to neutrality, drying, crushing, sieving with a sieve of 180-mesh and 200-mesh to obtain walnut shell-based activated carbon;
(2) adding nanometer yttrium oxide, zirconium oxide and walnut shell based active carbon into water, stirring and mixing for 0.5-3h, preferably 1-2h, then ultrasonically oscillating for 1-5h, preferably 2-3h at the frequency of 80-100Hz, 10-40 ℃, preferably 20-30 ℃, drying and grinding;
(3) dispersing the product obtained in the step (2) in a metal halide water solution, stirring for 5-20h, preferably 10-15h at 40-80 ℃, preferably 50-60 ℃, and drying to obtain the catalyst.
8. The method of claim 7, wherein in step (1), the activator is 10-60 wt% H3PO4Aqueous solution, preferably 30-50 wt% of H3PO4An aqueous solution.
9. The method according to claim 7 or 8, wherein in the step (2), the mass ratio of the yttrium oxide to the walnut shell-based activated carbon is (1-20): 100, preferably (5-10): 100, respectively; the mass ratio of the zirconium oxide to the walnut shell-based active carbon is (1-20): 100, preferably (5-10): 100, respectively; preferably, the mass ratio of yttrium oxide to zirconium oxide is between 0.5 and 2, preferably between 1 and 1.5.
10. The method as claimed in any one of claims 7 to 9, wherein in the step (3), the mass ratio of the metal halide to the walnut shell-based activated carbon (0.5 to 5): 100, preferably (1-3): 100.
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| CN115703702B (en) * | 2021-08-16 | 2024-05-28 | 安徽圣诺贝化学科技有限公司 | Method for preparing tea-flavored ketone by oxidizing alpha-isophorone |
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