CN112517075A - Isomerization catalyst, preparation method thereof and preparation method of beta-isophorone - Google Patents

Isomerization catalyst, preparation method thereof and preparation method of beta-isophorone Download PDF

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CN112517075A
CN112517075A CN202011369912.8A CN202011369912A CN112517075A CN 112517075 A CN112517075 A CN 112517075A CN 202011369912 A CN202011369912 A CN 202011369912A CN 112517075 A CN112517075 A CN 112517075A
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isophorone
catalyst
acetate
reaction
beta
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张弈宇
张涛
刘英瑞
吕英东
沈宏强
郭劲资
宋军伟
程晓波
杨宗龙
黎源
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Wanhua Chemical Group Co Ltd
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Abstract

The invention discloses an isomerization catalyst and a preparation method thereof, and a preparation method of beta-isophorone. The isomerization catalyst, the structural formula of which is shown as:

Description

Isomerization catalyst, preparation method thereof and preparation method of beta-isophorone
Technical Field
The invention relates to the field of catalysts and organic synthesis, in particular to an isomerization catalyst and a method for preparing beta-isophorone from alpha-isophorone.
Background
Beta-isophorone (3,5, 5-trimethylcyclohex-3-en-1-one) is an important intermediate for synthesizing vitamin E, carotenoids and various perfumes, especially an important raw material for preparing tea scented ketone (2,6, 6-trimethyl-2-cyclohexene-1, 4-dione, KIP).
The conventional preparation method of beta-isophorone is to take alpha-isophorone (3,5, 5-trimethylcyclohex-2-en-1-one) as a raw material and prepare the beta-isophorone through isomerization reaction under the action of a catalyst. The generation of the beta-isophorone relates to the equilibrium reaction of deconjugation, so the equilibrium concentration of the beta-isophorone is low, and the beta-isophorone needs to be continuously extracted by methods such as rectification and the like to promote the reaction to move towards the direction of generating the beta-isophorone.
Various methods have been reported for this isomerization reaction for a long time. The types of the used catalysts are mainly divided into acid catalysis and alkali catalysis, and the main process is as follows:
Figure BDA0002805667670000011
US patent US5907065A with Co3O4And metal oxides such as CaO and the like are used as catalysts, and the isomerization reaction is carried out by adopting a reduced pressure rectification mode. Although the purity of the obtained beta-isophorone can reach more than 97%, the reaction by-products are more, and the space-time yield is low.
In US4845303A, acetylacetone complexes of metals such as iron, cobalt, chromium, aluminum, etc. are used as catalysts to prepare beta-isophorone by reactive distillation. Although the reaction yield can reach 90-95%, the catalyst dosage is only 0.1-1 wt%. However, the space-time yield of the reaction is low, and the catalyst is dissolved in the reaction solution and is difficult to separate from the system, which is not favorable for industrial application.
US patent US4005145A discloses a process for carrying out an isomerisation reaction using acids. Acids used include adipic acid, trimethoxybenzoic acid, and the like. After reaction and rectification, the purity of the product can reach more than 91 percent, but the problems of more byproducts and serious equipment corrosion still exist.
Patents CN1288882A and CN1235954A disclose methods for preparing beta-isophorone by isomerization reaction using alkali metal compounds, including hydroxides and carbonates, as catalysts. Although the product obtained by the method has high purity, the catalyst has strong alkalinity and serious corrosion to equipment. And the catalyst is homogeneous and difficult to recycle.
In summary, there is a need to develop a novel catalyst for the isomerization reaction of beta-isophorone, which can solve the disadvantages of the prior art and process.
Disclosure of Invention
The invention provides an isomerization catalyst and a preparation method thereof. The catalyst is simple to prepare, active groups are loaded on the carrier through chemical bonds, the catalyst is high in stability, and no obvious activity loss exists after the catalyst can be reused. Also provides a preparation method of the beta-isophorone, which has high selectivity and high yield for the reaction of generating the beta-isophorone by isomerizing the alpha-isophorone and a catalyst. The reaction process is simple, has no corrosion to equipment and has strong industrial applicability.
In order to achieve the purpose, the invention adopts the following technical scheme:
an isomerization catalyst having the formula:
Figure BDA0002805667670000031
wherein R is-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、
Figure BDA0002805667670000032
Figure BDA0002805667670000033
preferably-CH2CH2-; m represents Cr, Mn, Fe, Co, Ni, Cu, Zn, preferably Zn; ac represents an acetoxy group;
Figure BDA0002805667670000034
magnetic nanoparticles Fe representing a core-shell structure3O4@SiO2。
A method of preparing the isomerization catalyst of the present invention comprises the steps of:
1) 3-Chloropropyltriethoxysilane (CPTES) on magnetic nanoparticles Fe with core-shell structure3O4@SiO2(SMNP) modifying to obtain halogenated alkyl modified magnetic nanoparticles (MN-Cl);
2) performing substitution reaction on the halogenated alkyl modified magnetic nanoparticles (MN-Cl) and primary diamine to obtain amino modified magnetic nanoparticles;
3) performing substitution reaction on the amino-modified magnetic nanoparticles and o-formylbenzoic acid to prepare o-formylbenzoic acid-modified magnetic nanoparticles;
4) coordinating the magnetic nano-particle modified by o-formylbenzoic acid with metal ions to obtain the magnetic nano-particle catalyst modified by secondary amino and metal complexes.
The catalyst preparation reaction equation is exemplified as follows:
Figure BDA0002805667670000041
in the step 1), the magnetic nanoparticles Fe with core-shell structure3O4@SiO2(SMNP), see literature "carboxylated core-shell magnetic Nano Fe3O4Preparation of adsorbentPreparation and counter Cu2+Adsorption Performance, Proc. of higher school chemistry 2012, 33(1): 107-.
As a preferred embodiment, in step 1) of the present invention, the reaction of 3-Chloropropyltriethoxysilane (CPTES) with SMNP is carried out in a solvent, wherein the solvent comprises one or more of methanol, ethanol, toluene, acetonitrile, dichloromethane, acetone, n-hexane, cyclohexane, etc., and toluene is preferred.
In the step 1) of the invention, the mass ratio of the SMNP to the CPTES is 1:0.5-5, preferably 1: 1-3.
The reaction temperature in step 1) of the present invention is 60 to 120 ℃, preferably 80 to 110 ℃. The reaction time is 8-30h, preferably 10-15 h.
In step 2), the primary diamine includes one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 1, 4-cyclohexanediamine, preferably one or more of ethylenediamine, propylenediamine, butylenediamine, and hexylenediamine, and more preferably ethylenediamine.
As a preferred embodiment, in step 2) of the present invention, the reaction of MN — Cl with the primary diamine is performed in a solvent, and the solvent includes one or more of methanol, ethanol, toluene, acetonitrile, water, acetone, n-hexane, cyclohexane, etc., preferably ethanol.
In the step 2) of the invention, the mass ratio of MN-Cl to primary diamine is 1:2-10, preferably 1: 4-8.
The reaction temperature of the step 2) of the present invention is 0 to 50 ℃, preferably 20 to 40 ℃. The reaction time is 15-50h, preferably 20-40 h.
As a preferable scheme, the reaction of the amine-group modified magnetic nanoparticles and o-formylbenzoic acid in step 3) of the present invention is performed in a solvent. The solvent includes one or more of methanol, ethanol, tetrahydrofuran, acetonitrile, dichloromethane, acetone, n-hexane, cyclohexane, ethyl acetate, etc., preferably acetonitrile.
In the step 3), the mass ratio of the amino-modified magnetic nanoparticles to the o-formylbenzoic acid is 1:5-30, preferably 1: 8-15.
In the step 3) of the present invention, the reaction temperature is 20 to 120 ℃, preferably 60 to 90 ℃. The reaction time is 10-60h, preferably 30-50 h.
In the step 4), the obtained o-formylbenzoic acid modified magnetic particles and metal ions are subjected to coordination reaction in a corresponding metal acetate aqueous solution, wherein the metal acetate comprises one or more of chromium acetate, manganese acetate, iron acetate, cobalt acetate, nickel acetate, copper acetate, zinc acetate and the like, and preferably zinc acetate.
In the step 4), the mass ratio of the o-formylbenzoic acid modified magnetic nanoparticles to the metal acetate is 1:1-40, preferably 1: 10-20.
In the step 4) of the present invention, the reaction temperature is 10 to 100 ℃, preferably 60 to 80 ℃. The reaction time is 5-80h, preferably 40-50 h.
In the preparation method of beta-isophorone, alpha-isophorone is subjected to isomerization reaction in the presence of an isomerization catalyst and an auxiliary agent to prepare beta-isophorone.
In the method for preparing beta-isophorone according to the present invention, the amount of the isomerization catalyst is 0.1-10 wt%, preferably 0.5-2 wt%, relative to alpha-isophorone.
In the preparation method of the beta-isophorone, the auxiliary agent is one or more of benzoquinone and naphthoquinone substances, preferably comprises one or more of benzoquinone, tert-butyl p-benzoquinone, methyl benzoquinone, 2-chloro-1, 4-benzoquinone, 1, 2-naphthoquinone, 1, 4-naphthoquinone, 5-hydroxy p-naphthoquinone and menadione; preference is given to naphthoquinones, more preferably 1, 4-naphthoquinone.
In the preparation method of the beta-isophorone, the amount of the auxiliary agent is 0.05-5 wt% relative to the amount of the alpha-isophorone, and preferably 0.2-2 wt%.
In the preparation method of beta-isophorone, the reaction can be carried out in a reactor known in the art, preferably in a tower reactor by a reactive distillation process, the theoretical plate number of the reactor is 20-50, preferably 30-40; the reaction temperature is 100 ℃ to 300 ℃, preferably 210 ℃ to 250 ℃. The reflux ratio is 10-50:1, preferably 30-40: 1.
The technical scheme of the invention has the following advantages:
(1) magnetic nanoparticles Fe of core-shell structure3O4@SiO2The (SMNP) is used as a catalyst carrier, so that the supported catalyst has a nano-scale dispersion effect, the dispersibility of the supported catalyst is improved, and the utilization rate of the catalyst is improved. In addition, SiO is coated on the surface of the magnetic nano particles2The layer forms a core-shell structure, so that the metal core can be prevented from being corroded by an acidic medium, the agglomeration of the catalyst is effectively avoided, and the service life of the catalyst is prolonged.
(2) Secondary amine groups playing a main catalytic role can be introduced on the surface of the magnetic carrier through further modification of 3-Chloropropyltriethoxysilane (CPTES) and primary diamine. And different substituted secondary amine groups can be introduced by adjusting the use of different primary diamines, so that the best catalytic effect is obtained. In addition, when secondary amine is introduced, the residual primary amine can further react with o-formylbenzoic acid to generate imine, imine bonds and carboxyl can be coordinated with metal ions to obtain a magnetic nanoparticle catalyst modified by the secondary amine and a metal complex, a carbanion intermediate generated in the process of alpha-isophorone isomerization reaction can be effectively stabilized, and the occurrence of Michael addition (the product structure is shown in the specification)
Figure BDA0002805667670000071
) And carbonyl condensation (product structure is
Figure BDA0002805667670000072
) And side reactions are carried out, so that the reaction selectivity is improved, and the accumulation of heavy components in a tower kettle in the reaction rectification process is avoided. Meanwhile, the conversion of the product beta-isophorone to alpha-isophorone is avoided.
(3) The auxiliary agent contains a polyatomic conjugated system, and plays a stabilizing role in charged intermediates including ions, free radicals and the like through a delocalization effect. Therefore, the method can also play a role in avoiding the accumulation of heavy components and the conversion of the beta-isophorone to the alpha-isophorone and improve the reaction selectivity.
(4) In addition, secondary amino and metal ions in the catalyst are connected to the catalyst carrier through chemical bonds, and the bonding effect is stronger than that of the common adsorption force, so that the stability of the catalyst in cyclic application can be improved, and the loss of active components of the catalyst is avoided. The catalyst can be used for 20 times, and the reaction conversion rate, the product selectivity and the product purity are not obviously reduced.
(5) Secondary amine groups with catalytic activity and metal ions are introduced on the surfaces of the magnetic particles through chemical modification, so that the defects that the catalyst is dissolved in a system and corrodes equipment and is difficult to recycle when organic base or inorganic base is used independently for catalysis are overcome. The catalyst is applied to the preparation of the beta-isophorone, has high catalytic efficiency and specificity, and is green and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the invention.
Gas chromatography conditions: performing Agilent gas chromatography, performing on-line measurement on chromatographic column HP-5, performing second-order temperature programming, maintaining the initial temperature at 50 deg.C for 1min, and increasing to 80 deg.C at a speed of 5 deg.C/min; then the temperature is increased to 250 ℃ at the speed of 10 ℃/min. Carrier gas high purity N2The split ratio is 100: 1. the temperature of the gasification chamber is 250 ℃, the temperature of the detector is FID, and the temperature of the detector is 250 ℃.
An infrared testing instrument: vetex-70 Fourier transform infrared spectrometer (Bruker, Germany).
Example 1
60g of magnetic nanoparticles (SMNP) with a core-shell structure are dispersed in 1.5L of toluene, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. 60g of CPTES was added with mechanical stirring, followed by N2Reacting for 12h at 110 ℃ under the atmosphere. And after the reaction is finished, cooling to room temperature, carrying out solid magnetic separation, washing with absolute ethyl alcohol, and drying to obtain the magnetic nanoparticles (MN-Cl) with the surfaces modified by halogenated alkyl. IR: 2923cm-1，2852cm-1(methylene vibration), 680cm-1(C-Cl bond).
60g of MN-Cl is taken and dispersed in 1.5L of ethanol, 300g of ethylenediamine is added, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. Then at N2Reacting for 24 hours at 25 ℃ under the atmosphere. Inverse directionAnd (3) after finishing the reaction, carrying out magnetic separation on the solid, washing the solid with absolute ethyl alcohol, and drying to obtain the amino modified magnetic nanoparticles. IR: 2922cm-1，2852cm-1(methylene vibration), 1590cm-1(primary amine linkage).
60g of amino modified magnetic nanoparticles are dispersed in 1.5L of acetonitrile, 600g of o-formylbenzoic acid is added, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed. Then at N2Reacting for 30h at 70 ℃ under the atmosphere. And after the reaction is finished, carrying out magnetic separation on the solid, washing with acetonitrile, and drying to obtain the o-formylbenzoic acid modified magnetic nanoparticles. IR: 2924cm-1，2851cm-1(methylene vibration), 1642cm-1(imine bond), 1700cm-1(carboxyl group).
60g of the o-formylbenzoic acid modified magnetic nanoparticles are dispersed in 1.5L of deionized water, and 600g of zinc acetate is added. And performing ultrasonic treatment for 30min to uniformly disperse the particles. Then at N2Reacting for 48h at 60 ℃ under the atmosphere. And after the reaction is finished, magnetically separating the solid, washing the solid with deionized water, and drying to obtain the magnetic nanoparticle catalyst (catalyst a) modified by the secondary amino and the metal complex. IR: 2922cm-1，2852cm-1(methylene vibration), 1640cm-1(imine bond), 560cm-1(metal coordinate bond).
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 98.2 percent, the selectivity of the beta-isophorone is 99.95 percent, the selectivity of heavy components is 0.05 percent, and the purity of the product beta-isophorone is 94.0 percent.
Heavy component containing
Figure BDA0002805667670000091
Example 2
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of benzoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 40: 1. The conversion rate of the alpha-isophorone is 97.8 percent, the selectivity of the beta-isophorone is 95.89 percent, the selectivity of heavy components is 4.11 percent, and the purity of the product beta-isophorone is 88.9 percent.
Example 3
60g of MN-Cl prepared in example 1 was dispersed in 1.5L of ethanol, 300g of hexamethylenediamine was added, and the mixture was dispersed uniformly by sonication for 30 min. Then at N2Reacting for 24 hours at 25 ℃ under the atmosphere. And after the reaction is finished, magnetically separating the solid, washing the solid with absolute ethyl alcohol, and drying to obtain the hexamethylene diamine modified magnetic nanoparticles.
Otherwise, referring to example 1, magnetic nanoparticles (catalyst b) modified with secondary amino groups and metal complex were obtained
1000g of alpha-isophorone containing 1.0 wt% of catalyst b and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of alpha-isophorone is 93.2%, the selectivity of beta-isophorone is 99.91%, the selectivity of heavy components is 0.09%, and the purity of product beta-isophorone is 93.7%.
Example 4
60g of the o-formylbenzoic acid-modified magnetic nanoparticles prepared in example 1 were dispersed in 1.5L of deionized water, and 600g of nickel acetate was added. And performing ultrasonic treatment for 30min to uniformly disperse the particles. Then at N2Reacting for 48h at 60 ℃ under the atmosphere. And after the reaction is finished, magnetically separating the solid, washing the solid with deionized water, and drying to obtain the magnetic nanoparticle catalyst (catalyst c) modified by the secondary amino and the metal complex.
1000g of alpha-isophorone containing 1.0 wt% of catalyst c and 0.5 wt% of 1, 4-naphthoquinone is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 98.0 percent, the selectivity of the beta-isophorone is 96.02 percent, the selectivity of heavy components is 3.98 percent, and the purity of the product beta-isophorone is 90.7 percent.
After the end of the catalyst reaction in example 1, the catalyst was magnetically separated and washed with ethanol. After drying, the catalyst is mechanically applied according to the conditions of the reaction rectification in the example 1, and the experimental data are shown in the following table 1:
TABLE 1 catalyst a application data
Figure BDA0002805667670000101
Comparative example 1
1000g of alpha-isophorone containing 1.0 wt% of catalyst a is added into a tower kettle of a plate tower reactor with 35 tower plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 97.5 percent, the selectivity of the beta-isophorone is 92.42 percent, the selectivity of heavy components is 7.58 percent, and the purity of the product beta-isophorone is 84.8 percent.
Comparative example 2
1000g of o-formylbenzoic acid-modified magnetic nanoparticles prepared in example 1 and 0.5 wt% of 1, 4-naphthoquinone-containing α -isophorone were added to a tray-type tower reactor having 35 trays, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 30:1 at 220 ℃. The conversion rate of the alpha-isophorone is 97.7 percent, the selectivity of the beta-isophorone is 93.20 percent, the selectivity of heavy components is 6.80 percent, and the purity of the product beta-isophorone is 83.9 percent.
Comparative example 3
Comparative catalyst 1 was prepared by substituting o-formylbenzoic acid with glyoxylic acid and otherwise referring to example 1.
1000g of alpha-isophorone containing 1.0 wt% of a comparative catalyst 1 and 0.5 wt% of 1, 4-naphthoquinone was added to the bottom of a plate-type tower reactor having 35 plates, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 220 ℃ and a reflux ratio of 30: 1. The conversion rate of the alpha-isophorone is 97.3 percent, the selectivity of the beta-isophorone is 93.80 percent, the selectivity of heavy components is 6.20 percent, and the purity of the product beta-isophorone is 85.3 percent.
Comparative example 4
Comparative catalyst 2, which was prepared without reactive secondary amine groups, was prepared by substituting ethylenediamine for N-benzylethylenediamine and the remaining conditions refer to example 1.
1000g of alpha-isophorone containing 1.0 wt% of a comparative catalyst 2 and 0.5 wt% of 1, 4-naphthoquinone was added to the column bottom of a plate-type column reactor having 35 plates, and a rectification reaction was carried out at an absolute pressure of 0.1MPa, a reflux ratio of 220 ℃ and a reflux ratio of 30: 1. The conversion rate of the alpha-isophorone is 45.6 percent, the selectivity of the beta-isophorone is 80.75 percent, the selectivity of heavy components is 19.25 percent, and the purity of the product beta-isophorone is 40.36 percent.
Comparative example 5
1000g of alpha-isophorone containing 1.0 wt% of catalyst a and 0.5 wt% of cyclohexanone is added into a tower kettle of a plate tower reactor with 35 plates, and rectification reaction is carried out under the conditions that the absolute pressure is 0.1MPa, the temperature is 220 ℃, and the reflux ratio is 30: 1. The conversion rate of the alpha-isophorone is 97.3 percent, the selectivity of the beta-isophorone is 92.82 percent, the selectivity of heavy components is 7.18 percent, and the purity of the product beta-isophorone is 85.0 percent.
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. An isomerization catalyst having the formula:
Figure FDA0002805667660000011
wherein R is-CH2CH2-、-CH2CH2CH2 --CH2CH2CH2CH2 -、
Figure FDA0002805667660000014
Figure FDA0002805667660000013
preferably-CH2CH2-; m represents Cr, Mn, Fe, Co, Ni, Cu, Zn, preferably Zn; ac represents an acetoxy group.
2. A process for preparing the isomerization catalyst of claim 1 comprising the steps of:
1) using 3-chloropropyltriethoxysilane to make core-shell structureMagnetic nanoparticles of Fe3O4@SiO2Modifying to obtain halogenated alkyl modified magnetic nanoparticles;
2) carrying out substitution reaction on the halogenated alkyl modified magnetic nanoparticles and primary diamine to obtain amino modified magnetic nanoparticles;
3) performing substitution reaction on the amino-modified magnetic nanoparticles and o-formylbenzoic acid to prepare o-formylbenzoic acid-modified magnetic nanoparticles;
4) coordinating the magnetic nano-particle modified by o-formylbenzoic acid with metal ions to obtain the magnetic nano-particle catalyst modified by secondary amino and metal complexes.
3. The method according to claim 2, wherein in step 1), Fe3O4@SiO2The mass ratio of the 3-chloropropyltriethoxysilane to the 3-chloropropyltriethoxysilane is 1:0.5-5, preferably 1: 1-3.
4. A method according to claim 2 or 3, wherein in step 2) the primary diamine comprises one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1, 4-cyclohexanediamine, preferably one or more of ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, more preferably ethylenediamine.
5. The method according to any one of claims 2 to 4, wherein in step 2) the mass ratio of the haloalkyl modified magnetic nanoparticles to the primary diamine is from 1:2 to 10, preferably from 1:4 to 8.
6. The method according to any one of claims 2 to 5, wherein the mass ratio of the amine-group-modified magnetic nanoparticles to the o-formylbenzoic acid in step 3) is 1:5 to 30, preferably 1:8 to 15.
7. The method as claimed in any one of claims 2 to 6, wherein in the step 4), the o-formylbenzoic acid modified magnetic particles obtained are subjected to coordination reaction with metal ions in a corresponding metal acetate aqueous solution, and the metal acetate comprises one or more of chromium acetate, manganese acetate, iron acetate, cobalt acetate, nickel acetate, copper acetate and zinc acetate.
8. The method as claimed in claim 7, wherein in the step 4), the mass ratio of the o-formylbenzoic acid modified magnetic nanoparticle to the metal acetate is 1:1-40, preferably 1: 10-20.
9. A preparation method of beta-isophorone comprises the following steps: alpha-isophorone is prepared by an isomerization reaction in the presence of an isomerization catalyst as described in claim 1 or a catalyst and auxiliaries prepared by the processes as described in claims 2 to 8.
10. The method according to claim 9, wherein the auxiliary agent is one or more of benzoquinone and naphthoquinone, preferably comprises one or more of benzoquinone, tert-butyl-p-benzoquinone, methyl benzoquinone, 2-chloro-1, 4-benzoquinone, 1, 2-naphthoquinone, 1, 4-naphthoquinone, 5-hydroxy-p-naphthoquinone and menadione; preferably naphthoquinones, more preferably 1, 4-naphthoquinone; and/or the amount of the auxiliary agent is 0.05 to 5 wt%, preferably 0.2 to 2 wt%, relative to the amount of the alpha-isophorone.
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