CN110721696A - Method for catalytically synthesizing tea scented ketone by adopting perovskite type composite oxide - Google Patents

Abstract

The invention discloses a method for catalyzing and synthesizing tea ketone by adopting perovskite-type composite oxide. , using molecular oxygen or air as oxidant, continuous oxidation reaction in trickle bed reactor to synthesize tea ketone. The invention has mild reaction conditions, high catalytic efficiency, good selectivity and high catalyst stability, and is suitable for industrial production.

Description

A kind of method that adopts perovskite type composite oxide to catalyze and synthesize tea ketone

technical field

The invention belongs to the technical field of organic chemical industry, and relates to a method for catalyzing and synthesizing tea ketone by adopting a perovskite-type composite oxide.

Background technique

Tea ketone, also known as 4-oxoisophorone (KIP for short), is a light yellow liquid or crystal, which is a natural compound existing in a variety of plants. Its pure product has a strong aroma and a long-lasting fragrance. The aroma is slightly sour, sweet and woody and dried fruit aroma, which has a significant effect on various cigarettes. Tea ketone is an important chemical and pharmaceutical intermediate. It can be used as a flavoring agent or spice in food additives, and can also be used in the synthesis of cosmetics. It is also an important intermediate in the preparation of vitamins and carotenoids. It has a wide range of uses.

At present, there are two main synthetic routes for KIP: oxidation of β-isophorone (abbreviated as β-IP) method and oxidation of α-isophorone (abbreviated as α-IP) method.

1. Oxidation of β-IP to synthesize KIP

This process is a commonly used method for preparing KIP. First, α-IP is converted into β-IP, and then β-IP is oxidized to obtain KIP. Among them, α-IP and β-IP are isomers. Due to the conjugation effect, α-IP is more thermodynamically stable than β-IP, and β-IP can be converted by isomerizing α-IP. The isomerization between α-IP and β-IP is a reversible reaction, and there is a chemical equilibrium. It is necessary to continuously remove the β-IP produced by reactive distillation, so that the reaction can continue to proceed in a favorable direction. This isomerization process is carried out under the action of catalysts such as strong acid and strong base, and the required temperature is high and the conversion rate is low, so the equipment conditions are required to be high, and the energy consumption is relatively large. The synthetic route is as follows:

2. Oxidation of α-IP to synthesize KIP

The method directly oxidizes α-IP to prepare KIP, eliminating the isomerization process; and compared with β-IP, α-IP is a bulk industrial chemical with abundant sources and low price, so the direct oxidation process has more obvious application advantages and broader prospects. The synthetic route is as follows:

At present, there have been many reports on the direct oxidation of α-IP to KIP, which can be divided into two categories according to the catalytic system: homogeneous catalytic system and heterogeneous catalytic system.

Homogeneous catalytic system:

Patent DE2459148 describes the use of V(acac) ₃ , Fe(acac) ₃ , Co(acac) ₃ and other transition metal complexes as catalysts to catalyze the oxidation of α-IP to prepare KIP, react at 130°C for 5 days, and the highest yield is 20% . Patent US3960966 reported that phosphomolybdic acid, silico-molybdic acid or vanadium molybdenum complex and copper sulfate were used as catalysts to catalyze the oxidation of α-IP to prepare KIP, and air was used as the oxidant to react at 100 ° C for 95h, the conversion rate could reach 98.5%, and the yield was 98.5%. 45%. Patent DE2526851 discloses a method for preparing KIP by catalytic oxidation of α-IP with the addition of molybdenum trioxide. The reaction is carried out at 80° C. for 72 hours, and the yield is 50%. Chemistry Letters, 1984, 2031 used phosphomolybdic acid, potassium dichromate and copper sulfate as catalysts, and air as oxidant, and reacted with continuous ventilation at 100 ° C for 84 hours, α-IP was basically converted, and the yield of tea ketone was 60%. . Journal of Molecular Catalysis A: Chemical, 2002, 179, 233 used phosphomolybdic acid/DMSO/KOBu ^t catalyst system to react at 115°C for 24h, the conversion rate of α-IP was 99.1%, and the selectivity of tea ketones could be maintained at 70.3%. The above technical solutions have the problems of higher reaction temperature, longer reaction time and lower yield.

Chemistry Letters, 1983, 1082 uses a catalytic system composed of Pd(II) (such as Pd(Ac) ₂ , (PhCN) ₂ PdCl ₂ ) and triethylamine or a CuCl catalytic system, tert-butyl hydroperoxide is the oxide, benzene As a solvent, the reaction was carried out at 25-50 °C for 19-24 h, and the yield was 49-55%. Patent CN101143810A uses V ₂ O ₅ or VO(acac) ₂ as catalyst, tert-butyl hydroperoxide as oxidant, acetone as solvent, catalyzes oxidation of α-IP to prepare KIP, and reacts at 50°C for 18h, with a yield of 40%. Patent CN101417936A adopts a metal-free catalytic system (a co-catalytic system consisting of N-hydroxyphthalimide and its analogs as the main catalyst and organic co-catalysts (such as benzoyl peroxide)), in the organic solvent ethyl acetate. In the presence of ester, oxygen or oxygen-enriched gas is used as oxidant to catalyze the oxidation of α-IP to prepare KIP. The reaction is carried out at 50 °C for 24 hours, and the selectivity can reach 93%, but the conversion rate is only 43%. Patent CN102329202B adopts metal-free catalytic system (co-catalytic system composed of N-hydroxyphthalimide and its analogs as main catalyst and metal salt co-catalyst (such as CuCl ₂ )), in the presence of organic solvent acetonitrile, Oxygen or oxygen-enriched gas was used as the oxidant to catalyze the oxidation of α-IP to prepare KIP. The reaction was carried out at 75°C for 5h, the selectivity was 86.8%, and the conversion rate was up to 90.3%. The above technical solution reduces the reaction temperature and shortens the reaction time, but there is a problem that the yield is relatively low.

Chemistry-AEuropean Journal, 2005, 11, 3899 used Ru ^IV (2,6-Cl ₂ tpp)Cl ₂ as catalyst, 2,6-Cl ₂ pyNO as oxidant, CH ₂ Cl ₂ as solvent, and reacted at 40°C for 6 -8h, the conversion rate is 75%, and the selectivity reaches 99%. The technical solution can achieve a higher yield at a lower reaction temperature and a shorter reaction time, but the oxidant is expensive and not environmentally friendly enough, which is not conducive to industrial production.

At the same time, the above technical solutions are all carried out in the presence of organic solvents, and there is generally a problem of solvent separation and recovery cost.

CN105601490B Under solvent-free conditions, using dirhodium complex Rh ₂ (esp) ₂ as catalyst, tert-butyl hydroperoxide aqueous solution as oxidant, catalytic oxidation of α-IP to prepare KIP, reaction at 25 ° C for 24 hours, conversion rate of 91%, The yield was 78%. The technical solution has the problems that the reaction time is long and the oxidant is not green enough.

In addition, the homogeneous catalytic system generally has the problem that the catalyst is not easily separated.

Heterogeneous catalytic systems:

Tetrahedron Letters, 1997, 38, 5659 used molybdenum vanadium phosphate or its supported activated carbon as catalyst, molecular oxygen as oxidant, toluene as solvent, and reacted at 80-100℃ for 20h under normal pressure, and the conversion rate of α-IP was up to 93%. , the KIP selectivity is up to 47%. This technical solution has the problem of low catalyst selectivity.

Catalysis Communication, 2007, 8, 1156 uses Ru/MgAl hydrotalcite as catalyst, tert-butyl hydroperoxide as oxidant, acetonitrile as solvent, and reacts at 60℃ for 48h, the selectivity is 100%, but the highest conversion rate is 60% . Applied Cataysis A: General, 2008, 345, 104 Using Cu/Co/Fe-MgAl hydrotalcite as catalyst, tert-butyl hydroperoxide as oxidant, acetonitrile as solvent, 60℃ for 48h, the selectivity is 100%, but the conversion The highest rate is 74%. The above technical solutions are highly selective, but the reaction time is relatively long.

To sum up, the existing research on the direct oxidation of α-IP to prepare KIP, the catalytic effect is generally not ideal, some reaction conditions are harsh, some catalysts have low activity selectivity, some catalysts are not easy to separate and apply, and some are used. A lot of solvent, and some oxidants are expensive. Therefore, there is no continuous direct oxidation of α-IP to prepare KIP with mild reaction conditions, high catalyst performance, long life, easy separation, cheap oxidant, environment-friendly, solvent-free and continuous.

SUMMARY OF THE INVENTION

In view of the above defects or improvement requirements of the prior art, the present invention provides a method for catalyzing the synthesis of tea ketones by using perovskite-type composite oxides. The method has high reaction conversion rate and selectivity, and at the same time, the catalyst has a long life and is easy to separate. .

The technical scheme of the present invention is as follows:

A method for catalyzing and synthesizing tea ketone by adopting perovskite-type composite oxide. Under the catalysis of perovskite-type composite oxide, oxygen or air is used as oxidant, and α-isophorone is oxidized under solvent-free conditions. reaction to obtain the tea ketone;

The perovskite-type composite oxide is La _1-x X _x Co _1-y Y _y O _3+δ ;

X is selected from a kind of in K, Ca, Sr, Ba; Y is selected from a kind of in Mn, Fe, Cu, Ru, Rh, Pd, Pt; Wherein, x takes 0.1-0.5, y takes 0.1-0.5; δ is used to denote lattice defects or oxygen vacancies.

In the present invention, the new perovskite-type composite oxide catalyst is applied to the reaction of α-isophorone oxidation to synthesize tea ketone, the reaction conversion rate is generally above 70%, and the reaction selectivity is generally above 90%; The catalyst life is high, and the conversion and selectivity are still at a high level during long-term operation.

The reaction of the present invention can be carried out in batch reactors, such as various reaction flasks or reactors, and can also be carried out in various continuous reactors, such as pipeline reactors or trickle bed reactors. Preferably, the oxidation reaction is carried out in a trickle-bed reactor;

The perovskite-type composite oxide is immobilized in a trickle-bed reactor, and α-isophorone and oxygen or air are continuously introduced into the trickle-bed reactor for reaction.

At this time, the reaction raw materials are continuously input into the trickle bed reactor, the reaction product tea ketone is continuously output, and the reaction efficiency is greatly improved.

In the trickle-bed reactor, the molar ratio of the reaction materials and the mass space velocity will affect the reaction result. Preferably, the molar ratio of the oxygen contained in the oxygen or air to α-isophorone is 1.1- 5:1.

Preferably, the mass space velocity of α-isophorone is 0.05-1.6 h ^-1 .

Preferably, the reaction pressure is 0.1-2MPa, and the reaction temperature is 30-90°C.

In the present invention, the preparation of the perovskite-type composite oxide is simple, and the specific steps are as follows:

Adding mixed salt and citric acid to the water, then ultrasonically promoting the dissolution, evaporating water to a sol state under heating conditions, and then drying and baking to obtain the perovskite-type composite oxide catalyst;

The mixed salt is obtained by mixing the salt formed by La, X, Co and Y, wherein, in the perovskite type composite oxide, the values of x and y are determined by the molar amount of the salt.

The amount of the water can be used to dissolve each component, and usually the amount added is 3-5 times the mass of the mixed salt.

Preferably, the evaporation temperature is 80-90 °C;

The drying process is carried out in an oven, and the drying temperature is 110-130 °C;

The baking temperature is 600-800°C, and the baking time is 1-3 hours.

In the present invention, the salt used is required to be easily dissolved and easily obtained. Preferably, the salt is one or more of nitrate, acetate, sulfate, chloride and oxalate.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The synthetic route of the present invention is simple, the α-isophorone isomerization process is omitted, and the energy consumption cost is reduced.

(2) The reaction of the present invention is carried out in a trickle bed reactor, and the whole process is a continuous process, which is beneficial to increase the production capacity and has low labor intensity.

(3) The reaction conditions of the catalytic system are mild, the raw material conversion rate is high, and the product selectivity is high.

(4) The catalyst adopted in the present invention has good stability, and the catalytic activity can be well maintained when used for a long time.

(5) The catalyst of the present invention is easy to prepare, and at the same time, the catalyst used is a heterogeneous catalyst, and the same product is easy to separate.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

Example 1

Preparation of catalyst: according to the stoichiometric molar ratio La:K:Co:Mn=9:1:9:1, weigh a certain amount of lanthanum nitrate, potassium nitrate, cobalt nitrate and manganese nitrate, and then molar ratio metal cation: citric acid =1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then the The sample was calcined at 700°C for 3 hours, and the perovskite composite oxide catalyst La _0.9 K _0.1 Co _0.9 Mn _0.1 O _3+δ was obtained, which was denoted as catalyst A.

Example 2

Preparation of catalyst: according to the stoichiometric molar ratio La:Ca:Co:Fe=1:1:1:1, weigh a certain amount of lanthanum nitrate, calcium nitrate, cobalt nitrate and ferric chloride, and then molar ratio metal cation: lemon Acid = 1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then The perovskite composite oxide catalyst La _0.5 Ca _0.5 Co _0.5 Fe _0.5 O _3+δ can be obtained by calcining the sample at 700°C for 3 hours, which is denoted as catalyst B.

Example 3

Preparation of catalyst: according to the stoichiometric molar ratio La:Sr:Co:Cu=9:1:5:5, weigh a certain amount of lanthanum acetate, strontium nitrate, cobalt chloride and copper sulfate, and then molar ratio metal cation: lemon Acid = 1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then The perovskite composite oxide catalyst La _0.9 Sr _0.1 Co _0.5 Cu _0.5 O _3+δ can be obtained by calcining the sample at 700°C for 3 hours, which is denoted as catalyst C.

Example 4

Preparation of catalyst: according to the stoichiometric molar ratio La:Ba:Co:Ru=5:5:9:1, weigh a certain amount of lanthanum nitrate, barium acetate, cobalt nitrate and ruthenium chloride, and then molar ratio metal cation: lemon Acid = 1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then The perovskite composite oxide catalyst La _0.5 Ba _0.5 Co _0.9 Ru _0.1 O _3+δ can be obtained by calcining the sample at 700°C for 3 hours, which is denoted as catalyst D.

Example 5

Preparation of catalyst: according to the stoichiometric molar ratio La:K:Co:Rh=7:3:8:2, weigh a certain amount of lanthanum nitrate, potassium acetate, cobalt nitrate and rhodium nitrate, and then molar ratio metal cation: citric acid =1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then the The sample was calcined at 700°C for 3 hours, and the perovskite composite oxide catalyst La _0.7 K _0.3 Co _0.8 Rh _0.2 O _3+δ was obtained, which was denoted as catalyst E.

Example 6

Preparation of catalyst: according to the stoichiometric molar ratio La:Ca:Co:Pd=8:2:6:4, weigh a certain amount of lanthanum nitrate, calcium nitrate, cobalt oxalate and palladium chloride, and then molar ratio metal cation: lemon Acid = 1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then The perovskite composite oxide catalyst La _0.8 Ca _0.2 Co _0.6 Pd _0.4 O _3+δ can be obtained by calcining the sample at 700°C for 3 hours, which is denoted as catalyst F.

Example 7

Preparation of catalyst: According to the stoichiometric molar ratio La:Sr:Co:Pt=6:4:7:3, weigh a certain amount of lanthanum nitrate, strontium nitrate, cobalt nitrate and chloroplatinic acid, and then molar ratio metal cation: lemon Acid = 1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then The sample was calcined at 700°C for 3 hours to obtain a perovskite composite oxide catalyst La _0.6 Sr _0.4 Co _0.7 Pt _0.3 O _3+δ , which was denoted as catalyst G.

Example 8

Preparation of catalyst: According to the stoichiometric molar ratio La:Ba:Co:Cu=6:4:5:5, weigh a certain amount of lanthanum nitrate, barium nitrate, cobalt oxalate and copper sulfate, and then molar ratio metal cation: citric acid =1:1.1 Weigh an appropriate amount of citric acid, add it to distilled water, and use ultrasonic vibration to promote its dissolution. At 80 °C, water bath stirring is evaporated to a sol state, placed in an oven at 120 °C for drying, and then the The sample was calcined at 700°C for 3 hours, and the perovskite composite oxide catalyst La _0.6 Ba _0.4 Co _0.5 Cu _0.5 O _3+δ was obtained, which was denoted as catalyst H.

Example 9

Preparation of catalyst: Weigh a certain amount of lanthanum nitrate, barium nitrate and cobalt oxalate according to the stoichiometric molar ratio La:Ba:Co=6:4:10, and then weigh an appropriate amount in molar ratio of metal cation:citric acid=1:1.1 The citric acid was added into distilled water, and ultrasonic vibration was used to promote its dissolution. At 80 °C, the water bath was stirred and evaporated to a sol state, then placed in an oven at 120 °C for drying, and then the sample was calcined at 700 °C for 3h, that is, The perovskite composite oxide catalyst La _0.6 Ba _0.4 CoO _3+δ can be obtained, denoted as catalyst I, as a comparative catalyst.

Example 10

Catalyst performance evaluation: 20 g of catalyst A was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the catalyst particle size was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 50°C, the space velocity was 1.0h ^-1 , and the molar ratio of oxygen to α-isophorone was 2.5:1 , the reaction was carried out under the pressure of 0.3MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 80.3%, and the selectivity was 93.7%. The catalyst is operated for a long period, and after 1000 hours, the conversion rate is 79.7-80.1%, and the selectivity is 93.5-94.0%, that is, the catalyst has good stability.

Example 11

Catalyst performance evaluation: 20 g of catalyst B was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the particle size of the catalyst was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 30°C, the space velocity was 0.05h ^-1 , and the molar ratio of oxygen to α-isophorone was 5:1 , the reaction was carried out under the pressure of 0.6MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 79.4%, and the selectivity was 94.8%.

Example 12

Catalyst performance evaluation: 20 g of catalyst C was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the particle size of the catalyst was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 90°C, the space velocity was 1.6h ^-1 , and the molar ratio of oxygen to α-isophorone was 1.1:1 , the reaction is carried out under the pressure of 0.1MPa, the liquid product is detected and analyzed by gas chromatography, the conversion rate is 77.2%, and the selectivity is 92.9%.

Example 13

Catalyst performance evaluation: 20 g of catalyst D was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the particle size of the catalyst was 10-20 mesh. The raw material α-isophorone and air were continuously fed into the reactor equipped with catalyst, the reaction temperature was 40°C, the space velocity was 0.3h ^-1 , and the molar ratio of oxygen to α-isophorone in the air was 1.5 : 1, the reaction is carried out under the condition of a pressure of 2MPa, the liquid product is detected and analyzed by gas chromatography, the conversion rate is 76.6%, and the selectivity is 93.1%.

Example 14

Catalyst performance evaluation: 20 g of catalyst E was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the catalyst particle size was 10-20 mesh. The raw material α-isophorone and air were continuously fed into the reactor equipped with catalyst, the reaction temperature was 60°C, the space velocity was 0.5h ^-1 , and the molar ratio of oxygen to α-isophorone in the air was 2.0 : 1, the reaction is carried out under the pressure of 0.5MPa, the liquid product is detected and analyzed by gas chromatography, the conversion rate is 75.4%, and the selectivity is 94.5%.

Example 15

Catalyst performance evaluation: 20 g of catalyst F was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the particle size of the catalyst was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 70°C, the space velocity was 0.8h ^-1 , and the molar ratio of oxygen to α-isophorone was 3.0:1 , the reaction was carried out under the pressure of 0.8MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 74.7%, and the selectivity was 92.0%.

Example 16

Catalyst performance evaluation: 20 g of catalyst G was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the particle size of the catalyst was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 80°C, the space velocity was 1.2h ^-1 , and the molar ratio of oxygen to α-isophorone was 3.5:1 , the reaction was carried out under the pressure of 1.0MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 73.8%, and the selectivity was 93.6%.

Example 17

Catalyst performance evaluation: 20 g of catalyst H was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the catalyst particle size was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 50°C, the space velocity was 1.4h ^-1 , and the molar ratio of oxygen to α-isophorone was 4.5:1 , the reaction was carried out under the pressure of 1.5MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 72.1%, and the selectivity was 92.8%.

Comparative Example

Catalyst performance evaluation: 20 g of catalyst I was added to a stainless steel tubular reactor with an inner diameter of 12 mm, and the catalyst particle size was 10-20 mesh. The raw material α-isophorone and oxygen were continuously fed into the reactor equipped with catalyst, the reaction temperature was 50°C, the space velocity was 1.4h ^-1 , and the molar ratio of oxygen to α-isophorone was 4.5:1 , the reaction was carried out under the pressure of 1.5MPa, the liquid product was detected and analyzed by gas chromatography, the conversion rate was 58.6%, and the selectivity was 80.7%.

The above are all preferred embodiments of the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention fall within the protection scope of the present invention.

Claims (8)

1. a method that adopts perovskite type composite oxide to catalyze and synthesize tea ketone, it is characterized in that, under the catalysis of perovskite type composite oxide, take oxygen or air as oxidant, α-isophorone is in Oxidation is carried out under solvent-free conditions to obtain the tea ketone; The perovskite-type composite oxide is La _1-x X _x Co _1-y Y _y O _3+δ ; X is selected from one of K, Ca, Sr, and Ba; Y is selected from one of Mn, Fe, Cu, Ru, Rh, Pd, and Pt; wherein, x is 0.1-0.5, and y is 0.1-0.5. 2. the method that adopts perovskite type composite oxide to catalyze and synthesize tea ketone according to claim 1, is characterized in that, described oxidation reaction is carried out in trickle-bed reactor; The perovskite-type composite oxide is immobilized in a trickle-bed reactor, and α-isophorone and oxygen or air are continuously introduced into the trickle-bed reactor for reaction. 3. the method that adopts perovskite type composite oxide to catalyze the synthesis of tea ketone according to claim 2, is characterized in that, the mol ratio of oxygen contained in described oxygen or air and α-isophorone is 1.1-5:1. 4 . The method for catalyzing and synthesizing tea ketone using perovskite-type composite oxide according to claim 2 , wherein the mass space velocity of α-isophorone is 0.05-1.6 h ⁻¹ . 5. The method for catalyzing and synthesizing tea ketone using perovskite-type composite oxide according to claim 1, wherein the reaction pressure is 0.1-2MPa, and the reaction temperature is 30-90°C. 6. the method that adopts perovskite type composite oxide to catalyze and synthesize tea ketone according to claim 1, is characterized in that, the preparation method of described perovskite type composite oxide is as follows: Adding mixed salt and citric acid to the water, then ultrasonically promoting the dissolution, evaporating water to a sol state under heating conditions, and then drying and baking to obtain the perovskite-type composite oxide catalyst; The mixed salt is obtained by mixing the salt formed by La, X, Co, and Y. 7. The method for preparing a perovskite-type composite oxide catalyst according to claim 6, wherein the evaporation temperature is 80-90°C; The drying process is carried out in an oven, and the drying temperature is 110-130 °C; The baking temperature is 600-800°C, and the baking time is 1-3 hours. 8. the preparation method of perovskite type composite oxide catalyst according to claim 6, is characterized in that, described salt is a kind of in nitrate, acetate, sulfate, chloride and oxalate or more.