Catalyst, preparation method therefor and use thereof in reaction for synthesizing high-carbon ketone by means of condensation coupling of α-h-containing ketone and alcohol

Abstract

The present application relates to a preparation method for a supported transition metal catalyst, a supported transition metal catalyst, and the use of the supported transition metal catalyst in a reaction for synthesizing high-carbon ketone by means of condensation coupling of an α-H-containing ketone and an alcohol. The preparation process of the supported transition metal catalyst comprises adding a porous catalyst carrier into a transition metal salt solution, dissolving same, leaving same to stand, and drying, roasting and reducing same. The transition metal salt is selected from one or more of a transition metal nitrate, a transition metal formate, a transition metal oxalate and a transition metal acetate; and the transition metal is selected from transition metal elements in Group VIIB, Group VIII, Group IB and Group IIB, and the transition metal is a non-noble metal. The raw materials of the catalyst of the present application are easily available, and the preparation cost is low. During the catalysis of a condensation coupling reaction of an α-H-containing ketone and a small molecular alcohol, by means of the method, a target high-carbon ketone can be obtained with high selectivity, and an additional solvent and a hydrogen source are also not needed in the reaction; in addition, long-time stable operation can be achieved, and the method has good industrial application prospects.

Description

A catalyst, a preparation method thereof and application thereof in condensation reaction of ketone and alcohol containing α-H into high-carbon ketone

[0001] The present application claims priority to the Chinese patent application No. 202410817116.8, filed on June 24, 2024, entitled “A preparation method of a supported transition metal catalyst, the supported transition metal catalyst and application thereof in condensation reaction of ketone and alcohol containing α-H into high-carbon ketone”, and the Chinese patent application No. 202411125706.0, filed on August 16, 2024, entitled “A preparation method of a supported transition metal catalyst, the supported transition metal catalyst and application thereof in condensation reaction of ketone and alcohol containing α-H into high-carbon ketone”, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present application relates to the field of catalysis technology, in particular to a catalyst, a preparation method thereof and application thereof in condensation reaction of ketone and alcohol containing α-H into high-carbon ketone. BACKGROUND

[0003] Ketone can be used as an excellent organic solvent, and also can be used as an important organic chemical raw material in the synthesis of perfumes, organic synthesis, synthesis of pharmaceutical intermediates, etc. The synthesis of ketone in the prior art has limited means, and the reaction process is generally more complicated and has more by-products. For example, the corresponding alcohol can be oxidized and dehydrogenated to obtain ketone, or ketone and aldehyde can be subjected to aldol condensation reaction and then hydrogenation, etc. However, these methods have high production cost and generally have low product selectivity. For example, US4146581 once reported a method for preparing pentanone by condensation, dehydration and hydrogenation of acetaldehyde and acetone in the presence of hydrogen. However, the product obtained by this method has complex components, the selectivity of the target product is low, and high-pressure hydrogen is required for the reaction, which puts forward higher requirements for the reaction conditions.

[0004] The size of a ketone molecule affects its reactivity and energy release during reactions. Compared to small ketones, higher ketones have relatively larger molecular structures, enabling more complex and diverse chemical reactions. Existing technologies have disclosed the use of α-H-containing ketones to react with other small molecule carbonyl compounds such as ketones and aldehydes containing active α-H to obtain condensation coupling products, which can be further dehydrated and hydrogenated to prepare alkyl-grafted higher ketones. Alcohols have also been used as condensation coupling agents to couple with α-H-containing ketones to prepare higher ketones. All of the above-mentioned higher ketone reactions in existing technologies require four steps: hydrogenation (dehydrogenation of alcohol to obtain small molecule carbonyl compounds containing active α-H), aldol condensation (with a ketone containing α-H as the substrate), dehydration, and hydrogenation. This places high demands on catalyst design; reported catalyst systems include supported noble metal catalysts, homogeneous catalysts, or composite oxide catalysts. For example, CN106732555A reports a Pd / C catalyst for the α-alkylation reaction of ketones and alcohols, but the reaction of acetophenone with n-butanol requires the use of the solvent 1,4-dioxane. CN111889105A discloses a bifunctional catalyst for the alkylation of methanol-butanone to prepare 3-pentanone, the catalyst composition of which includes 2-30% nickel oxide, 40-90% magnesium oxide, 10-30% aluminum oxide and 0-20% zinc oxide, the reaction temperature is 220-350℃, and the molar ratio of methanol / butanone is 5-15:1. CN110423190A and CN106905125A report an iron complex and a cobalt complex, respectively, for the α-alkylation reaction of ketones. The catalysts are obtained by reacting 4'-dimethylaminophenyl-2,2':6',2”-terpyridine with anhydrous ferrous chloride and 2,2;6,2”-terpyridine with cobalt chloride, respectively. It is not difficult to find problems in these publicly available technologies, such as expensive catalysts, complicated and demanding reaction conditions, and difficulties in product separation and catalyst recovery.

[0005] Summary of the Invention

[0006] To address the above problems, this application provides a method for preparing a supported transition metal catalyst, the supported transition metal catalyst, and its application in the condensation coupling of α-H-containing ketones and alcohols to form higher carbon ketones.

[0007] In a first aspect, this application provides a method for preparing a supported transition metal catalyst; the preparation steps include:

[0008] S1. Dissolve at least one transition metal salt in water to obtain a solution; wherein the transition metal salt is selected from one or more of transition metal nitrates, transition metal formates, transition metal oxalates, and transition metal acetates;

[0009] S2. Add a porous catalyst support to the solution and stir at room temperature until the mixture is homogeneous to obtain a mixture;

[0010] S3. The mixture is placed in an oven and dried at 80-110°C to constant weight to obtain a dried product;

[0011] S4. The dried product is calcined in a calcination device at 250-390°C for 5-8h to obtain a calcined product;

[0012] S5. The calcined product is heated to 250-450°C in a reaction device and reduced in a reducing atmosphere for 2-8h to obtain the supported transition metal catalyst;

[0013] The molar ratio n1:n2:n3 of the transition metal salt, water and porous catalyst support is: 1:50:5≤n1:n2:n3≤1:100:20.

[0014] Preferably, the heating rate of the calcination is 2-10°C / min and the calcination temperature is 300-350°C.

[0015] Preferably, the heating rate of the heating in step S5 is 2-10°C / min and the reduction temperature is 300-350°C.

[0016] Preferably, the transition metal in the transition metal salt is selected from at least one of Mn, Ni, Co, Fe, Zn and Cu.

[0017] Preferably, the transition metal salt is selected from two or more of transition metal nitrate, transition metal formate, transition metal oxalate and transition metal acetate.

[0018] Preferably, the porous catalyst support is selected from at least one of porous carbon material, alkaline earth oxide, silicon oxide, silicon-aluminum oxide and diatomite.

[0019] Preferably, the reducing atmosphere is a H2 / N2 mixed gas stream.

[0020] The volume percentage of H2 in the H2 / N2 mixed gas stream is 5%-50%.

[0021] In a second aspect, the application also provides a supported transition metal catalyst prepared by the preparation method described above.

[0022] Preferably, the supported transition metal catalyst is Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, Co2 / AC, Ni5-Fe1 / CNT or Ni5-Fe1 / MgO.

[0023] The AC in the Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC and Co2 / AC is activated carbon.

[0024] In a third aspect, the application further provides a method for catalytic synthesis of high-carbon ketones, comprising the following steps:

[0025] In a closed reaction device, the supported transition metal catalyst described in the technical solution above is used as a catalyst, and alcohol and an α-H-containing ketone are used as reaction substrates; under the conditions of normal pressure as the initial pressure and 120-250℃ as the reaction temperature, a high-carbon ketone is prepared through a condensation coupling reaction.

[0026] Preferably, the alcohol is selected from at least one of aliphatic alcohols, aromatic alcohols, alicyclic alcohols and alcohols containing heteroatom substituents.

[0027] Preferably, the α-H-containing ketone is selected from at least one of aliphatic ketones, aromatic ketones, alicyclic ketones and ketones containing heteroatom substituents.

[0028] Preferably, the molar ratio of the α-H-containing ketone to the alcohol is 1:2-2:1.

[0029] Preferably, the feeding ratio of the α-H-containing ketone to the supported transition metal catalyst is 0.2-0.3 g of the supported transition metal catalyst per 1 mol of ketone.

[0030] Preferably, the temperature of the condensation reaction is 160-210℃, and the reaction time is 30-300 min.

[0031] Preferably, the condensation coupling reaction is carried out in a tank reactor, a fixed bed or a fluidized bed process; and the condensation coupling reaction is carried out in a continuous method with simultaneous feeding and discharging.

[0032] The transition metal catalyst provided by the application can efficiently catalyze the condensation coupling reaction of ketones and small-molecule alcohols, and obtain target high-carbon ketones with high selectivity. Moreover, the metal used in the catalyst is a non-noble metal, and the raw materials used in the catalyst are easy to obtain, which significantly reduces the cost of the catalyst. When the ketone alcohol condensation reaction is catalyzed by the catalyst of the application, no external solvent is needed, no high-pressure hydrogen is needed, the reaction process is easy to implement, and the preparation method is simple. In addition, the conversion rate of the condensation coupling of the catalyst is high, and the types of alcohols applicable are wide. The conversion rates of the alcohol and the ketone can be as high as 80% or more, the selectivity of the target high-carbon ketone can be as high as 90% or more, and the catalyst can be stably operated for a long time, which has a good industrial application prospect. DETAILED DESCRIPTION

[0033] In order to better understand the technical solutions of the application, the embodiments of the application are described in detail below with reference to the drawings.

[0034] It should be understood that the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0035] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0036] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0037] In the description of this specification, it should be understood that the terms "substantially", "approximately", "about", "about", "generally", "largely" used in the claims and embodiments of this application refer to values ​​that can be generally agreed upon within a reasonable range of process operations or tolerances, rather than a precise value.

[0038] The present application will be further described below with reference to specific embodiments, but this does not limit the present application.

[0039] A method for preparing a supported transition metal catalyst includes the following preparation steps:

[0040] S1. Dissolve at least one transition metal salt in water to obtain a solution; wherein the transition metal salt is selected from one or more of transition metal nitrates, transition metal formates, transition metal oxalates, and transition metal acetates;

[0041] S2. Add a porous catalyst support to the solution and stir at room temperature until the mixture is homogeneous to obtain a mixture;

[0042] S3. Place the mixture in an oven and dry it at 80-110°C until constant weight to obtain the dried product;

[0043] S4. The dried material is heated to 250-390℃ in a calcination apparatus and calcined for 5-8 hours to obtain the calcined material;

[0044] S5. The calcined material is heated to 250-450°C in a reaction apparatus and reduced in a reducing atmosphere for 2-8 hours to obtain the supported transition metal catalyst.

[0045] The molar ratio n1:n2:n3 of the transition metal salt, water and porous catalyst carrier is: 1:50:5≤n1:n2:n3≤1:100:20.

[0046] In the present application, the molar ratio n1:n2:n3 of the transition metal salt, water and porous catalyst carrier is: 1:50:5≤n1:n2:n3≤1:100:20, preferably 1:60:8≤n1:n2:n3≤1:80:12. In the embodiment of the present application, the n1:n2:n3 can be 6:50:320.

[0047] In the present application, the heating rate of the calcination is preferably 2-10℃ / min, and the calcination temperature is preferably 300-350℃. In the embodiment of the present application, the heating rate of the calcination can be 3℃ / min, 5℃ / min, 7℃ / min or 9℃ / min; the temperature of the calcination can be 300℃, 250℃, 350℃, 330℃ or 300℃; and the time of the calcination can be 8h.

[0048] In the present application, the heating rate of the temperature rise in step S5 is preferably 2-10℃ / min, and the temperature of the reduction is preferably 300-350℃. In the embodiment of the present application, the heating rate of the reduction can be 5℃ / min; the temperature of the reduction can be 400℃, 300℃, 250℃ or 450℃; and the time of the reduction can be 8h.

[0049] In the present application, the transition metal element in the transition metal salt is preferably a transition metal element in Group ⅦB, Group Ⅷ, Group ⅠB or Group ⅡB of the chemical element periodic table, and the transition metal element is preferably a non-noble metal element; the transition metal element is preferably selected from at least one of Mn, Ni, Co, Fe, Zn and Cu; and the transition metal element is preferably selected from at least one of Ni, Co and Cu.

[0050] In the present application, the transition metal salt is preferably selected from two or more of transition metal nitrate, transition metal formate, transition metal oxalate and transition metal acetate. In the embodiment of the present application, the transition metal salt can be nickel nitrate hexahydrate and iron nitrate nonahydrate with a molar ratio of 5:1, nickel nitrate hexahydrate and iron nitrate nonahydrate with a molar ratio of 2:1, cobalt acetate and cobalt nitrate with a molar ratio of 5:1, nickel acetate and copper acetate with a molar ratio of 5:1, cobalt nitrate and zinc nitrate with a molar ratio of 5:1, manganese nitrate and copper nitrate with a molar ratio of 5:1, nickel nitrate and iron nitrate with a molar ratio of 5:1, nickel nitrate or cobalt nitrate.

[0051] In the present application, the transition metal element used in the catalyst is a non-noble metal, and the catalyst raw material is easy to obtain, which significantly reduces the cost of the catalyst.

[0052] In the present application, the porous catalyst carrier is preferably at least one selected from the group consisting of porous carbon material, alkaline earth oxide, aluminum oxide, silicon oxide, silicon aluminum oxide and diatomite; the porous carbon is preferably carbon nanotube or activated carbon; and more preferably selected from porous carbon and / or magnesium oxide.

[0053] In the present application, the pores and the connection between the pores of the porous catalyst carrier are small, and the catalyst is limited in the pores after being loaded, which is not easy to agglomerate, and the service life of the catalyst is significantly improved.

[0054] The present application also provides a supported transition metal catalyst prepared by the preparation method.

[0055] In the present application, the supported transition metal catalyst is preferably Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, Co2 / AC, Ni5-Fe1 / CNT or Ni5-Fe1 / MgO.

[0056] The AC in the Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC and Co2 / AC is preferably activated carbon.

[0057] In the present application, the subscript in the supported transition metal catalyst is preferably a molar ratio.

[0058] In addition, the present application also provides a catalytic synthesis method of high-carbon ketone, which comprises the following steps:

[0059] In a closed reaction device, the supported transition metal catalyst described in the above technical solution is used as a catalyst, and alcohol and ketone containing alpha-H are used as reaction substrates; high-carbon ketone is prepared by condensation coupling reaction under the condition that the initial pressure is normal pressure and the reaction temperature is 120-250℃.

[0060] In the present application, the alcohol is preferably at least one selected from the group consisting of aliphatic alcohol, aromatic alcohol, alicyclic alcohol and alcohol containing heteroatom substituent; and the alcohol is preferably at least one selected from the group consisting of ethanol, n-propanol, isopropanol, ethylene glycol, phenethyl alcohol, cyclohexanol and ethanolamine.

[0061] In the present application, the α-H containing ketone is preferably at least one selected from the group consisting of aliphatic ketone, aromatic ketone, alicyclic ketone and heteroatom containing substituted ketone, more preferably at least one selected from the group consisting of acetone, butanone, pentanone, phenyl ethyl ketone, cyclohexanone and 1-amino-2-propanone.

[0062] In the present application, the condensation coupling reaction is preferably carried out by a process such as a tank reactor, a fixed bed or a fluidized bed. Further preferably, the reaction is carried out by a continuous method with simultaneous feeding and discharging; the process operation steps can be further simplified to realize batch industrial production.

[0063] In the present application, the molar ratio of the α-H containing ketone and alcohol is preferably 1:2-2:1, and the usage ratio of the α-H containing ketone to the supported transition metal catalyst is preferably 1 mol:(0.2-0.3) g.

[0064] In the present application, the condensation coupling reaction is preferably carried out by a continuous method with simultaneous feeding and discharging; the temperature of the condensation coupling reaction is preferably 160-210°C, and the reaction time is preferably 30-300 min.

[0065] For example, refer to the following Examples 1-10:

[0066] Example 1

[0067] Dissolve nickel nitrate hexahydrate and iron nitrate nonahydrate in water, add activated carbon, stir at room temperature for 7-10 h, and then place in an oven at 100°C to dry to constant weight. The molar ratio of nickel nitrate hexahydrate, iron nitrate nonahydrate, activated carbon and water is 5:1:50:320. After drying to constant weight, place in a muffle furnace to calcine at 300°C for 6 h at an air atmosphere (heating rate 5°C / min), and then reduce at 400°C for 8 h in a 5% (volume percentage of hydrogen) H2 / N2mixed gas stream (heating rate 5°C / min) to obtain the catalyst, which is recorded as Ni5-Fe1 / AC.

[0068] Examples 2-6

[0069] Use the same method as in Catalyst Preparation Example 1, but change the transition metal nitrate and its ratio, reaction conditions, and the calcination temperature is set to 300°C, 250°C, 350°C, 330°C and 300°C, respectively; the heating rate is set to 5°C / min, 7°C / min, 9°C / min, 3°C / min and 5°C / min, respectively; and the reduction temperature is preferably 400°C, 300°C, 250°C, 450°C and 400°C, respectively.

[0070] The obtained catalysts are recorded as Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn1 / AC, Mn5-Cu1 / AC, respectively. The specific feeding ratio is shown in Table 1 below.

[0071] Examples 7-8

[0072] Using the same method and reaction conditions as catalyst preparation example 1, changing the catalyst carrier, using carbon nanotubes CNT, MgO as catalyst carrier, the obtained catalysts are respectively recorded as: Ni5-Fe1 / CNT, Ni5-Fe1 / MgO.

[0073] Examples 9-10

[0074] Using the same method and reaction conditions as catalyst preparation example 1, using a single transition metal nitrate as the substrate, the obtained catalysts are respectively recorded as: Ni5 / AC, Co2 / AC.

[0075] Table 1: Substrate feeding table for preparation of transition metal catalysts

[0076] Exemplarily, please refer to the following condensation coupling reaction examples 11-31:

[0077] Condensation coupling reaction example 11

[0078] In a 100 mL high-pressure reactor, 0.05 g of catalyst Ni5-Fe1 / AC, 20 mL of ethanol and 20 mL of acetone were sequentially added, and the reaction was carried out at a temperature of 175°C for 1.7 h, and the stirring speed of the stirring assembly was maintained at 500 r / min during the reaction. After the reaction was completed, gas chromatography analysis showed that the conversion rate of ethanol was 92%, the conversion rate of acetone was 87%, and the selectivity of 2-pentanone was 83%.

[0079] Condensation coupling reaction examples 12-31

[0080] Using a method similar to reaction example 11, changing the reaction conditions and substrates, and analyzing the composition of the reaction products, the reaction conditions and catalytic performance results of the coupling reaction examples are shown in Table 2 below:

[0081] Table 2. Reaction conditions and catalytic performance results of condensation coupling reaction examples

[0082] When the catalysts of the present application are used to catalyze the condensation reaction of ketones and alcohols, no external solvent or high-pressure hydrogen gas is required, the reaction process is easy to implement, and the preparation method is simple. In addition, the catalyst has a high conversion rate for condensation coupling and is widely applicable to various types of alcohols, with a conversion rate of alcohol and ketone of up to 80% or more, a selectivity of target high-carbon ketone of up to 90% or more, and long-term stable operation, which has a good industrial application prospect.

Claims

1. A process for the preparation of a supported transition metal catalyst, characterized in that, The preparation method comprises the following steps: S1. Dissolving at least one transition metal salt in water to obtain a solution; the transition metal salt is selected from one or more of transition metal nitrate, transition metal formate, transition metal oxalate and transition metal acetate; S2. Adding a porous catalyst carrier to the solution and stirring at room temperature until mixed uniformly to obtain a mixture; S3. Placing the mixture in an oven and drying at 80-110°C until constant weight to obtain a dry substance; S4. Heating the dry substance in a calcination device to 250-390°C and calcining for 5-8h to obtain a calcined substance; S5. Heating the calcined substance in a reaction device to 250-450°C and reducing in a reducing atmosphere for 2-8h to obtain the supported transition metal catalyst. The molar ratio of the transition metal salt, water and the porous catalyst carrier n1:n2:n3 is 1:50:5≤n1:n2:n3≤1:100:

20.

2. The production method according to claim 1, characterized by, The heating rate of the calcination is 2-10°C / min and the calcination temperature is 300-350°C.

3. The preparation method according to claim 1, characterized in that, The heating rate of the heating in step S5 is 2-10°C / min and the reduction temperature is 300-350°C.

4. The production method according to claim 1, characterized by, The transition metal in the transition metal salt is selected from at least one of Mn, Ni, Co, Fe, Zn and Cu.

5. The method of claim 1, wherein, The transition metal salt is selected from two or more of transition metal nitrate, transition metal formate, transition metal oxalate and transition metal acetate.

6. The method of claim 1, wherein, The porous catalyst carrier is selected from at least one of porous carbon material, alkaline earth oxide, silicon oxide, silicon-aluminum oxide and diatomite.

7. The preparation method according to claim 1, characterized in that, The reducing atmosphere is H2 / N2 mixed gas stream; The volume percentage of H2 in the H2 / N2 mixed gas stream is 5%-50%.

8. The supported transition metal catalyst prepared by the preparation method in any one of claims 1-7.

9. The supported transition metal catalyst of claim 8, wherein, The supported transition metal catalyst is Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, Co2 / AC, Ni5-Fe1 / CNT or Ni5-Fe1 / MgO; The AC in the Ni5-Fe1 / AC, Ni2-Fe1 / AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC and Co2 / AC is activated carbon.

10. The use of the supported transition metal catalyst in claim 8 or 9 in the condensation coupling of an α-H-containing ketone and an alcohol to form a high-carbon ketone.

11. A process for the catalytic synthesis of a higher carbon ketone, characterized by, The steps are: In a closed reaction device, the supported transition metal catalyst in claim 8 or 9 is used as a catalyst, an alcohol and an α-H-containing ketone are used as reaction substrates, and a high-carbon ketone is prepared by condensation coupling reaction under the conditions of normal pressure as the initial pressure and 120-250°C as the reaction temperature.

12. The catalytic synthesis method of claim 11, wherein, The alcohol is selected from at least one of aliphatic alcohol, aromatic alcohol, alicyclic alcohol and alcohol containing heteroatom substituent.

13. The catalytic synthesis method of claim 11, wherein, The α-H containing ketone is selected from at least one of aliphatic ketone, aromatic ketone, alicyclic ketone and heteroatom containing substituted ketone.

14. The catalytic synthesis method according to claim 11, wherein the molar ratio of the α-H containing ketone and alcohol is 1:2-2:

1.

15. The catalytic synthesis method of claim 14, wherein, The feeding ratio of the α-H containing ketone to the supported transition metal catalyst is 0.2-0.3 g of the supported transition metal catalyst per 1 mol of ketone.

16. The catalytic synthesis method of claim 11, wherein, The temperature of the condensation coupling reaction is 160-210 ℃, and the reaction time is 30-300 min.

17. The catalytic synthesis method according to claim 11 or 16, characterized in that, The condensation coupling reaction is carried out in a tank reactor, a fixed bed or a fluidized bed process; the condensation coupling reaction is carried out by a continuous method with simultaneous feeding and discharging.

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