Catalyst, manufacturing process and use in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols thereof

Abstract

The present application relates to a manufacturing process for a supported transition metal catalyst, a supported transition metal catalyst, and its use in the synthesis of high-carbon ketones by acyloin condensation of α-hydrogen-containing ketones and alcohols. The manufacturing process of the supported transition metal catalyst comprises adding a porous catalyst support to a solution of a transition metal salt, dissolving, standing, drying, calcining, and reducing. The transition metal salt is selected from one or more of the transition metal nitrate, transition metal formate, transition metal oxalate, and transition metal acetate. The transition metal is selected from the transition metal elements of Group VIIB, VIII, IB, or IIB, and the transition metal is not a non-precious metal. The raw materials for the catalyst according to the present application are readily available and inexpensive to produce.The acyloin condensation of α-hydrogen-containing ketones and low-molecular-weight alcohols allows for the highly selective production of desired high-carbon ketones without the need for solvents or hydrogen sources during the reaction. The catalyst is also stable under long-term operating conditions and therefore has good prospects for industrial applications.

Description

TECHNICAL AREA

[0001] The present application claims priority from the Chinese application number 202410817116.8 entitled "Process for a supported transition metal catalyst, supported transition metal catalyst and its use in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols", filed with the Chinese Patent Office on June 24, 2024, and priority from the application number 202411125706.0 entitled "Process for a supported transition metal catalyst, supported transition metal catalyst and its use in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols", filed with the Chinese Patent Office on August 16, 2024, the contents of which are incorporated into the present application by reference. STATE OF THE ART

[0002] The present application relates to the field of catalysis technology, in particular a catalyst, a manufacturing process and a use in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols thereof.

[0003] Ketones are excellent organic solvents and, as important organic chemical feedstocks, find widespread use in the synthesis of fragrances, organic synthesis, and the production of pharmaceutical intermediates. Prior art methods for ketone synthesis are limited, and the reaction processes are generally relatively complex and generate many byproducts. For example, ketones can be prepared by oxidation and dehydrogenation of the corresponding alcohol or by aldol condensation of ketone and aldehyde followed by hydrogenation. However, these processes are associated with high production costs and generally exhibit low product selectivity. As described, for example, in US patent 4146581, acetaldehyde and acetone can be prepared in the presence of hydrogen by condensation, dehydration, and hydrogenation to give pentanone.However, the product components obtained in this process are complex, the selectivity for the target product is low, and the reaction requires the addition of hydrogen under high pressure, which places high demands on the reaction conditions.

[0004] The size of ketone molecules influences their reactivity and energy release during reaction processes. High-carbon ketones have a relatively large molecular structure compared to low-molecular-weight ketones, which enables more complex and diverse chemical reactions. Prior art processes are known in which α-hydrogen-containing ketones and other low-molecular-weight carbonyl compounds, such as active α-hydrogen-containing ketones and aldehydes, are used to obtain products via acyloin condensation. These products can then be further processed by dehydration and hydrogenation to yield alkyl-branched, high-carbon ketones. There are also processes in which alcohol is used as a reagent for acyloin condensation to produce high-carbon ketones via coupling reactions with α-hydrogen-containing ketones.In the prior art, the reactions mentioned above for high-carbon ketones require four steps: hydrogen transfer (dehydrogenation of alcohols to low-molecular-weight, active α-hydrogen-containing carbonyl compounds), aldol condensation (substrates with α-hydrogen-containing ketones), dehydration, and hydrogenation, which places high demands on the design of the catalysts. Catalyst systems known from the prior art include supported noble metal catalysts, homogeneous catalysts, and mixed oxide catalysts. For example, CN106732555A describes a Pd / C catalyst for the α-alkylation of ketones with alcohols, although the solvent 1,4-dioxane was required for the catalysis of the reaction of acetophenone with n-butanol. CN111889105A discloses a bifunctional catalyst for the production of 3-pentanone by alkylation of methanol with butanone.The catalyst composition consists of 2 to 30% nickel oxide, 40 to 90% magnesium oxide, 10 to 30% aluminum oxide, and 0 to 20% zinc oxide. The reaction temperature is between 220 °C and 350 °C, and the molar ratio of methanol to butanone is 5–15:1. CN110423190A and CN106905125A each describe the catalysis of the α-alkylation of ketones by iron complexes and cobalt complexes, respectively, with the catalysts being obtained by reacting 4'-dimethylaminophenyl-2,2':6',2"-terpyridine with anhydrous iron chloride and 2,2':6',2"-terpyridine with cobalt chloride, respectively. With these published technologies, problems such as expensive catalysts, complicated and strict reaction conditions, difficult product separation and catalyst recovery are easily identifiable. CONTENT OF THE PRESENT INVENTION

[0005] To solve the problems mentioned above, the present application provides a manufacturing process for a supported transition metal catalyst, a supported transition metal catalyst and its use in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols.

[0006] In a first aspect, the present application provides for a manufacturing process for a supported transition metal catalyst, comprising the following steps: S1. Dissolving 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 nitrate, transition metal formate, transition metal oxalate and transition metal acetate; S2. Add a porous catalyst support to the solution and stir at room temperature until homogeneous mixing is achieved to obtain a mixture; S3. Place the mixture in an oven and dry at 80 °C to 110 °C until constant weight is achieved to obtain a dried product; S4. Heating the dried product in a calcining device to 250 °C to 390 °C and calcining for 5 to 8 hours to obtain a calcined product; and S5. Heating the calcined product in a reaction apparatus to 250 °C to 450 °C and reducing in a reducing atmosphere for 2 to 8 hours to obtain the supported transition metal catalyst, wherein The molar ratio n1 : n2 : n3 between the transition metal salt, water and the porous catalyst support is 1 : 50 : 5 ≤ n1 : n2 : n3 ≤ 1 : 100 : 20.

[0007] Preferably, the heating rate during calcination is 2 to 10 °C / min and the calcination temperature is 300 °C to 350 °C.

[0008] Preferably, it is provided that in step S5 the heating rate is 2 to 10 °C / min and the temperature during reduction is 300 °C to 350 °C.

[0009] Preferably, a transition metal in the transition metal salt is selected from at least one of Mn, Ni, Co, Fe, Zn and Cu.

[0010] 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.

[0011] Preferably, the porous catalyst support is selected from at least one of porous carbon material, alkaline earth oxide, silicon dioxide, silicon aluminum oxide and diatomaceous earth.

[0012] Preferably, the reducing atmosphere refers to an H2 / N2 mixed gas stream. where the volume fraction of H2 in the H2 / N2 mixed gas stream is 5% to 50%.

[0013] In a second aspect, the present application provides for a supported transition metal catalyst which is produced by a manufacturing process according to the above technical solution.

[0014] Preferably, the supported transition metal catalyst is Ni5-Fe1AC, Ni2-Fe1AC, Ni5Co1AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC, Co2 / AC, Ni5-Fe1CNT or Ni5-Fe1 / MgO, where the AC consisting of Ni5-Fe1 / AC, Ni2-Fe1AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / AC, Ni5 / AC and Co2 / AC is activated carbon.

[0015] In a third aspect, the present application provides a method for the catalytic synthesis of high-carbon ketones, comprising the following steps: Production of a high-carbon ketone by acyloin condensation using a supported transition metal catalyst according to the above technical solution as catalyst and an alcohol and an α-H-containing ketone as reaction substrates in a closed reaction apparatus at an initial pressure of atmospheric pressure and a reaction temperature of 120 °C to 250 °C.

[0016] Preferably, the alcohol is selected from at least one of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol and an alcohol with heteroatom-containing substituents.

[0017] Preferably, the α-H-containing ketone is selected from at least one of aliphatic ketone, aromatic ketone, alicyclic ketone and ketone with heteroatom-containing substituents.

[0018] Preferably, the molar ratio between the α-H-containing ketone and the alcohol is 1 : 2 to 2 : 1.

[0019] Preferably, the addition ratio of the supported transition metal catalyst to the α-H-containing ketone is such that 0.2 to 0.3 g of the supported transition metal catalyst are added per 1 mol of ketone.

[0020] Preferably, the temperature of the acyloin condensation is 160 °C to 210 °C and the reaction time is 30 to 300 minutes.

[0021] Preferably, the acyloin condensation is carried out in a boiler reactor, a fixed bed process or a fluidized bed process; and the acyloin condensation is carried out in a continuous process with simultaneous feeding and removal.

[0022] The transition metal catalyst according to the present application enables the efficient catalysis of the acyloin condensation of ketones and low-molecular-weight alcohols, thereby yielding highly selective, desired high-carbon ketones. The metals used in the catalyst are non-precious metals whose raw materials are readily available, significantly reducing the catalyst's cost. The catalysis of the acyloin condensation of ketones and alcohols using the catalyst of the present application eliminates the need for an additional solvent and high-pressure hydrogen, resulting in a simple reaction process and a simplified manufacturing procedure. Furthermore, this catalysis exhibits a high conversion rate for the acyloin condensation and broad applicability to various types of alcohols.The conversion rate of alcohols and ketones can exceed 80%, while the selectivity for the desired high-carbon ketones can exceed 90%. Furthermore, this catalysis is stable over the long term and therefore has good prospects for industrial applications. DETAILED DESCRIPTION

[0023] To better understand the technical solution of the present application, the embodiments of the present application are described in detail below with reference to the attached drawings.

[0024] It goes without saying that the described embodiments represent only a portion of the embodiments of the present application and do not encompass all embodiments. All further embodiments that would be apparent to the person skilled in the art without inventive step, starting from the embodiments of the present application, also fall within the scope of protection of the present application.

[0025] The terms used in the embodiments of this application serve only to describe certain embodiments and are not to be understood as limiting the present application. The singular forms "a / an", "the" and "this" used in the embodiments and in the claims of this application also include plural forms, unless the context clearly indicates otherwise.

[0026] It is understood that the terms "and / or" used here serve only to describe a relationship between related objects and can denote three possible relationships, e.g., A and / or B, which can mean three cases: A exists alone, A and B exist simultaneously, B exists alone. Incidentally, the symbol " / " in this text normally means that the preceding and following objects are in an "or" relationship to each other.

[0027] The description points out that the terms “essentially”, “approximately”, “about”, “roughly” and “on the whole” used in the claims and embodiments of the present application have a general meaning within the scope of reasonable technical handling or a reasonable tolerance range and do not denote exact values.

[0028] The present application will be explained in more detail below using specific examples, but will not be limited to them.

[0029] A manufacturing process for a supported transition metal catalyst is provided, comprising the following steps: S1. Dissolving 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 nitrate, transition metal formate, transition metal oxalate and transition metal acetate; S2. Add a porous catalyst support to the solution and stir at room temperature until homogeneous mixing is achieved to obtain a mixture; S3. Place the mixture in an oven and dry at 80 °C to 110 °C until constant weight is achieved to obtain a dried product; S4. Heating the dried product in a calcining device to 250 °C to 390 °C and calcining for 5 to 8 hours to obtain a calcined product; and S5. Heating the calcined product in a reaction apparatus to 250 °C to 450 °C and reducing in a reducing atmosphere for 2 to 8 hours to obtain the supported transition metal catalyst, wherein The molar ratio n1: n2 : n3 between the transition metal salt, water and the porous catalyst support is 1 : 50 : 5 ≤ n1 : n2 : n3 ≤ 1 : 100 : 20.

[0030] Within the scope of the present invention, the molar ratio n1 : n2 : n3 between the transition metal salt, water, and the porous catalyst support is 1 : 50 : 5 ≤ n1 : n2 : n3 ≤ 1 : 100 : 20, preferably 1 : 60 : 8 ≤ n1 : n2 : n3 ≤ 1 : 80 : 12. In an embodiment of the present invention, n1 : n2 : n3 can be 6 : 50 : 320.

[0031] Within the scope of the present invention, it is provided that during calcination, the heating rate is preferably 2 to 10 °C / min and the calcination temperature is preferably 300 °C to 350 °C. In an embodiment of the present invention, it is provided that during calcination, the heating rate can be 3 °C / min, 5 °C / min, 7 °C / min or 9 °C / min, the temperature 300 °C, 250 °C, 350 °C, 330 °C or 300 °C, and the time 8 h.

[0032] Within the scope of the present invention, it is provided that in step S5 the heating rate is preferably 2 to 10 °C / min and the temperature during reduction is preferably 300 °C to 350 °C. In an embodiment of the present invention, it is provided that during reduction the heating rate can be 5 °C / min, the temperature 400 °C, 300 °C, 250 °C or 450 °C and the time 8 h.

[0033] Within the scope of the present invention, it is provided that the transition metal elements in the transition metal salt are transition metal elements of group VIIB, VIII, IB or IIB of the chemical periodic table, wherein the transition metal elements are preferably non-precious metal elements; that the transition metal element is preferably selected from at least one of Mn, Ni, Co, Fe, Zn and Cu; and that the transition metal element is preferably selected from at least one of Ni, Co and Cu.

[0034] Within the scope of the present invention, 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 one embodiment of the present invention, the transition metal salt is nickel(II) nitrate hexahydrate and iron(III) nitrate nonahydrate in a molar ratio of 5:1, nickel(II) nitrate hexahydrate and iron(III) nitrate nonahydrate in a molar ratio of 2:1, nickel nitrate and cobalt nitrate in a molar ratio of 5:1, nickel nitrate and copper acetate in a molar ratio of 5:1, cobalt nitrate and zinc nitrate in a molar ratio of 5:1, manganese nitrate and copper nitrate in a molar ratio of 5:1, nickel nitrate and iron nitrate, or nickel nitrate or cobalt nitrate in a molar ratio of 5:1.

[0035] Within the scope of the present invention, it is provided that the transition metal elements used in the catalyst are non-precious metals whose raw materials are readily available, which significantly reduces the cost of the catalyst.

[0036] Within the scope of the present invention, it is provided that the porous catalyst support is preferably selected from at least one of porous carbon material, alkaline earth oxide, aluminum oxide, silicon dioxide, silicon aluminum oxide and diatomaceous earth, wherein the porous carbon is preferably carbon nanotube or activated carbon; and that the porous catalyst support is more preferably selected from porous carbon and / or magnesium oxide.

[0037] Within the scope of the present invention, it is provided that connecting openings between the pores of the porous catalyst support are relatively small, the catalyst remains enclosed in the pores after loading, does not agglomerate easily, and the lifetime of the catalyst is significantly increased.

[0038] The present invention further provides a supported transition metal catalyst which is produced by a manufacturing process according to the above technical solution.

[0039] Within the scope of the present invention, it is provided that 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, wherein the AC consisting of 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.

[0040] Within the scope of the present invention, it is provided that the subscription in the supported transition metal catalyst preferably represents the molar ratio.

[0041] Furthermore, the present application provides a method for the catalytic synthesis of high-carbon ketones, comprising the following steps: Production of a high-carbon ketone by acyloin condensation using a supported transition metal catalyst according to the above technical solution as catalyst and an alcohol and an α-H-containing ketone as reaction substrates in a closed reaction apparatus at an initial pressure of atmospheric pressure and a reaction temperature of 120 °C to 250 °C.

[0042] Within the scope of the present invention, it is provided that the alcohol is preferably selected from at least one of aliphatic alcohol, aromatic alcohol, alicyclic alcohol and alcohol with heteroatom-containing substituents; and that the alcohol is preferably selected from at least one of ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, phenethyl alcohol, cyclohexanol and monoethanolamine.

[0043] Within the scope of the present invention, it is provided that the α-H-containing ketone is preferably selected from at least one of aliphatic ketone, aromatic ketone, alicyclic ketone and ketone with heteroatom-containing substituents, more preferably selected from at least one of acetone, butanone, pentanone, acetophenone, cyclohexanone and aminoacetones.

[0044] Within the scope of the present invention, it is provided that the acyloin condensation preferably takes place in a boiler reactor, a fixed-bed process, or a fluidized-bed process. Furthermore, it is preferably provided that the reaction is carried out in a continuous process with simultaneous loading and unloading, so that the process steps can be further simplified and industrial series production becomes possible.

[0045] Within the scope of the present invention, it is provided that the molar ratio between the α-H-containing ketone and the alcohol is preferably 1 : 2 to 2 : 1, and the amount of the supported transition metal catalyst for the α-H-containing ketones is preferably 1 mol : (0.2 to 0.3) g.

[0046] Within the scope of the present invention, it is provided that the acyloin condensation is preferably carried out in a continuous process with simultaneous feeding and removal, and that the temperature of the acyloin condensation is preferably 160 °C to 210 °C and the reaction time is preferably 30 to 300 minutes. The following exemplary embodiments I to X are referenced as examples: Example I

[0047] Nickel(II) nitrate hexahydrate and iron(III) nitrate nonahydrate are dissolved in water, mixed with activated carbon, stirred for 7 to 10 hours at room temperature, and dried in an oven at 100 °C until constant weight is achieved. The molar ratio of nickel(II) nitrate hexahydrate, iron(III) nitrate nonahydrate, activated carbon, and water is 5 : 1 : 50 : 320. After drying to constant weight, the product is placed in a muffle furnace and calcined for 6 hours at 300 °C in an air atmosphere at a heating rate of 5 °C / min. It is then reduced for 8 hours in a 5% hydrogen / nitrogen mixture (by volume) at 400 °C (heating rate 5 °C / min), yielding the catalyst designated Ni5-Fe1 / AC. Exemplary Implementation II-VI

[0048] The same method as in embodiment 1 is used to produce the catalyst, however, the transition metal nitrates and their proportions as well as the reaction conditions are varied by successively setting the calcination temperature to 300 °C, 250 °C, 350 °C, 330 °C and 300 °C and the heating rate successively to 5 °C / min, 7 °C / min, 9 °C / min, 3 °C / min and 5 °C / min and the reduction temperature preferably to 400 °C, 300 °C, 250 °C, 450 °C and 400 °C.

[0049] The resulting catalysts are designated as follows: Ni2-Fe1AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn1 / AC, Mn5-Cu1 / AC. The exact addition ratio is shown in Table 1 below. Exemplary Implementation VII-VIII

[0050] The same procedure and reaction conditions as in embodiment 1 are used to prepare the catalyst; however, the catalyst support is varied, and carbon nanotubes (CNT) and MgO are used as catalyst supports. The resulting catalysts are designated Ni5-Fe1 / CNT and Ni5-Fe1 / MgO. Example 87-X

[0051] The same procedure and reaction conditions as in embodiment 1 are used to produce the catalyst, a single transition metal nitrate is used as the substrate, and the catalysts obtained are designated as Ni5 / AC and Co2 / AC, respectively. Table 1: Substrate addition for the production of transition metal catalysts Example of implementation Transition metal nitrate catalyst carrier Manufactured catalyst species molar ratio Example I Nickel nitrate : Iron nitrate 5 : 1 Activated carbon (AC) Ni5-Fe1 Example II Nickel nitrate : Iron nitrate 2 : 1 Activated carbon (AC) Ni2-Fe1 Example III Nickel acetate : Cobalt nitrate 5 : 1 Activated carbon (AC) Ni5-Co1 Example IV Nickel nitrate :copper acetate 5 : 1 Activated carbon (AC) Ni5-Cu1 Example V Cobalt nitrate : Zinc nitrate 5 : 1 Activated carbon (AC) Co5-Zn1 Example VI Manganese nitrate :Copper nitrate 5 : 1 Activated carbon (AC) Mn5-Cu1 Example VII Nickel nitrate : Iron nitrate 5 : 1 Carbon nanotube (CNT) Ni5-Fe1 / CNT Example VIII Nickel nitrate : Iron nitrate 5 : 1 Magnesium oxide (MgO) Ni5-Fe1 / MgO Example VIII Nickel nitrate 5 Activated carbon (AC) Ni5 / AC Example X Cobalt nitrate 2 Activated carbon (AC) CO2 / AC The following examples of acyloin condensation, XI to XXXI, are provided as examples: Acyloin condensation example XI

[0052] In a 100 mL high-pressure reactor, 0.05 g of Ni5-Fe1 / AC catalyst, 20 mL of ethyl alcohol, and 20 mL of acetone are added successively. The mixture is reacted at 175 °C for 1.7 hours with stirring at 500 rpm. At the end of the reaction, gas chromatographic analysis shows a conversion rate of 92% for ethanol, 87% for acetone, and a selectivity of 83% for 2-pentanone. Acyloin condensation - embodiment XII-XXXI

[0053] A similar procedure to that in embodiment 11 is used, whereby the reaction conditions and the substrate are varied and the composition of the reaction products is analyzed. The reaction conditions and the catalytic properties of the coupling reaction are listed in Table 2 below: Table 2: Results of the reaction conditions and catalytic properties from the acyloin condensation examples Example of implementation catalyst Temperature°C Zeith Ketone substrate alcohol substrate Ketone substrate conversion rate % Alcohol-substrate conversion rate % Corresponding selectivity for high-carbon ketones % 11 Ni5-Fe1 / AC 175 1,7 Acetone Ethyl alcohol 87 92 93 12 Ni5-Fe1 / AC 175 1,0 Acetone Ethyl alcohol 88 81 91 13 Ni5-Fe1 / AC 175 1 Acetone Ethyl alcohol 82 87 94 14 Ni5-Fe1 / AC 175 0,5 Acetone Ethyl alcohol 87 89 90 15 Ni3-Fe1 / AC 190 1 Acetone Ethyl alcohol 93 88 92 16 Ni5-Fe1 / AC 175 1 Acetone n-Propyl alcohol 80 85 90 17 Ni5-Fe1 / AC 175 1 Acetone Ethylene glycol 81 83 89 18 Ni5-Fe1 / AC 175 1 Acetone Glycerin 80 81 91 19 Ni5-Fe1 / AC 175 1 Butanone Monoethanolamine 80 86 93 20 Ni5-Fe1 / AC 175 1 2-Pentanone Ethyl alcohol 76 85 92 21 Ni5-Fe1 / AC 175 1 Acetophenone Ethyl alcohol 82 86 90 22 Ni5-Fe1 / AC 175 1 Butanone n-Propyl alcohol 81 80 92 23 Ni5-Fe1 / AC 175 1 Cyclohexanone Ethyl alcohol 85 83 93 24 Ni5-Fe1 / AC 175 1 Butanone Isopropyl alcohol 88 85 90 25 Love l / AC 175 1 Acetone Ethylene glycol 92 87 91 26 Co5-Zn1 / AC 175 1 Acetone Phenethyl alcohol 77 83 88 27 Mn5- Cu1 / AC 175 1 Acetone Cyclohexanol 82 87 90 28 Ni5-Fe1 / CNT 175 1 Aminoacetone Ethyl alcohol 85 90 91 29 Ni5-Fe1 / MgO 175 1 Acetone Ethyl alcohol 72 77 81 30 Ni5 / AC 175 1 Acetone Ethyl alcohol 61 70 87 31 Co2 / AC 175 1 Acetone Ethyl alcohol 66 67 89

[0054] The catalysis of the acyloin condensation of ketones and alcohols using the catalyst of the present application eliminates the need for an additional solvent and high-pressure hydrogen, resulting in a simple reaction process and a simplified manufacturing procedure. Furthermore, this catalysis exhibits a high conversion rate for the acyloin condensation and broad applicability to various types of alcohols. The conversion rate for alcohols and ketones can exceed 80%, while the selectivity for the desired high-carbon ketones can exceed 90%. Moreover, this catalysis is stable over the long term and therefore has good prospects for industrial applications. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] US 4146581

[0003] CN 106732555A

[0004] CN 111889105A

[0004] CN 110423190A

[0004] CN 106905125A

[0004] Cited non-patent literature

[0000] (II)-nitrate hexahydrate, iron(III) nitrate nonahydrate, activated carbon and water is 5 : 1 : 50 : 320

[0047]

Claims

[1] Manufacturing process for a supported transition metal catalyst, characterized by that it includes the following steps: S1. Dissolving 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 nitrate, transition metal formate, transition metal oxalate and transition metal acetate; S2. Add a porous catalyst support to the solution and stir at room temperature until homogeneous mixing is achieved to obtain a mixture; S3. Place the mixture in an oven and dry at 80 °C to 110 °C until constant weight is achieved to obtain a dried product; S4. Heating the dried product in a calcining device to 250 °C to 390 °C and calcining for 5 to 8 hours to obtain a calcined product; and S5. Heating the calcined product in a reaction apparatus to 250 °C to 450 °C and reducing in a reducing atmosphere for 2 to 8 hours to obtain the supported transition metal catalyst, wherein The molar ratio n1 : n2 : n3 between the transition metal salt, water and the porous catalyst support is 1 : 50 : 5 ≤ n1 : n2 : n3 ≤ 1 : 100 :

20. [2] Manufacturing process according to claim 1, characterized by , that during calcination a heating rate of 2 to 10 °C / min and a calcination temperature of 300 °C to 350 °C. [3] Manufacturing process according to claim 1, characterized by , that in step S5 the heating rate is 2 to 10 °C / min and the temperature during reduction is 300 °C to 350 °C. [4] Manufacturing process according to claim 1, characterized by , that a transition metal in the transition metal salt is selected from at least one of Mn, Ni, Co, Fe, Zn and Cu. [5] Manufacturing process according to claim 1, characterized by that 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] Manufacturing process according to claim 1, characterized by , that the porous catalyst support is selected from at least one of porous carbon material, alkaline earth oxide, silicon dioxide, silicon aluminum oxide and diatomaceous earth. [7] Manufacturing process according to claim 1, characterized by , that the reducing atmosphere refers to an H2 / N2 mixed gas stream, where the volume fraction of H2 in the H2 / N2 mixed gas stream is 5% to 50%. [8] Supported transition metal catalyst, produced according to a manufacturing process according to any one of claims 1 to 7. [9] Supported transition metal catalyst according to claim 8, characterized by, that the supported transition metal catalyst is Ni5-Fe1 / AC, Ni2-Fe1AC, Ni5-Co1 / AC, Ni5-Cu1 / AC, Co5-Zn / AC, Mn5-Cu1 / Ae, Ni5 / AC, Co2 / AC, Ni5-Fe1 / CNT or Ni5-Fe1 / MgO, where the AC consisting of 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] Use of a supported transition metal catalyst according to claim 8 or 9 in the synthesis of high-carbon ketones by acyloin condensation of α-H-containing ketones and alcohols. [11] Method for the catalytic synthesis of a high-carbon ketone, characterized by that it includes the following steps: Production of a high-carbon ketone by acyloin condensation using a supported transition metal catalyst according to claim 8 or 9 as a catalyst and an alcohol and an α-H-containing ketone as reaction substrates in a closed reaction apparatus at an initial pressure of atmospheric pressure and a reaction temperature of 120 °C to 250 °C. [12] Process for catalytic synthesis according to claim 11, characterized by that the alcohol is selected from at least one of aliphatic alcohols, aromatic alcohols, alicyclic alcohols and alcohols with heteroatom-containing substituents. [13] Process for catalytic synthesis according to claim 11, characterized by , that the α-H-containing ketone is selected from at least one of aliphatic ketone, aromatic ketone, alicyclic ketone and ketone with heteroatom-containing substituents. [14] Process for catalytic synthesis according to claim 11, wherein the molar ratio between the α-H-containing ketone and the alcohol is 1 : 2 to 2 :

1. [15] Process for catalytic synthesis according to claim 14, characterized by , that the addition ratio of the supported transition metal catalyst to the α-H-containing ketone is such that 0.2 to 0.3 g of the supported transition metal catalyst are added per 1 mol of ketone. [16] Process for catalytic synthesis according to claim 11, characterized by , that the temperature of the acyloin condensation is 160 °C to 210 °C and the reaction time is 30 to 300 minutes. [17] Process for catalytic synthesis according to claim 11 or 16, characterized by that the acyloin condensation is carried out in a boiler reactor, a fixed bed process or a fluidized bed process; and that the acyloin condensation is carried out in a continuous process with simultaneous feeding and removal.