Supported catalyst and preparation method therefor, and method for preparing high-carbon ketone

Abstract

The present application belongs to the technical field of chemical catalysis, and particularly relates to a supported catalyst and a preparation method therefor, and a method for preparing a high-carbon ketone. The preparation method for the supported catalyst comprises: taking a transition metal nitrate and / or transition metal acetate as a reaction substrate, a porous polyolefin powder material as a catalyst carrier, and water as a reaction medium, uniformly mixing the reaction substrate, the catalyst carrier and the reaction medium, and drying and roasting the resulting mixture to prepare the supported catalyst. The supported catalyst can be directly used in a condensation coupling reaction for synthesizing a high-carbon ketone by means of in-situ reduction in the preparation process, without a reduction process of the catalyst, thus simplifying the preparation process of the catalyst, and reducing the production cost. The supported catalyst can enable the high-carbon ketone to be produced with a high selectivity, without the need for additional solvent or hydrogen source during the reaction, resulting in a process that is simple, cost-effective, highly efficient, easy to control, safe, and produces few by-products.

Description

[0001] The present disclosure belongs to the technical field of chemical catalysis, and in particular relates to a supported catalyst and a preparation method thereof, and a method for preparing a high-carbon ketone. BACKGROUND

[0002] It is known that the size of ketone molecules would affect reactivity and energy release during the reaction. Compared with small-molecule ketones, high-carbon ketones have relatively large molecular structures and could achieve more complex and diverse chemical reactions. In industrial production, the high-carbon ketones could be used as an excellent organic solvent, as well as an important organic chemical raw material that is widely used in the synthesis of fragrances, organic synthesis, and synthesis of pharmaceutical intermediates. However, the existing methods for synthesizing high-carbon ketones are limited, and generally have a complicated reaction process and many by-products. For example, high-carbon ketones could be prepared through oxidative dehydrogenation of the corresponding alcohols, or through aldol condensation of ketones and aldehydes followed by hydrogenation. However, these methods have the disadvantages of high production costs and generally low product selectivity. In addition, a method for preparing pentanone by condensation of acetaldehyde and acetone, dehydration, and hydrogenation in the presence of hydrogen has been reported in the prior art. However, a target product obtained by the method has complex components and low selectivity, and the method requires high-pressure hydrogen to participate in the reactions, thus placing high demands on the reaction conditions.

[0003] In addition, it is also disclosed in the prior art that a-H-containing ketones and other active a-H-containing carbonyl compounds, such as ketones and aldehydes small-molecules, are subjected to aldol condensation to obtain condensation coupling products, and then the condensation coupling products are subjected to dehydration and hydrogenation to obtain alkyl-grafted high-carbon ketones. There are also methods of using alcohols as a condensation coupling reagent to couple with the a-H-containing ketones to prepare high-carbon ketones. However, the synthesis of high-carbon ketones above requires four steps of hydrogen borrowing (alcohol dehydrogenation to obtain smallmolecule carbonyl compounds containing active a-H), aldol condensation (the substrate containing a-H ketones), dehydration, and hydrogenation, which puts forward extremely high requirements on the design of catalysts. The catalyst systems reported in the prior art include supported noble metal catalysts, homogeneous catalysts, or composite oxide catalysts. For example, Chinese patent CN106732555A reports a Pd / C catalyst for the a-alkylation of ketones and alcohols. However, a catalytic reaction of acetophenone and / z-butanol requires a solvent 1,4-di oxane, which easily forms explosive peroxides, requires precise process control during production, and has low safety. For another example, Chinese patent CN111889105A discloses a bifunctional catalyst for preparing 3-pentanone by alkylation of methanol and butanone, where the bifunctional catalyst includes 2% to 30% of nickel oxide, 40% to 90% of magnesium oxide, 10% to 30% of aluminum oxide, and 0% to 20% of zinc oxide. The raw materials methanol and butanone undergo a reaction at 220 °C to 350 °C in a molar ratio of (5-15):1. However, the reaction has high temperature, great control difficulty, and poor yield of 3-pentanone. For example, Chinese patents CN110423190A and CN106905125A report an iron complex and a cobalt complex as catalysts in catalyzing a-alkylation of ketones, respectively. The catalysts are prepared by reacting 4'-dimethylaminophenyl-2,2':6',2"-terpyridine with anhydrous ferrous chloride, and 2,2:6,2"-terpyridine with cobalt chloride, respectively. However, the above patents generally have problems such as expensive catalysts, complicated and harsh reaction conditions, and difficulty in product separation and catalyst recovery. SUMMARY

[0004] In view of the above-mentioned existing technical problems, the present disclosure is to provide a supported catalyst and a preparation method thereof, and a method for preparing a high-carbon ketone.

[0005] The present disclosure provides a method for preparing a supported catalyst, including:

[0006] mixing a transition metal nitrate and / or a transition metal acetate as a reaction substrate, a polyolefin powder porous material as a catalyst carrier, and water as a reaction medium evenly to obtain a mixture, and subjecting the mixture to drying and calcination in sequence to obtain the supported catalyst.

[0007] In some embodiments, a transition metal in the transition metal nitrate and / or the transition metal acetate is an element selected from the group consisting of Group VIIB, Group VIII, Group IB, and Group IIB in periodic table of elements, and the transition metal is a non-precious metal element.

[0008] In some embodiments, the transition metal is selected from a transition metal element in a fourth period of the periodic table of elements.

[0009] In some embodiments, the method for preparing the supported catalyst includes the following steps:

[0010] SI, dissolving the reaction substrate in an appropriate amount of the water to obtain a solution;

[0011] S2, adding the catalyst carrier into the solution obtained in step SI and mixing evenly by stirring at ambient temperature to obtain a mixed system;

[0012] S3, placing the mixed system obtained in step S2 in an oven, and drying the mixed system at a temperature of 80 °C to 120 °C to a constant weight to obtain a dried material; and

[0013] S4, placing the dried material obtained in step S3 in a calcination device, heating and calcinating the dried material at a calcination temperature of 700 °C to 900 °C for 2 h to 8 h to reduce the transition metal in situ during calcination decomposition, and then cooling a resulting material to obtain the supported catalyst.

[0014] In some embodiments, the heating is conducted at a heating rate of 2 °C / min to 10 °C / min, and the calcination temperature is in a range of 750 °C to 850 °C.

[0015] In some embodiments, a transition metal in the transition metal nitrate and / or the transition metal acetate is one or more selected from the group consisting of Mn, Ni, Co, Fe, Zn and Cu.

[0016] In some embodiments, the polyolefin powder porous material is one or more selected from the group consisting of a polyethylene powder porous material and a polypropylene powder porous material.

[0017] In some embodiments, the method further comprises: standing the mixed system obtained in step S2 for 2-10 hours before placing the mixed system obtained in step S2 in the oven.

[0018] In some embodiments, in step SI, a weight ratio of the water to the reaction substrate is in a range of 100 : 0.1-50.

[0019] In some embodiments, in step S2, a weight ratio of the reaction substrate to the catalyst carrier is in a range of 3-50 : 100.

[0020] In some embodiments, the step S2 is replaced by:

[0021] S2a, adding the polyolefin powder porous material into the solution obtained in step SI, and mixing evenly by stirring at ambient temperature to obtain a mixed system;

[0022] S2b, dispersing an appropriate amount of an inorganic porous material in an organic solvent, and mixing evenly by stirring to obtain a mixed material; pressurizing the mixed material to a pressure of 0.5-3 MPa and maintaining at the pressure for 3-10 min, then reducing to a normal pressure at a speed of 0.1-0.3 MPa / min; and filtering a resulting system to obtain a pretreated inorganic porous material; and

[0023] S2c, adding the pretreated inorganic porous material into the mixed system obtained in step S2a, and mixing evenly by stirring.

[0024] In some embodiments, the inorganic porous material is one or more selected from the group consisting of a porous ceramic material, a porous molecular sieve, a porous activated carbon and a natural inorganic porous material.

[0025] In some embodiments, the polyolefin powder porous material has a particle size of not greater than 1 gm.

[0026] In some embodiments, the inorganic porous material has a particle size of not greater than 10 mm.

[0027] In some embodiments, a pore size of the inorganic porous material is not great than 1.2 times the particle size of the polyolefin powder porous material.

[0028] In some embodiments, in step S2b, a weight ratio of the inorganic porous material to the polyolefin powder porous material is in a range of 3-5 : 1.

[0029] In some embodiments, in step S2b, a weight ratio of the inorganic porous material to the organic solvent is in a range of 0.1-0.3 : 1.

[0030] In some embodiments, in step S2b, the organic solvent is selected from a nonpolar organic solvent; and the nonpolar organic solvent comprises one or more selected from the group consisting of cyclohexane and benzene.

[0031] In some embodiments, the supported catalyst is prepared by the method for preparing the supported catalyst described above.

[0032] In some embodiments, the supported catalyst is one or more selected from the group consisting of Ni5-Cul / PP, Ni5 / PP, Ni2-Cul / PP, Ni5-Col / PP, Ni5-Fel / PP, Co5-Znl / PP, Mn5-Cul / PP, Ni5-Cul / PE and Ni5-Cul / PE.

[0033] The present disclosure also provides a method for preparing a high-carbon ketone, including:

[0034] subjecting an alcohol and an a-H-containing ketone that serve as reaction substrates to condensation coupling reaction in the presence of the supported catalyst described above as a reaction catalyst in a closed reactor at a temperature of 120 °C to 250 °C under an initial pressure of atmospheric pressure to obtain the high-carbon ketone.

[0035] In some embodiments, the alcohol is one or more selected from the group consisting of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol and an alcohol containing other heteroatom substituents; and

[0036] the a-H-containing ketone is one or more selected from the group consisting of an aliphatic ketone, an aromatic ketone, an alicyclic ketone and a ketone containing other heteroatom substituents.

[0037] In some embodiments, in the reaction substrates, a molar ratio of the a-H-containing ketone to the alcohol is in a range of 1:2 to 2:1, and a feeding ratio of the a-H-containing ketone to the supported catalyst is 0.2 g to 0.3 g of the supported catalyst per 1 mol of the a-H-containing ketone; and

[0038] the condensation coupling reaction is conducted at a temperature of 160-210 °C for 30-300 min.

[0039] The embodiments of present disclosure have the following beneficial effects:

[0040] In the present disclosure, the supported catalyst prepared through in-situ reduction can be directly used for the condensation coupling for synthesizing high-carbon ketone without reduction of the supported catalyst, thereby simplifying the catalyst preparation and reducing production costs.

[0041] On this basis, the supported catalyst according to the present disclosure does not contain precious metals, has low cost, and is easy to be manufactured.

[0042] In addition, the supported catalyst according to the present disclosure can be directly used to catalyze the condensation coupling of a-H-containing ketone and small-molecule alcohol, and the target product high-carbon ketone can be obtained with a high selectivity. Moreover, no external solvent and hydrogen source are required during the reaction. The preparation method has simple operations, a low cost, and a simple, efficient, and easy-to-control reaction process, as well as high safety, few by-products and high product selectivity. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0043] The technical solutions of the present disclosure will be clearly and completely described below with reference to the embodiments. Apparently, the described embodiments are merely some rather than all of the embodiments of the present disclosure. All other embodiments obtained by those skilled in the art based on the described embodiments of the application shall fall within the scope of the application.

[0044] It should be understood that the term "and / or" in this specification merely describes associations between associated objects, and it indicates three types of relationships. For example, A and / or B may indicate that A exists alone, A and B coexist, or B exists alone. In addition, the character " / " in this specification generally indicates that the associated objects are in an "or" relationship.

[0045] In the description of this specification, it should be understood that the terms such as "substantially", "approximate to", "approximately", "about", "roughly", and "in general" described in the claims and embodiments of the present disclosure mean general agreement within a reasonable process operation range or tolerance range, rather than an exact value.

[0046] It should be noted that terms "including", "comprising", or any other variants thereof in the present disclosure are intended to cover non-exclusive inclusion such that a process, method, article, or apparatus including a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element qualified by the phrase "including a ..." does not exclude the presence of an additional identical element in the process, method, article, or apparatus including the element. In addition, it should be noted that the scope of the methods and devices in the embodiments of the present disclosure is not limited to conducting functions in the order shown or discussed, and may also include conducting functions in a substantially simultaneous manner or in reverse order depending on the functions involved. For example, the described methods may be conducted in an order different from that described, and various steps may be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.

[0047] The present disclosure provides a method for preparing a supported catalyst, including:

[0048] mixing a transition metal nitrate and / or a transition metal acetate as a reaction substrate, a polyolefin powder porous material as a catalyst carrier, and water as a reaction medium evenly to obtain a mixture, and subjecting the mixture to drying and calcination in sequence to obtain the supported catalyst.

[0049] In some embodiments, a transition metal in the transition metal nitrate and / or the transition metal acetate is an element selected from the group consisting of Group VIIB, Group VIII, Group IB, and Group IIB in periodic table of elements, and the transition metal is a non-precious metal element.

[0050] In some embodiments, the transition metal is selected from a transition metal element in a fourth period of the periodic table of elements.

[0051] As some embodiments of the present disclosure, the transition metal in the transition metal nitrate and / or the transition metal acetate is one or more selected from the group consisting of Mn, Ni, Co, Fe, Zn, and Cu. In some embodiments, the transition metal is one or more selected from the group consisting of Ni, Co, and Cu.

[0052] As some embodiments of the present disclosure, the polyolefin powder porous material is one or more selected from the group consisting of a polyethylene (PE) powder porous material and a polypropylene (PP) powder porous material. In some embodiments, the polyolefin powder porous material is the PP powder porous material.

[0053] In some embodiments, the method for preparing the supported catalyst includes the following steps:

[0054] SI, dissolving the reaction substrate in an appropriate amount of the water to obtain a solution;

[0055] S2, adding the catalyst carrier into the solution obtained in step SI and mixing evenly by stirring at ambient temperature to obtain a mixed system;

[0056] S3, subjecting the mixed system obtained in step S2 to standing for 2 h to 10 h, placing a resulting system in an oven, and drying at a temperature of 80 °C to 120 °C to a constant weight to obtain a dried material; and

[0057] S4, placing the dried material obtained in step S3 in a calcination device, heating and calcinating the dried material at a calcination temperature of 700 °C to 900 °C for 2 h to 8 h to reduce the transition metal in situ during calcination decomposition, and then cooling a resulting material to obtain the supported catalyst.

[0058] As some embodiments of the present disclosure, in step SI, a weight ratio of the water to the reaction substrate is in a range of 100:0.1 to 100:50.

[0059] In some embodiments, in step S2, a weight ratio of the reaction substrate to the catalyst carrier is in a range of 3:100 to 50:100.

[0060] In some embodiments, in step S4, the heating is conducted at a heating rate of 2 °C / min to 10 °C / min, and the calcination temperature is in a range of 750 °C to 850 °C.

[0061] In some embodiments, the method for preparing the supported catalyst includes the following steps:

[0062] SI, dissolving the transition metal nitrate and / or the transition metal acetate in an appropriate amount of the water to obtain a solution;

[0063] S2a, adding the polyolefin powder porous material into the solution obtained in step SI and mixing evenly by stirring at ambient temperature to obtain a mixed system;

[0064] S2b, dispersing an appropriate amount of an inorganic porous material in an organic solvent, and mixing evenly by stirring to obtain a mixed material; pressurizing the mixed material to a pressure of 0.5-3 MPa and maintaining at the pressure for 3-10 min, then reducing to a normal pressure at a speed of 0.1-0.3 MPa / min; and filtering a resulting system to obtain a pretreated inorganic porous material;

[0065] S2c, adding the pretreated inorganic porous material into the mixed system obtained in step S2a, and mixing evenly by stirring to obtain a mixture system;

[0066] S3, subjecting the mixture system obtained in step S2c to standing for 2 h to 10 h and drying in an oven at a temperature of 80 °C to 120 °C to a constant weight to obtain a dried material; and

[0067] S4, placing the dried material obtained in step S3 in a calcination device, heating and calcinating the dried material at a calcination temperature of 700 °C to 900 °C for 2 h to 8 h to reduce the transition metal in situ during calcination decomposition, and then cooling a resulting material to obtain the supported catalyst.

[0068] As some embodiments of the present disclosure, the inorganic porous material is one or more selected from the group consisting of porous ceramic materials, porous molecular sieves, porous activated carbon, and natural inorganic porous materials. In some embodiments, the inorganic porous material is a natural zeolite and / or a diatomaceous earth. In some embodiments, the inorganic porous material is the porous ceramic material.

[0069] In some embodiments, the filtering in step S2b is normal-pressure filtering.

[0070] In some embodiments, the polyolefin powder porous material has a particle size of less than or equal to 1 pm.

[0071] In some embodiments, the inorganic porous material has a particle size of less than or equal to 10 mm, and preferably, the inorganic porous material has a particle size of less than or equal to 1 mm.

[0072] As an embodiment of the present disclosure, the pore size of the inorganic porous material is less than or equal to 1.2 times the particle size of the polyolefin powder porous material.

[0073] In some embodiments, in step S2b, a weight ratio of the inorganic porous material to the polyolefin powder porous material is in a range of 3:1 to 5:1.

[0074] In some embodiments, in step S2b, a weight ratio of the inorganic porous material to the organic solvent is in a range of 0.1:1 to 0.3:1.

[0075] As some embodiments of the present disclosure, in step S2b, the organic solvent is a nonpolar organic solvent. In some embodiments, the non-polar organic solvent comprises cyclohexane and / or benzene.

[0076] In the process of preparing the supported catalyst, a carrier of the polyolefin powder porous material is formed by the inorganic porous material. On this basis, by pre-filling the inorganic porous material with an organic solvent that is immiscible with water, the organic solvent can be used to preemptively fill and occupy the pores inside the inorganic porous material. When the inorganic porous material is mixed with the mixed system obtained in step S2a, the polyolefin powder porous material therein can preferentially adhere to and combine with a surface of the inorganic porous material, maintaining the high activity of a catalyst polymer formed after the polyolefin powder porous material adheres to the surface of the inorganic porous material. At the same time, by using large-particle inorganic porous materials, efficient and convenient recovery of the supported catalyst is achieved.

[0077] In addition, the present disclosure further provides a supported catalyst for preparing a high-carbon ketone, where the supported catalyst is prepared by the method described above.

[0078] As some embodiments of the present disclosure, the supported catalyst is any one selected from the group consisting of Ni5-Cul / PP, Ni5 / PP, Ni2-Cul / PP, Ni5-Col / PP, Ni5-Fel / PP, Co5-Znl / PP, Mn5-Cul / PP, Ni5-Cul / PE, and Ni5-Cul / PE. In some embodiments, “5” and “1” in Ni5-Cul / PP represent proportional relationship (molar ratio) between nickel salt (nickel nitrate or nickel acetate) and copper salt (copper nitrate) used for preparing Ni5-Cul / PP.

[0079] In the present disclosure, the catalyst prepared by calcination has a fluffy porous structure and a large specific surface area, shows the characteristics of highly dispersed active components and rich oxygen vacancies, and can catalyze condensation coupling efficiently and stably.

[0080] Furthermore, the present disclosure further provides a method for preparing a high-carbon ketone, including:

[0081] subjecting an alcohol and an a-H-containing ketone that serve as reaction substrates to condensation coupling in the presence of the supported catalyst as described above as a reaction catalyst in a closed reactor at a reaction temperature of 120 °C to 250 °C under an initial pressure of atmospheric pressure to obtain the high-carbon ketone.

[0082] In some embodiments, the alcohol is one or more selected from the group consisting of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol, and an alcohol containing other heteroatom substituents.

[0083] In some embodiments, the alcohol is one or more selected from the group consisting of ethanol, / / -propanol, isopropanol, ethylene glycol, phenyl ethanol, cyclohexanol, and ethanolamine.

[0084] In some embodiments, the a-H-containing ketone is one or more selected from the group consisting of an aliphatic ketone, an aromatic ketone, an alicyclic ketone, and a ketone containing other heteroatom substituents.

[0085] In some embodiments, the a-H-containing ketone is one or more selected from the group consisting of acetone, butanone, pentanone, acetophenone, cyclohexanone, and l-amino-2-propanone.

[0086] In some embodiments, a molar ratio of the a-H-containing ketone to the alcohol is in a range of 1:2 to 2:1; and a feeding ratio of the a-H-containing ketone to the supported catalyst is 0.2 g to 0.3 g of the supported catalyst per 1 mol of the a-H-containing ketone. The condensation coupling is conducted at a temperature of 160 °C to 210 °C for 30 min to 300 min.

[0087] In the present disclosure, the polyolefin powder is used as a catalyst carrier, which could reduce the transition metal in situ during the calcination decomposition. The catalyst obtained after cooling can be directly used for the condensation coupling of a-H-containing ketone and alcohol to obtain the high-carbon ketone with a high selectivity without an independent reduction step. Moreover, the catalyst is cheap and easy to be obtained. When the catalyst prepared above is used in the condensation coupling of a-H-containing ketone and alcohol, the reaction does not require an external solvent or high-pressure hydrogen. The reaction is easy to be implemented, the catalyst raw materials used are easy to be obtained, and the preparation method is simple. In addition, a catalytic conversion rate for condensation coupling is high and the applicable alcohol categories are wide. The abundant small-molecule alcohol and a-H-containing ketone can be efficiently reacted to obtain the high-carbon ketone, with conversion rates of the alcohol and ketone of not less than 80% respectively, and a selectivity of high-carbon ketone of not less than 90%. In addition, the preparation method can operate stably for a long time and has desirable industrial application prospects.

[0088] The present disclosure will be further described in detail below with reference to the examples, but the present disclosure is not limited to the content of the examples.

[0089] Example 1

[0090] Preparation of a supported catalyst:

[0091] A certain amount of nickel nitrate and copper nitrate were fully dissolved in an appropriate amount of water at ambient temperature, and then a PP porous powder material was added thereto and mixed evenly. After standing for 4 h, a resulting mixture was placed and dried in a muffle furnace at 100 °C. A resulting dried material was placed in a calcination device, heated and calcinated at 800 °C for 4 h, where the dried material was heated at a heating rate of 9 °C / min. After the calcination was completed, a resulting material was cooled to ambient temperature with the furnace to obtain a target catalyst, recorded as Ni5-Cul / PP.

[0092] Examples 2-7

[0093] Preparation of supported catalysts:

[0094] Examples 2-7 were conducted according to the method of Example 1, except that the kind of the transition metal nitrate, the ratio of the transition metal nitrate, the calcination temperature, the heating rate, and the calcination time were adjusted. The calcination temperatures were set to 800 °C, 850 °C, 900 °C, 750 °C, 800 °C, and 750 °C, respectively. The heating rates were set to 7 °C / min, 8 °C / min, 9 °C / min, 10 °C / min, 6 °C / min, and 4 °C / min, respectively. The calcination time was set to 2 h, 3 h, 5 h, 6 h, 7 h, and 8 h, respectively. The catalysts obtained finally were recorded as: Ni5 / PP, Ni2-Cul / PP, Ni5-Col / PP, Ni5-Fel / PP, Co5-Znl / PP, and Mn5-Cul / PP, respectively.

[0095] Example 8

[0096] Preparation of a supported catalyst:

[0097] A certain amount of nickel acetate and copper nitrate were fully dissolved in an appropriate amount of water at ambient temperature, and then a PE porous powder material was added thereto and mixed evenly. After standing for 2 h, a resulting mixture was placed and dried in a muffle furnace at 80 °C. A resulting dried material was placed in a calcination device, heated and calcinated at 700 °C for 4 h, where the dried material was heated at a heating rate of 2 °C / min. After the calcination was completed, a resulting material was cooled to ambient temperature with the furnace to obtain a target catalyst, recorded as Ni5-Cui / PE.

[0098] Example 9

[0099] Preparation of a supported catalyst:

[0100] A certain amount of nickel nitrate and copper nitrate were fully dissolved in an appropriate amount of water at ambient temperature, and then a PE porous powder material was added thereto and mixed evenly. After standing for 2 h, a resulting mixture was placed and dried in a muffle furnace at 80 °C. A resulting dried material was placed in a calcination device, heated and calcinated at 700 °C for 4 h, where the dried material was heated at a heating rate of 2 °C / min. After the calcination was completed, a resulting material was cooled to ambient temperature with the furnace to obtain a target catalyst, recorded as Ni5-Cui / PE.

[0101] Example 10

[0102] Preparation of a supported catalyst:

[0103] A certain amount of nickel nitrate and copper nitrate were fully dissolved in an appropriate amount of water at ambient temperature, and then a PE porous powder material was added thereto and mixed evenly to obtain a mixed system. An appropriate amount of ceramic porous material was dispersed in an organic solvent, stirred and mixed evenly, and then pressurized to 1 MPa and maintained for 5 min, and reduced to an atmospheric pressure at 0.2 MPa / min, then, a resulting material was filtered to obtain a pretreated ceramic porous material. The pretreated ceramic porous material was added into the mixed system of nickel nitrate, copper nitrate, and PE porous powder material, stirred until evenly mixed to obtain a mixture. The mixture was subjected to standing for 5 h, and then placed and dried in an oven at 90 °C to a constant weight. A resulting dried material was placed in a calcination device, heated and calcinated at 700 °C for 4 h, where the dried material was heated at a heating rate of 2°C / min. After the calcination was completed, a resulting material was cooled to ambient temperature with the furnace to obtain a target catalyst, recorded as Ni5-Cul / PE / ceramic.

[0104] The substrate feeding conditions during the preparation of the catalysts in Examples 1 to 10 were shown in Table 1:

[0105] Table 1 Substrate feeding during preparation of catalysts

[0106] Examples for catalyst preparation Transition metal nitrate / Transition metal acetate Catalyst carrier Catalyst obtained Type ratio Example 1 Nickel nitrate, copper nitrate 5:1 PP Ni5-Cul / PP Example 2 Nickel nitrate - PP Ni5 / PP Example 3 Nickel nitrate, copper nitrate 2 1 PP Ni2-Cul / PP Example 4 Nickel nitrate, cobalt nitrate 5 1 PP Ni5-Col / PP Example 5 Nickel nitrate, ferric nitrate 5 1 PP Ni5-Fel / PP Example 6 Cobalt nitrate, zinc nitrate 5 1 PP Co5-Znl / PP Example 7 Manganese nitrate, copper nitrate 5 1 PP Mn5-Cul / PP Example 8 Nickel acetate, copper nitrate 5 1 PE Ni5-Cul / PE Example 9 Nickel nitrate, copper nitrate 5 1 PE Ni5-Cul / PE Example 10 Nickel nitrate, copper nitrate 5 1 PE Ni 5 -C u 1 / PE / cerami c

[0107] In the supported catalysts of the present disclosure, po yolefin powder was selected as a catalyst carrier, having a large specific surface area, high porosity, and uniform pore size distribution, which could increase a contact area between the catalyst and the reactant, thereby increasing a reaction rate. At the same time, the polyolefin powder shows excellent mechanical properties and corrosion resistance. When the post-transition metal loaded by the polyolefin powder is used as a catalyst for the ketone-alcohol condensation coupling, the catalyst has a stable catalytic performance, and could operate stably for a long time, which shows desirable industrial application prospects.

[0108] More importantly, the polyolefin powder is used as a catalyst carrier, which could reduce the transition metal in situ during the calcination decomposition. The catalyst obtained after cooling could be directly used for the condensation coupling of a-H-containing ketone and alcohol to obtain the high-carbon ketone with a high selectivity without an independent reduction step. Moreover, the catalyst is cheap and easy to be obtained.

[0109] Example 11

[0110] Preparation of a high-carbon ketone:

[0111] 0.05 g of the catalyst bTt5-Cul / PP, 20 mL of ethanol, and 20 mL of acetone were added into a 100 mL high-pressure reactor in sequence, and a reaction was conducted at 175 °C for 5 h under stirring at 500 r / min. The results of gas chromatography analysis show that the reaction results in a conversion rate of ethanol of 89%, a conversion rate of acetone of 84%, and a selectivity of 2-pentanone of 90%.

[0112] Examples 12-30

[0113] Examples 12-30 were conducted according to the method of Example 11, except that the reaction conditions and substrates were adjusted. The composition of the product after reaction was analyzed. The reaction conditions and catalytic performance results of condensation coupling examples are shown in Table 2.

[0114] Table 2 Reaction conditions and catalytic performance results of condensation coupling examples

[0115] Exampl es Catalyst Temperature, °C Time, h Substrate ketone Substrate alcohol A conversi on rate of substrate ketone, % A conversi on rate of substrate alcohol, % A selectivity of correspond! ng high-carbon ketone. % 11 Ni5-Cul / PP 175 5 Acetone Ethanol 84 89 90 12 Ni5- Cul / PP 185 1 Acetone Ethanol 83 84 91 13 Ni5- Cul / PP 195 0.5 Acetone Ethanol 85 88 93 14 Ni5- Cul / PP 200 0.5 Acetone w-propanol 82 82 92 15 Ni5- Cul / PP 190 1.5 Acetone Ethanol 88 90 93 16 Ni2- Cul / PP 200 2 Acetone Isopropano 1 86 83 93 17 Ni5- Col / PP 210 2.5 Acetone Ethylene glycol 82 84 92 18 Ni5 / PP 220 3 Acetone Glycerol 81 86 90 19 Ni5- Fel / PP 175 3.5 Butanone Ethanol 88 82 91 20 Co5-Znl / PP 130 4 2-Pentanone Ethanol 80 80 90 21 Mn5-Cul / PP 175 4.5 Butanone Ethanol 86 89 92 22 Ni5- Cul / PP 175 5 Acetophen one Ethanol 82 83 91 23 Ni5-Cul / PP 120 3 Cyclohexa none Ethanol 85 89 90 24 Ni5-Cul / PP 240 4 l-amino-2-propanone Ethanol 81 88 94 25 Ni5- Cul / PP 160 1 Acetone Phenethyl alcohol 86 90 91 26 Ni5- Cul / PP 250 1 Acetone Cyclohexa nol 81 80 92 27 Ni5- Cul / PP 145 1 Acetone Ethanolami ne 85 86 90 28 Ni5- Cul / PP 175 1 Cyclohexa none Cyclohexa nol 86 81 91 29 Ni5- Cul / PE 175 1 Butanone Propanol 82 88 91 30 Ni5- Cul / PE / cer amic 210 0.5 Cyclohexa none Ethanol 86 89 93

[0116] At the same time, it is verified that although different process parameters were used in Examples 11 to 30, the performance of the catalysts prepared therefrom is basically the same, proving that the supported catalyst of the present disclosure could efficiently catalyze the condensation coupling of a-H ketone and alcohol.

[0117] In summary, when the catalyst prepared above is used in the condensation coupling of a-H-containing ketone and alcohol, the reaction does not require an external solvent or high-pressure hydrogen. The reaction is easy to be implemented, the catalyst raw materials used are easy to be obtained, and the preparation method is simple. In addition, a catalytic conversion rate for condensation coupling is high and the applicable alcohol categories are wide. The abundant smallmolecule alcohol and a-H-containing ketone can be efficiently reacted to obtain the high-carbon ketone, with conversion rates of the alcohol and ketone of not less than 80% respectively, and a selectivity of high-carbon ketone of not less than 90%. In addition, the preparation method can operate stably for a long time and has desirable industrial application prospects.

[0118] Although the application is described in detail by the above-mentioned embodiments, the above-mentioned embodiments are only a part of the application, but not all of it. Other embodiments obtained by those skilled in the art according to the above-mentioned embodiments without creative labor all belong to the scope of the application.

Claims

1. A method for preparing a supported catalyst, comprising:mixing a transition metal nitrate and / or a transition metal acetate as a reaction substrate, a polyolefin powder porous material as a catalyst carrier, and water as a reaction medium evenly to obtain a mixture, andsubjecting the mixture to drying and calcination in sequence to obtain the supported catalyst.

2. The method of claim 1, wherein a transition metal in the transition metal nitrate and / or the transition metal acetate is an element selected from the group consisting of Group VIIB, Group VIII, Group IB, and Group IIB in periodic table of elements, and the transition metal is a non-precious metal element.

3. The method of claim 2, wherein the transition metal is selected from a transition metal element in a fourth period of the periodic table of elements.

4. The method of claim 1, 2, or 3, comprising the following steps:SI, dissolving the reaction substrate in an appropriate amount of the water to obtain a solution;S2, adding the catalyst carrier into the solution obtained in step SI and mixing evenly by stirring at ambient temperature to obtain a mixed system;S3, placing the mixed system obtained in step S2 in an oven, and drying the mixed system at a temperature of 80 °C to 120 °C to a constant weight to obtain a dried material; andS4, placing the dried material obtained in step S3 in a calcination device, heating and calcinating the dried material at a calcination temperature of 700 °C to 900 °C for 2 h to 8 h to reduce the transition metal in situ during calcination decomposition, and then cooling a resulting material to obtain the supported catalyst.

5. The method of claim 4, wherein the heating is conducted at a heating rate of 2 °C / min to 10 °C / min, and the calcination temperature is in a range of 750 °C to 850 °C.

6. The method of claim 1, wherein a transition metal in the transition metal nitrate and / or the transition metal acetate is one or more selected from the group consisting of Mn, Ni, Co, Fe, Zn and Cu.

7. The method of claim 1, wherein the polyolefin powder porous material is one or more selected from the group consisting of a polyethylene powder porous material and a polypropylene powder porous material.

8. The method of claim 4, further comprising: standing the mixed system obtained in step S2 for 2-10 hours before placing the mixed system obtained in step S2 in the oven.

9. The method of claim 4, wherein in step SI, a weight ratio of the water to the reaction substrate is in a range of 100 : 0.1-50.

10. The method of claim 4, wherein in step S2, a weight ratio of the reaction substrate to the catalyst carrier is in a range of 3-50 : 100.

11. The method of claim 4, wherein the step S2 is replaced by:S2a, adding the polyolefin powder porous material into the solution obtained in step SI, and mixing evenly by stirring at ambient temperature to obtain a mixed system;S2b, dispersing an appropriate amount of an inorganic porous material in an organic solvent, and mixing evenly by stirring to obtain a mixed material; pressurizing the mixed material to a pressure of 0.5-3 MPa and maintaining at the pressure for 3-10 min, then reducing to a normal pressure at a speed of 0.1-0.3 MPa / min; and filtering a resulting system to obtain a pretreated inorganic porous material; andS2c, adding the pretreated inorganic porous material into the mixed system obtained in step S2a, and mixing evenly by stirring.

12. The method of claim 11, wherein the inorganic porous material is one or more selected from the group consisting of a porous ceramic material, a porous molecular sieve, a porous activated carbon and a natural inorganic porous material.

13. The method of claim 1, wherein the polyolefin powder porous material has a particle size of not greater than 1 pm.

14. The method of claim 11 or 12, wherein the inorganic porous material has a particle size of not greater than 10 mm.

15. The method of claim 11, wherein a pore size of the inorganic porous material is not great than 1.2 times the particle size of the polyolefin powder porous material.

16. The method of claim 11, wherein in step S2b, a weight ratio of the inorganic porous material to the polyolefin powder porous material is in a range of 3-5:1.

17. The method of claim 11, wherein in step S2b, a weight ratio of the inorganic porous material to the organic solvent is in a range of 0.1-0.3 : 1.

18. The method of claim 11, wherein in step S2b, the organic solvent is selected from a nonpolar organic solvent; and the nonpolar organic solvent comprises one or more selected from the group consisting of cyclohexane and benzene.

19. A supported catalyst, wherein the supported catalyst is prepared by the method for preparing the supported catalyst of any one of claims 1-18.

20. The supported catalyst of claim 19, wherein the supported catalyst is one or more selected from the group consisting of Ni5-Cul / PP, Ni5 / PP, Ni2-Cul / PP, Ni5-Col / PP, Ni5-Fel / PP, Co5-Znl / PP, Mn5-Cul / PP, Ni5-Cul / PE and Ni5-Cul / PE.

21. A method for preparing a high-carbon ketone, comprising:subjecting an alcohol and an a-H-containing ketone that serve as reaction substrates to condensation coupling reaction in the presence of the supported catalyst of any one of claims 19 to 20 as a reaction catalyst in a closed reactor at a temperature of 120 °C to 250 °C under an initial pressure of atmospheric pressure to obtain the high-carbon ketone.

22. The method of claim 21, wherein the alcohol is one or more selected from the group consisting of an aliphatic alcohol, an aromatic alcohol, an alicyclic alcohol and an alcohol containing other heteroatom substituents; andthe a-H-containing ketone is one or more selected from the group consisting of an aliphatic ketone, an aromatic ketone, an alicyclic ketone and a ketone containing other heteroatom substituents.

23. The method of claim 21, wherein in the reaction substrates, a molar ratio of the a-H-containing ketone to the alcohol is in a range of 1:2 to 2:1, and a feeding ratio of the a-H-containingketone to the supported catalyst is 0.2 g to 0.3 g of the supported catalyst per 1 mol of the a-H-containing ketone; andthe condensation coupling reaction is conducted at a temperature of 160-210 °C for 30-300 min.