Porous carbon composite material, and preparation method therefor and use thereof

Abstract

The present invention relates to a composite material, wherein the composite material comprises porous carbon and cerium nitrohalide within the porous carbon. In addition, the present invention relates to a method for preparing the composite material, comprising: enabling a haloalkylated resin to react with a nitrogen-containing organic compound to obtain a nitrogen-modified halogen-containing resin; optionally, washing the nitrogen-modified halogen-containing resin by means of a halide salt solution; and mixing the nitrogen-modified halogen-containing resin with a cerium precursor, and then calcining the mixture in an inert gas atmosphere to obtain the composite material. When such a cerium-carbon porous composite material is used as a catalyst in a transesterification reaction, the conversion rate of the reaction can be significantly improved.

Description

A porous carbon composite material, its preparation method and application

[0001] Cross-reference to related applications

[0002] This application claims priority to the patent application filed by the applicant on October 14, 2024 with the China Patent Office, application number 202411432622.1, entitled "A composite material and its synthesis method and application", the contents of which are hereby incorporated herein by reference in their entirety. Technical Field

[0003] This application relates to a porous carbon composite material, its preparation method, and its applications. In particular, this application relates to a novel cerium-carbon porous composite material, its preparation method, and its applications. Background Technology

[0004] Rare earth elements, often referred to as "industrial gold," possess excellent optical, electrical, and catalytic properties, and are widely used in science, technology, and defense. Cerium, an important rare earth element, is typically used in scientific research and industrial production in the form of cerium dioxide. Nano-cerium dioxide, due to its surface effect, volume effect, quantum size effect, and macroscopic quantum tunneling effect, has enormous application value in fields such as gas sensing, ultraviolet shielding, catalysis, and device polishing.

[0005] Currently, cerium in cerium-containing materials is mostly supported on carrier materials in the form of cerium dioxide, especially on carbon materials such as activated carbon. Firstly, in this form of cerium-carbon composite material, because the cerium is primarily supported on the outer surface of the carbon material, the large amount of cerium accumulated together is difficult to function effectively, and when the cerium content on the outer surface of the carbon material is high, it is easily affected by environmental factors, leading to detachment or deformation. Secondly, even when cerium dioxide exists in a certain amount within the carbon material, the effect of cerium in this form is not ideal. For example, when such cerium-carbon composite materials are used as catalysts in transesterification reactions, it is difficult to achieve the desired conversion rate. Therefore, current cerium-carbon composite materials are insufficient to meet the needs of scientific research and industrial production.

[0006] Therefore, a novel cerium-carbon composite material is needed, in which cerium is loaded onto the carbon material in a larger quantity in a non-cerium dioxide form, so that cerium can play a more effective role, for example, when used as a catalyst in transesterification reactions, it can effectively improve the conversion rate of the reaction. Summary of the Invention

[0007] The purpose of this invention is to provide a novel cerium-carbon porous composite material, its preparation method, and its application.

[0008] In a first aspect, the present invention relates to a composite material comprising porous carbon and cerium nitride within the porous carbon, wherein the content of cerium is 1 wt.% or more based on the total weight of the elements within the porous carbon.

[0009] In a second aspect, the present invention relates to a method for preparing a composite material according to the first aspect, comprising:

[0010] 1) React haloalkylated resins with nitrogen-containing organic compounds to obtain nitrogen-modified halogenated resins;

[0011] 2) Optionally, the nitrogen-modified halogenated resin is washed with a halide salt solution, and

[0012] 3) Mix the nitrogen-modified halogenated resin (optionally washed with a halide solution) with a cerium precursor, and then calcine the mixture in an inert gas atmosphere to obtain the composite material.

[0013] Thirdly, the present invention relates to a method for producing carbonates via transesterification, comprising reacting a first carbonate with a hydroxyl-containing compound in the presence of a catalyst to obtain a second carbonate, wherein the catalyst is a composite material according to the first aspect or a composite material prepared according to the method of the second aspect.

[0014] In the cerium-carbon porous composite material of the present invention, cerium nitride, as a novel form of cerium-containing compound, can be distributed in a relatively large quantity within the porous carbon. This cerium-carbon porous composite material allows cerium to function more effectively, particularly when used as a catalyst in transesterification reactions, significantly improving the reaction conversion rate. Attached Figure Description

[0015] The accompanying drawings are provided to further understand this application and form part of the specification. They are used together with the following detailed description to explain this application, but do not constitute a limitation of the invention.

[0016] Figure 1 is the XRD pattern of the cerium-carbon composite material C1 in Example 1;

[0017] Figure 2a is a 120x magnified SEM image of the particle surface of the cerium-carbon composite material C1 in Example 1;

[0018] Figure 2b is a 1000x magnified SEM image of the particle surface of the cerium-carbon composite material C1 in Example 1;

[0019] Figure 2c is the EDX plot of the mapping mode on the particle surface corresponding to Figure 2b;

[0020] Figure 2d is a 150x magnified SEM image of the particle profile of the cerium-carbon composite material C1 in Example 1.

[0021] Figure 2e is a 20,000x magnified SEM image of the particle profile of the cerium-carbon composite material C1 in Example 1.

[0022] Figure 2f is the EDX plot of the mapping mode of the particle profile corresponding to Figure 2e;

[0023] Figure 3 shows the XRD pattern of the cerium-carbon composite material DC1 in Comparative Example 1;

[0024] Figure 4a is a 150x magnified SEM image of the particle surface of the cerium-carbon composite material DC1 in Comparative Example 1.

[0025] Figure 4b is a magnified SEM image of the detached layer on the particle surface of the cerium-carbon composite material DC1 in Comparative Example 1, magnified 87 times.

[0026] Figure 4c is an EDX plot of the mapping mode of the particle surface detachment layer corresponding to Figure 4b;

[0027] Figure 5 shows the XRD pattern of the cerium-carbon composite material DC2 of Comparative Example 2. Detailed Implementation

[0028] The present application will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present application, and do not limit the present invention in any way.

[0029] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0030] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0031] The expressions “comprising” or “including” in this document should be interpreted as including all specifically mentioned features as well as optional, additional, or unspecified features. As used herein, the use of the term “comprising” also discloses schemes in which no other features besides the specifically mentioned features are present, such as expressions “consistently composed of” and “composed of”.

[0032] In the context of this application, the terms "one or more" and "at least one" have the same meaning and are therefore used interchangeably; the terms "one or more" and "at least one" have the same meaning and are therefore used interchangeably.

[0033] In a first aspect, the present invention relates to a composite material comprising porous carbon and cerium nitride within the porous carbon, wherein the content of cerium is 1 wt.% or more based on the total weight of the elements within the porous carbon.

[0034] Preferably, based on the total weight of all elements in the porous carbon body, the content of cerium is from 1 wt.% to 70 wt.%.

[0035] More preferably, based on the total weight of the elements in the porous carbon body, the content of cerium is from 5 wt.% to 68 wt.%.

[0036] More preferably, based on the total weight of the elements in the porous carbon body, the content of cerium is 10 wt.% to 65 wt.%.

[0037] For example, based on the total weight of the elements in the porous carbon body, the content of cerium can be 1.5 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 6 wt.%, 8 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 30 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, or a range consisting of any two of the above values ​​or one of the above values ​​and one end of one of the above ranges or one end of one of the above ranges and one end of another of the above ranges.

[0038] According to the present invention, the porous carbon can serve as a support for loading cerium nitride.

[0039] According to the present invention, the term "porous carbon body" is used in contrast to "porous carbon outer surface" and refers to all parts of porous carbon except for the outer surface, such as the pores within the body, including the pore surface. For example, the "porous carbon body" includes a porous carbon framework and substances such as cerium chloride within the porous carbon pores.

[0040] According to the present invention, the term "total weight of elements in a porous carbon body" refers to the total weight of all elements in the body, specifically including the total weight of elements including carbon, cerium, nitrogen, halogens and optional oxygen.

[0041] According to the present invention, the content of each element (including the content of cerium) in the porous carbon body is measured by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDX).

[0042] To measure the content of various elements within porous carbon, including cerium, the porous carbon can be physically cut open and then measured using SEM coupled with EDX. In this regard, the term "within porous carbon" can also be understood as the portion that can only be measured using SEM coupled with EDX after physically cutting open porous carbon with a large particle size, such as 10 μm or even 100 μm or larger.

[0043] For example, for porous carbon with a particle size of 600 μm to 800 μm, the location for measuring the cerium content is 25 μm or more away from the porous carbon shell or outer surface (excluding grooves or pores), preferably 40 μm or more, such as 50 μm, 70 μm, 80 μm, 100 μm, 200 μm, 300 μm.

[0044] For example, porous carbon with a particle size of 600 μm to 800 μm (e.g., along the maximum cross-section) can be physically cut, and then approximately 0.01 μm particles can be obtained using SEM coupled with EDX. 2 up to 1μm 2 The elemental content within a porous carbon mass is measured by its area. For example, an area of ​​approximately 0.01 μm can be randomly selected from a cut cross-section. 2 up to 1μm 2 The area is used to measure the elemental content within the porous carbon mass; multiple elements (e.g., 2 to 10) of approximately 0.01 μm can be randomly selected. 2 up to 1μm 2 The elemental content within the porous carbon body was measured by area, and the maximum value was selected as the final elemental content value; alternatively, multiple elements (e.g., 2 to 10) of approximately 0.01 μm in size could be randomly selected. 2 up to 1μm 2 The elemental content within the porous carbon body was measured by measuring the area of ​​each element, and then the average value of each element content was calculated as the final elemental content value.

[0045] In one embodiment, the present invention relates to a composite material comprising a porous carbon support and cerium nitride within the pores of the porous carbon support, wherein the cerium content is from 1 wt.% to 70 wt.%, preferably from 10 wt.% to 65 wt.%, based on the total weight of carbon, cerium, nitrogen, halogen and optionally oxygen in the porous carbon body.

[0046] Preferably, the cerium content is 1 wt.% to 50 wt.% or 3 wt.% to 40 wt.% based on the total weight of the elements on the outer surface of the porous carbon.

[0047] For example, based on the total weight of each element on the outer surface of the porous carbon, the content of cerium can be 1 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or a range consisting of any two of the above values ​​or one of the above values ​​and one end of one of the above ranges or one end of one of the above ranges and one end of another of the above ranges.

[0048] According to the present invention, the term "total weight of elements on the external surface of porous carbon" refers to the total weight of all elements on the external surface, specifically including the total weight of elements including carbon, cerium, nitrogen, halogens and optional oxygen.

[0049] The content of various elements on the external surface of porous carbon, including the content of cerium, can be directly measured using SEM coupled with EDX (without physical cutting).

[0050] It can be seen that most of the cerium element loaded in the porous carbon according to the present invention is located within the porous carbon, for example, within the pores. Preferably, the cerium content based on the total weight of the elements within the porous carbon is w1, and the cerium content based on the total weight of the elements on the outer surface of the porous carbon is w2, where w1 is greater than w2; more preferably, w1 is greater than or equal to 1.2 times w2; even more preferably, w1 is 1.2 to 5 times w2, for example, 1.3 times, 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, or 5 times.

[0051] As shown in Figure 2b, a small amount of cerium nitride is coated on the outer surface of the porous carbon. The cerium nitride is dispersed and cannot completely cover the outer surface of the porous carbon. As shown in Figure 2f, the cerium nitride is uniformly distributed within the porous carbon.

[0052] Preferably, in the composite material of the present invention, cerium nitride is distributed within the pores of the porous carbon, for example, on the surface of the pores. The content of cerium within the porous carbon pores has a value or range as defined above and is measured using the method described above.

[0053] Preferably, the cerium halide is at least one of cerium chloride and cerium bromide.

[0054] Preferably, the average pore size of the composite material is 50 nm to 500 nm. More preferably, the average pore size of the composite material is 50 nm to 300 nm.

[0055] For example, the average pore size of the composite material is 55nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 150nm, 160nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 350nm, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one endpoint of one of the above ranges or one endpoint of one of the above ranges and one endpoint of another of the above ranges.

[0056] According to the present invention, the average pore size can be measured using any type of instrument and method commonly used in the chemical engineering field. For example, the average pore size can be measured using mercury porosimetry with a Thermo Fisher Scientific Pascal 140 / 240.

[0057] Such a specific average pore size is conducive to the distribution of a large amount of cerium chloride nitrogen within the porous carbon material.

[0058] Preferably, the specific surface area of ​​the composite material is 5 m². 2 / g to 100m 2 / g. More preferably, the specific surface area of ​​the composite material is 10m². 2 / g to 60m 2 / g.

[0059] For example, the specific surface area of ​​the composite material is 10 m². 2 / g、12m 2 / g, 15m 2 / g、20m 2 / g、25m 2 / g、30m 2 / g、35m 2 / g、40m 2 / g、45m 2 / g, 50m 2 / g、55m 2 / g、60m 2 / g, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one endpoint of one of the above ranges or one endpoint of one of the above ranges and one endpoint of another of the above ranges.

[0060] According to the present invention, the specific surface area can be measured using any type of instrument and method commonly used in the chemical engineering field. For example, the specific surface area can be measured using the fully automated specific surface area and microporous physical adsorption analyzer (ASAP) from Micron Instruments, Inc.

[0061] Preferably, the particle size of the composite material is from 0.1 mm to 3 mm. More preferably, the particle size of the composite material is from 0.3 mm to 2 mm.

[0062] For example, the particle size of the composite material is 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one endpoint of one of the above ranges or one endpoint of one of the above ranges and one endpoint of another of the above ranges.

[0063] In the context of this application, the term "particle size" preferably refers to the average particle size, particularly the D50 particle size. The term "D50 particle size" refers to the particle size at which the cumulative particle size distribution percentage of a sample reaches 50%. The particle size can be measured using any conventionally used instruments and methods in the chemical engineering field. For example, it can be measured using sieving or laser methods. Preferably, sieving is used, employing a sieve screen for measurement.

[0064] Preferably, the porous carbon is derived from the carbonization of a halogenated alkylating resin. More preferably, the porous carbon is derived from the carbonization of a nitrogen-modified halogenated resin.

[0065] Preferably, the nitrogen content is 1 wt.% to 15 wt.% based on the total weight of the composite material. More preferably, the nitrogen content is 3 wt.% to 10 wt.% based on the total weight of the composite material.

[0066] Preferably, based on the total weight of the composite material, the nitrogen content is 3.1 wt.%, 3.2 wt.%, 3.3 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 8.0 wt.%, 10.0 wt.%, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one endpoint of one of the above ranges or one endpoint of one of the above ranges and one endpoint of another of the above ranges.

[0067] According to the present invention, the nitrogen content can be measured using any conventional instruments and methods in the field of chemical materials. For example, the nitrogen content can be measured using an elemental analyzer.

[0068] In the cerium-carbon porous composite material of the present invention, cerium nitride, as a novel form of cerium-containing compound, can be uniformly and stably distributed in a relatively large quantity within the porous carbon mass. Therefore, the cerium-carbon porous composite material of the present invention enables cerium to play a better role.

[0069] The composite material of the present invention can be applied in a variety of fields. For example, the composite material of the present invention can be used as a material for functional devices, such as sensors and semiconductors, and can also be used as a catalyst in, for example, transesterification reactions, or as a catalyst support for further loading other active components, such as metals or their oxides, and then applied to hydrogenation, oxidation, and other reactions, or it can be used as a support for electrocatalysts.

[0070] In a second aspect, the present invention relates to a method for preparing a composite material according to the first aspect, comprising:

[0071] 1) React haloalkylated resins with nitrogen-containing organic compounds to obtain nitrogen-modified halogenated resins;

[0072] 2) Optionally, the nitrogen-modified halogenated resin is washed with a halide salt solution, and

[0073] 3) The nitrogen-modified halogenated resin washed with a halide solution is mixed with a cerium precursor, and then the mixture is calcined in an inert gas atmosphere to obtain the composite material.

[0074] According to the present invention, the term "nitrogen-containing organic compound" refers to a compound containing nitrogen, carbon, and optionally hydrogen.

[0075] When halogenated alkyl resins come into contact with nitrogen-containing organic compounds, it is presumed that the chemical bonds between the halogen and the alkyl group break, and the nitrogen in the nitrogen-containing organic compound attaches to both the alkyl group and the halogen, forming a nitrogen-modified halogen-containing resin. The nitrogen attached to the alkyl group and the halogen can enhance the anchoring of active metals (e.g., cerium), allowing the active metals (e.g., cerium) to be distributed in a larger quantity and more uniformly within the porous carbon body.

[0076] According to the present invention, the term "alkyl" has a conventional definition in the chemical field.

[0077] Specifically, the term "alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group, preferably having 1 to 10, more preferably 1 to 5, and more preferably 1 to 3 carbon atoms. For example, "alkyl" can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or n-pentyl.

[0078] Preferably, the content of cerium nitride is from 3 wt.% to 85 wt.% based on the total weight of the resulting composite material. More preferably, the content of cerium nitride is from 5 wt.% to 70 wt.% based on the total weight of the composite material. Even more preferably, the content of cerium nitride is from 8 wt.% to 55 wt.% based on the total weight of the composite material.

[0079] For example, based on the total weight of the resulting composite material, the content of cerium nitride is 3 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one endpoint of one of the above ranges or one endpoint of one of the above ranges and one endpoint of another of the above ranges.

[0080] According to the present invention, the content of cerium nitride is obtained by dividing the weight of cerium nitride calculated using the amount of the raw material cerium precursor at a conversion rate of 100% by the total weight of the resulting composite material.

[0081] Preferably, the halogenated alkylating resin is a chloroalkylating resin and / or a brominated alkylating resin, with chloroalkylating resin being more preferred.

[0082] Preferably, the halogenated alkylated resin is a halogenated methyl resin.

[0083] More preferably, the halogenated alkylating resin is one or more selected from chloromethyl polystyrene, chloromethyl polyethylene, chloromethyl carboxyl resin, and chloromethyl phenolic resin. Even more preferably, the halogenated alkylating resin is chloromethyl polystyrene.

[0084] Preferably, the particle size of the halogenated alkyl resin is substantially the same as that of the composite material.

[0085] Preferably, the particle size of the halogenated alkylating resin is from 0.1 mm to 3 mm. More preferably, the particle size of the halogenated alkylating resin is from 0.3 mm to 2 mm.

[0086] For example, the particle size of the haloalkylated resin is 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one end of one of the above ranges or one end of one of the above ranges and one end of another of the above ranges.

[0087] Preferably, the halogen (preferably chlorine) content is greater than 1 wt.% based on the weight of the halogenated alkylating resin. More preferably, the halogen (preferably chlorine) content is from 10 wt.% to 25 wt.% based on the weight of the halogenated alkylating resin.

[0088] For example, based on the weight of the halogenated alkylated resin, the halogen (preferably chlorine) content is 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, 25 wt.%, or a value within a range consisting of any two of the above values ​​or one of the above values ​​and one end of one of the above ranges or one end of one of the above ranges and one end of another of the above ranges.

[0089] According to the present invention, the halogen content can be measured using any conventional instruments and methods in the field of chemical materials. For example, the halogen content can be measured using ion chromatography.

[0090] Preferably, the haloalkylated resin is spherical. According to the present invention, the shape of the haloalkylated resin can be determined visually using a scanning electron microscope (SEM).

[0091] Preferably, the reaction in step 1) is carried out in the presence of a first solvent. Preferably, the first solvent is one or more selected from toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, trichloromethane, amides, and ethers. More preferably, the first solvent is an alkylamide. Even more preferably, the first solvent is N,N-dimethylformamide.

[0092] Preferably, the weight ratio of the halogenated alkylating resin to the first solvent is 1:1 to 1:10.

[0093] More preferably, the weight ratio of the halogenated alkylating resin to the first solvent is 1:3 to 1:10.

[0094] According to the present invention, the nitrogen-containing organic compound may have a straight chain, a branched chain, and / or a cyclic structure, and may be any aliphatic or aromatic nitrogen-containing compound.

[0095] Preferably, the nitrogen-containing organic compound is selected from one or more of piperazine, amine, pyridine, imidazole, quinoline, and pyrrole. More preferably, the nitrogen-containing organic compound is one or more of methylamine, ethylamine, piperazine, imidazole, and pyridine, wherein the methylamine is preferably trimethylamine.

[0096] Preferably, the weight ratio of the nitrogen-containing organic compound to the halogenated alkylating resin is 0.5 to 5.0. More preferably, the weight ratio of the nitrogen-containing organic compound to the halogenated alkylating resin is 0.8 to 2.0. Even more preferably, the weight ratio of the nitrogen-containing organic compound to the halogenated alkylating resin is 0.8 to 1.5.

[0097] Preferably, the reaction in step 1) is carried out at a temperature of 50°C to 150°C. More preferably, the reaction in step 1) is carried out at a temperature of 70°C to 90°C.

[0098] Preferably, the reaction in step 1) is carried out for 1 hour to 24 hours. More preferably, the reaction in step 1) is carried out for 10 hours to 14 hours.

[0099] According to the present invention, the halide solution can be an aqueous solution of a metal salt containing fluoride, chloride, bromide, and iodide ions. Preferably, the halide solution can be an aqueous solution of a metal salt containing chloride and / or bromide ions.

[0100] Preferably, the brine solution in step 2) is one or more of sodium chloride, potassium chloride, zinc chloride, sodium bromide, potassium bromide and zinc bromide.

[0101] When washing with metal bromide salts, such as sodium bromide, potassium bromide, or zinc bromide, bromide ions can at least partially (preferably completely) replace chloride ions on nitrogen-modified halogen-containing resins. Mixing this modified resin, with at least partial (preferably complete) bromide ion replacement, with a cerium precursor and then calcining the mixture under an inert gas atmosphere yields cerium nitrogen bromide.

[0102] Preferably, the mixing in step 3) is carried out in the presence of a second solvent. Preferably, the second solvent is at least one of water and alcohol. More preferably, the second solvent is one or more of water, methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, and pentanol. Even more preferably, the second solvent is at least one of water, ethylene glycol, and glycerol.

[0103] Preferably, the weight ratio of the nitrogen-modified halogenated resin to the second solvent is 1:1 to 1:10. More preferably, the weight ratio of the nitrogen-modified halogenated resin to the second solvent is 1:2 to 1:8.

[0104] Preferably, the mixing in step 3) is carried out under heating and stirring.

[0105] Preferably, the heating and stirring are performed at a temperature of 20°C to 90°C. More preferably, the heating and stirring are performed at a temperature of 30°C to 70°C.

[0106] Preferably, the heating and stirring are performed at a rate of 50 rpm to 1000 rpm. More preferably, the heating and stirring are performed at a rate of 400 rpm to 600 rpm.

[0107] Preferably, the heating and stirring is carried out for 1 hour to 24 hours. More preferably, the heating and stirring is carried out for 2 hours to 6 hours.

[0108] Preferably, the cerium precursor is a cerium salt. More preferably, the cerium precursor is cerium nitrate and / or cerium chloride.

[0109] Preferably, the weight ratio of the cerium precursor to the nitrogen-modified halogen-containing resin is 0.01 to 1.5. More preferably, the weight ratio of the cerium precursor to the nitrogen-modified halogen-containing resin is 0.05 to 1.2. Even more preferably, the weight ratio of the cerium precursor to the nitrogen-modified halogen-containing resin is 0.1 to 1.2.

[0110] Preferably, step 3) further includes a drying step before calcination. Preferably, the drying is carried out at a temperature of 70°C to 150°C for a duration of 2 hours to 48 hours.

[0111] Preferably, the inert gas is one or more of nitrogen, carbon dioxide, and argon. More preferably, the inert gas is nitrogen and / or argon.

[0112] Preferably, the calcination is carried out at a temperature of 300°C to 1200°C for 1 hour to 48 hours. More preferably, the calcination is carried out at a temperature of 400°C to 900°C for 2 hours to 36 hours. Even more preferably, the calcination is carried out at a temperature of 600°C to 800°C for 4 hours to 10 hours. Through the calcination step, cerium nitride can be uniformly and abundantly formed within the porous carbon body.

[0113] By means of the method according to the second aspect, a cerium-carbon porous composite material according to the first aspect can be obtained, wherein cerium nitride, as a novel form of cerium-containing compound, can be uniformly and stably distributed in a relatively large amount within the porous carbon body.

[0114] Thirdly, the present invention relates to a method for producing carbonates via transesterification, comprising reacting a first carbonate with a hydroxyl-containing compound in the presence of a catalyst to obtain a second carbonate, wherein the catalyst is a composite material according to the first aspect or a composite material prepared according to the method of the second aspect.

[0115] Preferably, the first carbonate is at least one selected from alkylene carbonate and dialkyl carbonate. More preferably, the first carbonate is at least one selected from ethylene carbonate, propylene carbonate, and dimethyl carbonate.

[0116] Preferably, the hydroxyl-containing compound is at least one selected from alkyl alcohols and alkoxy alcohols. More preferably, the hydroxyl-containing compound is at least one selected from methanol, ethanol, and ethylene glycol monomethyl ether.

[0117] Preferably, the second carbonate is at least one selected from dialkyl carbonate and di(alkoxyalkyl) carbonate. More preferably, the second carbonate is at least one selected from dimethyl carbonate and di(2-methoxyethyl) carbonate.

[0118] The term "alkyl" has the definition described above.

[0119] According to the present invention, the terms "alkylene" and "alkoxy" have conventional definitions in the chemical field.

[0120] Specifically, the term "alkylene" indicates that one hydrogen atom of the alkyl group defined above has been further substituted. For example, "alkylene" can be methylene, ethylene, n-propylene, or isopropylene.

[0121] The term "alkoxy" refers to an alkyl group that is attached to the parent molecule by an oxygen atom, such as having the structure RO-, where the R group has the definition of "alkyl" above. For example, "alkoxy" can be methoxy, ethoxy, n-propoxy, or isopropoxy.

[0122] In one embodiment, the first carbonate is ethylene carbonate, the hydroxyl-containing compound is methanol, and the second carbonate is dimethyl carbonate.

[0123] In one embodiment, the first carbonate is propylene carbonate, the hydroxyl-containing compound is methanol, and the second carbonate is dimethyl carbonate.

[0124] In one embodiment, the first carbonate is dimethyl carbonate, the hydroxyl-containing compound is ethylene glycol monomethyl ether, and the second carbonate is di(2-methoxyethyl) carbonate.

[0125] Preferably, the transesterification reaction is carried out at a temperature of 70°C to 150°C. More preferably, the transesterification reaction is carried out at a temperature of 100°C to 120°C.

[0126] Preferably, the transesterification reaction is carried out for 1 hour to 15 hours. More preferably, the transesterification reaction is carried out for 5 hours to 10 hours.

[0127] Preferably, the molar ratio of the hydroxyl-containing compound to the first carbonate is (1-15):1. More preferably, the molar ratio of the hydroxyl-containing compound to the first carbonate is (3-12):1.

[0128] Preferably, the weight ratio of catalyst to first carbonate is (0.05-0.8):1. More preferably, the weight ratio of catalyst to first carbonate is (0.05-0.6):1. Even more preferably, the weight ratio of catalyst to first carbonate is (0.08-0.5):1.

[0129] Preferably, the molar ratio of the first carbonate to the hydroxyl-containing compound is (1-15):1. More preferably, the molar ratio of the first carbonate to the hydroxyl-containing compound is (3-12):1.

[0130] Preferably, the weight ratio of catalyst to hydroxyl-containing compound is (0.5-3):1. More preferably, the weight ratio of catalyst to hydroxyl-containing compound is (0.5-2):1. Even more preferably, the weight ratio of catalyst to hydroxyl-containing compound is (0.5-1):1.

[0131] The composite material of the present invention exhibits good activity and selectivity when used as a catalyst in transesterification reactions. Furthermore, the composite material of the present invention can be reused. After multiple cycles, for example, 1 to 10 cycles (e.g., 1 to 5 cycles), the composite material of the present invention still exhibits good activity and selectivity when used as a catalyst in transesterification reactions.

[0132] In the cerium-carbon composite material of the present invention, cerium exists in the form of a novel cerium-containing compound, namely cerium nitride, and can be uniformly distributed in a high content within the porous carbon mass. Compared with cerium-carbon composite materials supported on carbon materials in the form of cerium dioxide, the novel cerium-carbon composite material of the present invention significantly improves the conversion rate of the transesterification reaction when used as a catalyst due to the stronger basicity of cerium nitride. In transesterification reactions, especially in the transesterification of carbonates, the novel cerium-carbon composite material of the present invention can achieve a conversion rate greater than 99% and a selectivity greater than 99% as a catalyst. Even after repeated use in the transesterification reaction for 5 times, a conversion rate greater than 99% and a selectivity greater than 99% can still be achieved.

[0133] Preferably, the transesterification reaction is carried out in a reactor (e.g., a batch reactor) equipped with a distillation unit, both the reactor and the distillation unit containing a catalyst. Preferably, the catalyst loading in the distillation unit accounts for 30 wt.% to 70 wt.% of the total catalyst content. More preferably, the catalyst loading in the distillation unit accounts for 40 wt.% to 60 wt.% of the total catalyst content.

[0134] Preferably, in the distillation apparatus, the catalyst is packed in the lower part, and the upper part is packed with inert packing. According to the invention, the inert packing refers to any substance that does not undergo a chemical reaction under the conditions of transesterification. For example, the inert packing can be one or more of ceramics, glass, and stainless steel. Preferably, the volume ratio of catalyst to inert packing is (0.05-1):1. More preferably, the volume ratio of catalyst to inert packing is (0.1-0.8):1.

[0135] Preferably, the particle size of the inert filler is 1 mm to 30 mm.

[0136] Preferably, the reflux ratio of the distillation apparatus is (1-3):1.

[0137] By utilizing the combination of the reactor and the distillation unit, and by simultaneously placing the catalyst in both the reactor and the distillation unit, the conversion rate of the transesterification reaction can be further improved when using the composite material of the present invention as a catalyst. Furthermore, the specific catalyst-to-inert packing volume ratio, inert packing particle size, and reflux ratio of the distillation unit described above can further enhance the conversion rate of the transesterification reaction.

[0138] This application relates to the following technical solutions:

[0139] [1] A composite material, characterized in that: the composite material comprises cerium chloride and carbon.

[0140] [2] The composite material described in Project [1] is characterized in that: based on the mass of the composite material, the mass content of cerium chloride is 0.1%-70%.

[0141] [3] The composite material according to item [1] or [2] is characterized in that: the average pore size of the composite material is 50-500 nm and the specific surface area is 5-100 m². 2 / g.

[0142] [4] The composite material according to item [1] or [2] is characterized in that: the carbon originates from the carbonization of nitrogen-modified chloromethyl resin;

[0143] And / or, in the composite material, the total mass content of nitrogen is 1%-15%, preferably 3%-10%.

[0144] [5] A method for synthesizing the composite material described in any one of items [1]-[4], including:

[0145] 1) Chloromethyl resin is mixed with a first solvent, a nitrogen-containing organic compound is added to react, and the mixture is dried to obtain modified chloromethyl resin;

[0146] 2) The modified chloromethyl resin is mixed with cerium precursor and second solvent under heating and stirring conditions, dried, and then calcined in an inactive gas atmosphere to obtain the composite material.

[0147] [6] The synthesis method according to Project [5] is characterized in that: the chloromethyl resin in step 1) is one or more of chloromethyl polystyrene, chloromethyl polyethylene, chloromethyl carboxylic acid resin and chloromethyl phenolic resin, preferably chloromethyl polystyrene;

[0148] And / or, the chloromethyl resin has a particle size of 0.1 mm-3 mm, preferably 0.3 mm-2 mm;

[0149] And / or, the chlorine content in the chloromethyl resin is greater than 1%, preferably 10%-25% by mass;

[0150] And / or, the chloromethyl resin is spherical.

[0151] [7] The synthesis method according to Project [5] is characterized in that: in step 1), the first solvent is one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, chloroform, amide and ether;

[0152] And / or, in step 1), the mass ratio of the chloromethyl resin to the first solvent is 1:1 to 1:10;

[0153] And / or, the nitrogen-containing organic compound in step 1) is selected from one or more of piperazine, amine, pyridine, imidazole, quinoline, and pyrrole, preferably one or more of methylamine, ethylamine, piperazine, imidazole, and pyridine;

[0154] And / or, the mass ratio of the nitrogen-containing organic compound to the chloromethyl resin in step 1) is 0.5-5.0;

[0155] And / or, the reaction conditions in step 1) include: a reaction temperature of 50-150°C and a reaction time of 1-24h.

[0156] [8] The synthesis method according to item [5] is characterized in that: in step 2), the second solvent is at least one of water and alcohol, preferably one or more of water, methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, and pentanol;

[0157] And / or, in step 2), the mass ratio of the modified chloromethyl resin to the second solvent is 1:1 to 1:10;

[0158] And / or, in step 2), the heating and stirring conditions include: a heating temperature of 20-150℃; a stirring rate of 50-1000 rpm; and a stirring time of 1-24 h;

[0159] And / or, in step 2), the cerium precursor is selected from cerium salts;

[0160] And / or, in step 2), the mass ratio of the cerium precursor to the modified chloromethyl resin is 0.01-1.5;

[0161] And / or, in step 2), the drying conditions include a temperature of 70-150°C and a time of 2-48 hours;

[0162] And / or, in step 2), the inactive gas is one or more of nitrogen, carbon dioxide, and argon; the calcination temperature is 300-1200℃, and the calcination time is 1-48h.

[0163] [9] A method for preparing dialkyl carbonate, comprising the step of reacting alkylene carbonate and methanol under the action of a catalyst to obtain dialkyl carbonate, characterized in that the catalyst is any one of the catalysts in [1]-[4] or a catalyst prepared by any one of the preparation methods in [5]-[8].

[0164]

[0010] The preparation method according to item [9] is characterized in that the reaction conditions include: the reaction temperature is 70℃-150℃, preferably 70℃-120℃;

[0165] And / or, the reaction time is 1h-15h, preferably 2h-12h;

[0166] And / or, the alkylene carbonate is one or more of ethylene carbonate or propylene carbonate;

[0167] And / or, the molar ratio of methanol to alkylene carbonate is (2-15):1, preferably (3-12):1;

[0168] And / or, the total amount of catalyst to alkylene carbonate is in a mass ratio of (0.05-0.8):1, preferably (0.05-0.6):1.

[0169]

[0011] A method for preparing di(2-methoxyethyl) carbonate, comprising the step of reacting ethylene glycol methyl ether and dimethyl carbonate under the action of a catalyst to obtain di(2-methoxyethyl) carbonate, characterized in that the catalyst is any one of the catalysts in items [1]-[4] or a catalyst prepared by any one of the preparation methods in items [5]-[8].

[0170]

[0012] The preparation method according to item

[0011] is characterized in that the reaction conditions include: the reaction temperature is 70℃-130℃, preferably 70℃-120℃;

[0171] And / or, the reaction time is 1h-15h, preferably 2h-12h;

[0172] And / or, the molar ratio of dimethyl carbonate to ethylene glycol methyl ether is (2-15):1, preferably (3-12):1;

[0173] And / or, the total amount of catalyst used to the mass ratio of ethylene glycol methyl ether is (0.5-3):1, preferably (0.5-2):1.

[0174]

[0013] The preparation method according to any one of items [9]-

[0012] is characterized in that the reaction is carried out in a batch reactor with a distillation device, both the reactor and the distillation device contain a catalyst, wherein the catalyst loading in the distillation device accounts for 30%-70% of the total catalyst loading, by mass.

[0175] And / or, in the distillation apparatus, the catalyst is packed in the lower part and the inert packing is packed in the upper part, with the volume ratio of catalyst to inert packing being (0.05-1):1, preferably (0.1-1):1;

[0176] And / or, the particle size of the inert filler is 1mm-30mm;

[0177] And / or, the reflux ratio of the distillation unit is (1-3):1.

[0178] Example

[0179] The following embodiments will further illustrate the implementation of the present invention, but do not limit the scope of this application.

[0180] The relevant parameters in the various embodiments and comparative examples were measured using the following instruments and methods:

[0181] X-ray diffractometer (XRD): Bruker D8 Advance SS type, CuKα radiation, 40 kV, 300 mA, scanning speed of 2° / min, scanning range of 5-80°.

[0182] Scanning electron microscope (SEM): Hitachi S4800.

[0183] The nitrogen content was measured using a Therm2000 elemental analyzer, and the testing method was elemental analysis.

[0184] Cerium content was measured using a combination of a Zeiss Merkin scanning electron microscope (SEM) and an OxfordMAX energy-dispersive X-ray spectrometer (EDX). The cerium content within the cerium-carbon composite material (porous carbon) was obtained by cutting the composite material and measuring the cerium content of five randomly selected regions on the cross-section, then averaging the results. The cerium content on the outer surface of the cerium-carbon composite material (porous carbon) was obtained by directly measuring the cerium content of five randomly selected regions on the surface of the composite material and then averaging the results.

[0185] The specific surface area was measured using the fully automated specific surface area and microporous physical adsorption analyzer (ASAP) from Micron Instruments, Inc.

[0186] The average pore size of the cerium-carbon composite material was measured using mercury porosimetry with a Thermo Fisher Scientific Pascal 140 / 240.

[0187]

Example 1

[0188] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt.%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70℃, and then 50g of imidazole was added. After reacting for 12h, the mixture was cooled and the solid and liquid were separated. The separated solid was washed with deionized water and then dried overnight at 100℃ to obtain nitrogen-modified chlorine-containing resin. 10g of nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 3.8g of cerium nitrate was added to a 100ml flask, and water was added until 80g of aqueous solution was obtained. This 80g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2h at 50℃, and then dried in an oven at 100℃ for 24h. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C1, wherein the content of cerium chloride was 30 wt.% and the total nitrogen content was 5.1 wt.%. The average pore size of cerium-carbon composite material C1 was 200 nm, and the specific surface area was 34.3 m². 2 / g.

[0189] The XRD characterization results of the cerium-carbon composite C1 are shown in Figure 1. Its characteristic peaks are consistent with those of cerium chloride, and no characteristic peaks of cerium dioxide are observed.

[0190] The SEM characterization results of the cerium-carbon composite C1 are shown in Figure 2. The cerium content in the cerium-carbon composite C1 is 32.2 wt.% within the composite material and 16.7 wt.% outside the composite material.

[0191] Cerium-carbon composite material C1 was used as a catalyst in the preparation of dimethyl carbonate: 10.0 g of catalyst C1 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 256 g (8 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 1. The reaction was considered complete when the addition was finished. Calculations showed that the conversion rate of ethylene carbonate was 99.2%, and the selectivity of dimethyl carbonate was 99.5%.

[0192] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50 wt.% of the total catalyst volume.

[0193] Catalyst C1 was reused 5 times with fresh raw materials, and the conversion rate of ethylene carbonate was greater than 99% and the selectivity of dimethyl carbonate was greater than 99% in each reaction.

[0194] Cerium-carbon composite material C1 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst C1 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1. The reaction was considered complete when the addition was finished. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 99.5%, and the selectivity of di(2-methoxyethyl) carbonate was 99.5%.

[0195] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50 wt.% of the total catalyst volume.

[0196] Catalyst C1 was reused 5 times with fresh feedstock, and the conversion rate of ethylene glycol monomethyl ether was greater than 99% and the selectivity of di(2-methoxyethyl) carbonate was greater than 99% in each reaction.

[0197]

Example 2

[0198] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 90℃, and then 50g of imidazole was added. After reacting for 12 hours, the mixture was cooled and the solid and liquid were separated. The separated solid was washed with deionized water and then dried overnight at 100℃ to obtain nitrogen-modified chlorine-containing resin. 10g of nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 1.3g of cerium nitrate was added to a 100ml flask, and water was added until a 40g aqueous solution was obtained. This 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 70℃ and then dried in an oven at 100℃ for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C2, wherein the content of cerium chloride was 15 wt.% and the total nitrogen content was 3.6 wt.%. The average pore size of cerium-carbon composite material C2 was 200 nm, and the specific surface area was 25.2 m². 2 / g.

[0199] The XRD pattern of the cerium-carbon composite C2 is similar to that in Figure 1.

[0200] The SEM characterization results of the cerium-carbon composite C2 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C2 is 19.3 wt.% within the composite material and 9.4 wt.% outside the composite material.

[0201] Cerium-carbon composite material C2 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 30.0 g of catalyst C2 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 2. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 99.8%, and the selectivity of di(2-methoxyethyl) carbonate was 99.6%.

[0202] The distillation column consists of a catalyst layer at the bottom, 60 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.6:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0203]

Example 3

[0204] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70℃, and then 50g of trimethylamine was added. After reacting for 12 hours, the mixture was cooled and the solid and liquid were separated. The separated solid was washed with deionized water and then dried overnight at 100℃ to obtain nitrogen-modified chlorine-containing resin. 10g of nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 5g of cerium nitrate was added to a 100ml flask, and water was added until a 40g aqueous solution was obtained. This 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 6 hours at 30℃ and then dried in an oven at 100℃ for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 600°C for 8 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C3, wherein the content of cerium chloride was 40 wt.% and the total nitrogen content was 5.5 wt.%. The average pore size of cerium-carbon composite material C3 was 100 nm, and the specific surface area was 44.5 m². 2 / g.

[0205] The XRD pattern of the cerium-carbon composite C3 is similar to that in Figure 1.

[0206] The SEM characterization results of the cerium-carbon composite C3 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C3 is 47.6 wt.% within the composite material and 30.9 wt.% outside the composite material.

[0207] Cerium-carbon composite material C3 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst C3 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 270 g (3 mol) of dimethyl carbonate was added dropwise over 8 hours. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1.5. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 99.8%, and the selectivity of di(2-methoxyethyl) carbonate was 99.7%.

[0208] The lower section of the rectification column is a catalyst layer, 40 cm high, and above it is a glass packing layer, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the rectification column is 0.4:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the rectification column accounts for 50% of the total catalyst volume.

[0209]

Example 4

[0210] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70℃, and 50g of imidazole was added. After reacting for 12 hours, the mixture was cooled and the solid and liquid phases were separated. The separated solid was washed with deionized water and then dried overnight at 100℃ to obtain a nitrogen-modified chlorine-containing resin. 10g of the nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 11g of cerium nitrate was added to a 100ml flask, followed by water until a 40g aqueous solution was obtained. This 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 50℃ and then dried in an oven at 100℃ for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 6 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C4, wherein the content of cerium chloride was 50 wt.% and the total nitrogen content was 6.8 wt.%. The average pore size of the cerium-carbon composite material C4 was 100 nm, and the specific surface area was 45.7 m². 2 / g.

[0211] The XRD pattern of the cerium-carbon composite C4 is similar to that in Figure 1.

[0212] The SEM characterization results of the cerium-carbon composite C4 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C4 is 62.3 wt.% within the composite material and 39.6 wt.% outside the composite material.

[0213] Cerium-carbon composite material C4 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst C4 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 180 g (2 mol) of dimethyl carbonate was added dropwise over 8 hours. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1.5. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 99.5%, and the selectivity of di(2-methoxyethyl) carbonate was 99.5%.

[0214] The distillation column consists of a catalyst layer at the bottom, 40 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.4:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0215]

Example 5

[0216] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt%, spherical, D50 particle size 0.7mm) and 300ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70°C, and 40g of piperazine was added. After reacting for 12 hours, the mixture was cooled and the solid and liquid were separated. The separated solid was washed with deionized water and then dried overnight at 100°C to obtain nitrogen-modified chlorine-containing resin. 10g of nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 1g of cerium nitrate was added to a 100ml flask, followed by water until a 40g solution was obtained. This 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 50°C and then dried in an oven at 100°C for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C5, wherein the content of cerium chloride was 9.7 wt.% and the total nitrogen content was 3.3 wt.%. The average pore size of cerium-carbon composite material C5 was 60 nm, and the specific surface area was 30.3 m². 2 / g.

[0217] The XRD pattern of the cerium-carbon composite C5 is similar to that in Figure 1.

[0218] The SEM characterization results of the cerium-carbon composite C5 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C5 is 12.4 wt.% within the composite material and 4.2 wt.% outside the composite material.

[0219] Cerium-carbon composite material C5 was used as a catalyst in the preparation of dimethyl carbonate: 30.0 g of catalyst C5 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 320 g (10 mol) of methanol was added dropwise over 8 hours. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 2. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene carbonate was 99.4%, and the selectivity of dimethyl carbonate was 99.8%.

[0220] The distillation column consists of a catalyst layer at the bottom, 40 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 40% of the total catalyst volume.

[0221]

Example 6

[0222] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 19wt.%, spherical, D50 particle size 0.7mm) and 400ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70℃, and 50g of trimethylamine aqueous solution was added. After reacting for 12h, the mixture was cooled and the solid and liquid were separated. The separated solid was washed with deionized water and then dried overnight at 100℃ to obtain nitrogen-modified chlorine-containing resin. 10g of nitrogen-modified chlorine-containing resin was added to another 500ml three-necked flask. 6.3g of cerium nitrate was added to a 100ml flask, and water was added until a solution of 40g was obtained. The 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2h at 50℃ and then dried in an oven at 100℃ for 24h. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C6, wherein the content of cerium chloride was 45 wt.% and the total nitrogen content was 5.6 wt.%. The average pore size of cerium-carbon composite material C6 was 300 nm, and the specific surface area was 15.5 m². 2 / g.

[0223] The XRD pattern of the cerium-carbon composite C6 is similar to that in Figure 1.

[0224] The SEM characterization results of the cerium-carbon composite C6 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C6 is 51.3 wt.% in vivo and 36.7 wt.% in vitro.

[0225] Cerium-carbon composite material C6 was used as a catalyst in the preparation of dimethyl carbonate: 20.0 g of catalyst C6 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 192 g (6 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 2. The reaction was considered complete when the addition was finished. Calculations showed that the conversion rate of ethylene carbonate was 99.2%, and the selectivity of dimethyl carbonate was 99.3%.

[0226] The distillation column consists of a catalyst layer at the bottom, 60 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.4:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 60% of the total catalyst volume.

[0227]

Example 7

[0228] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 90℃, and 50g of imidazole was added. After reacting for 12 hours, the mixture was cooled, and solid-liquid separation was performed. The separated solid was washed with 200ml of 5wt.% sodium bromide solution, then washed with deionized water, and dried overnight at 100℃ to obtain nitrogen-modified bromine-containing resin. 10g of the nitrogen-modified bromine-containing resin was added to another 500ml three-necked flask. 1.3g of cerium nitrate was added to a 100ml flask, and more were added until a solution of 40g was obtained. This 40g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 70°C, and then dried in an oven at 100°C for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material C7, wherein the content of cerium bromide was 15 wt.% and the total nitrogen content was 3.6 wt.%. The average pore size of cerium-carbon composite material C7 was 200 nm, and the specific surface area was 29.9 m². 2 / g.

[0229] The XRD pattern of the cerium-carbon composite C7 is similar to that in Figure 1.

[0230] The SEM characterization results of the cerium-carbon composite C7 are similar to those shown in Figure 2. The cerium content in the cerium-carbon composite C7 is 20.6 wt.% within the composite material and 9.4 wt.% outside the composite material.

[0231] Cerium-carbon composite material C7 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 30.0 g of catalyst C2 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 2. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 99.7%, and the selectivity of di(2-methoxyethyl) carbonate was 99.8%.

[0232] The distillation column consists of a catalyst layer at the bottom, 60 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.6:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0233] Comparative Example 1

[0234] Catalyst preparation: 10 g of chloromethyl styrene resin (commercially purchased, chlorine content 17 wt.%, spherical, D50 particle size 0.7 mm) was added to a 500 ml three-necked flask. 3.8 g of cerium nitrate was added to a 100 ml flask, followed by water until 80 g of solution was obtained. This 80 g aqueous solution was then added to the 500 ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 h at 50 °C and dried in an oven at 100 °C for 24 h. The mixture was then transferred to a muffle furnace and calcined at 700 °C for 4 h under a nitrogen atmosphere to obtain cerium-carbon composite material DC1, wherein the cerium dioxide content was 32 wt.%.

[0235] The XRD characterization results of the cerium-carbon composite DC1 are shown in Figure 3. No characteristic peaks of cerium chloride (N-C) were found; only characteristic peaks of cerium dioxide (C₂O₃) were present. The total nitrogen content in composite DC1 was 0 wt.%. The average pore size of the cerium-carbon composite DC1 was 200 nm, and its specific surface area was 20.3 m². 2 The SEM characterization results of the cerium-carbon composite DC1 are shown in Figure 4. The cerium content in DC1 is less than 1 wt.% in vivo and 83.2 wt.% in vitro.

[0236] Cerium-carbon composite material DC1 was used as a catalyst in the preparation of dimethyl carbonate: 10.0 g of catalyst DC1 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 256 g (8 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene carbonate was 49.2%, and the selectivity of dimethyl carbonate was 99.3%.

[0237] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0238] Cerium-carbon composite material DC1 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst DC1 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 39.7%, and the selectivity of di(2-methoxyethyl) carbonate was 99.4%.

[0239] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0240] Comparative Example 2

[0241] Catalyst preparation: 10g of commercially available activated carbon was added to a 500ml three-necked flask. 11g of cerium nitrate was added to a 100ml flask, followed by water until a 100ml aqueous solution was obtained. This 100ml aqueous solution was then added to the 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 50°C and dried in an oven at 100°C for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material DC2, wherein the cerium dioxide content was 30wt.%. The average pore size of the cerium-carbon composite material DC2 was 2nm, and the specific surface area was 189.3m². 2 The XRD characterization results of the cerium-carbon composite DC2 are shown in Figure 5. No characteristic peaks of cerium chloride (N-C) are present; only characteristic peaks of cerium dioxide (C) are observed. The total nitrogen content in composite DC1 is 0 wt.%.

[0242] The cerium content in the cerium-carbon composite DC2 is less than 1 wt.% in vivo and 81.8 wt.% in vitro.

[0243] Cerium-carbon composite material DC2 was used as a catalyst in the preparation of dimethyl carbonate: 10.0 g of catalyst DC2 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 256 g (8 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene carbonate was 53.7%, and the selectivity of dimethyl carbonate was 99.1%.

[0244] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst filling the distillation column accounts for 50% of the total catalyst volume.

[0245] The catalyst DC2 was reused 5 times with fresh feedstock, and the conversion rate of ethylene carbonate was reduced to 24.3% in each reaction, while the selectivity of dimethyl carbonate was greater than 99%.

[0246] Cerium-carbon composite material DC2 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst DC2 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 47.6%, and the selectivity of di(2-methoxyethyl) carbonate was 99.2%.

[0247] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0248] Comparative Example 3

[0249] Catalyst preparation: 10g of commercially available activated carbon and 10g of ammonium chloride were added to a 500ml three-necked flask. 11g of cerium nitrate was added to a 100ml flask, followed by water until a 100ml solution was obtained. This 100ml aqueous solution was then added to the 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 50°C and dried in an oven at 100°C for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain cerium-carbon composite material DC2, wherein the cerium chloride content was 31.2 wt.%. The cerium-carbon composite material DC3 had an average pore size of 2nm and a specific surface area of ​​165.6m². 2 / g.

[0250] The XRD characterization results of the cerium-carbon composite DC3 are similar to those shown in Figure 1, and the characteristic peaks of cerium chloride nitrogen are present.

[0251] The cerium content in the cerium-carbon composite DC3 is less than 1 wt.% in vivo and 73.5 wt.% in vitro.

[0252] Cerium-carbon composite material DC3 was used as a catalyst in the preparation of dimethyl carbonate: 10.0 g of catalyst DC3 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 256 g (8 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene carbonate was 74.8%, and the selectivity of dimethyl carbonate was 99.2%.

[0253] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst filling the distillation column accounts for 50% of the total catalyst volume.

[0254] The catalyst DC3 was reused 5 times with fresh raw materials. The conversion rate of ethylene carbonate was reduced to 38.9% in each reaction, and the selectivity of dimethyl carbonate was greater than 99%.

[0255] Cerium-carbon composite material DC3 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst DC3 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 47.6%, and the selectivity of di(2-methoxyethyl) carbonate was 99.2%.

[0256] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0257] Comparative Example 4

[0258] Catalyst preparation: 50g of chloromethylstyrene resin (commercially purchased, chlorine content 17wt.%, spherical, D50 particle size 0.7mm) and 200ml of N,N-dimethylformamide were added to a 500ml three-necked flask. The mixture was stirred at 500 rpm while the temperature was raised to 70℃, and 50g of imidazole was added. After reacting for 12 hours, the mixture was cooled, and solid-liquid separation was performed. The separated solid was washed with 100ml of 10wt.% sodium nitrate solution, followed by washing with deionized water, and then dried overnight at 100℃ to obtain nitrogen-modified non-halogenated resin. 10g of nitrogen-modified non-halogenated resin was added to another 500ml three-necked flask. 3.8g of cerium nitrate was added to a 100ml flask, and water was added until an 80g aqueous solution was obtained. This 80g aqueous solution was then added to the other 500ml three-necked flask. The resulting mixture was stirred at 600 rpm for 2 hours at 50°C, and then dried in an oven at 100°C for 24 hours. The mixture was then transferred to a muffle furnace and calcined at 700°C for 4 hours under a nitrogen atmosphere to obtain the cerium-carbon composite material DC4, wherein the cerium dioxide content was 30 wt.% and the total nitrogen content was 1.8 wt.%. The cerium-carbon composite material DC4 had an average pore size of 200 nm and a specific surface area of ​​23.3 m². 2 / g.

[0259] The XRD characterization results of the cerium-carbon composite DC4 are similar to those shown in Figure 3, and its characteristic peaks are consistent with those of cerium dioxide.

[0260] The SEM characterization results of the cerium-carbon composite DC4 are similar to those shown in Figure 4. The cerium content in the cerium-carbon composite DC4 is 34.1 wt.% in vivo and 14.3 wt.% in vitro.

[0261] Cerium-carbon composite material DC4 was used as a catalyst in the preparation of dimethyl carbonate: 10.0 g of catalyst DC4 and 88.0 g (1 mol) of ethylene carbonate were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 100 °C, and 256 g (8 mol) of methanol was added dropwise over 5 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through the distillation column at a reflux ratio of 1. The reaction was considered complete when the addition was finished. Calculations showed that the conversion rate of ethylene carbonate was 58.2%, and the selectivity of dimethyl carbonate was 99.3%.

[0262] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

[0263] Cerium-carbon composite material DC4 was used as a catalyst in the preparation of di(2-methoxyethyl) carbonate: 20.0 g of catalyst DC4 and 38.0 g (0.5 mol) of ethylene glycol monomethyl ether were added to a 1000 ml three-necked flask equipped with a gas delivery tube, a temperature-controlled thermocouple, a constant-pressure dropping funnel, and a distillation column. The reactants were heated to 120 °C, and 360 g (4 mol) of dimethyl carbonate was added dropwise over 10 h. Simultaneously, the azeotrope of dimethyl carbonate and methanol was distilled off through a distillation column at a reflux ratio of 1. The reaction was considered complete when the addition ended. Calculations showed that the conversion rate of ethylene glycol monomethyl ether was 49.5%, and the selectivity of di(2-methoxyethyl) carbonate was 99.5%.

[0264] The distillation column consists of a catalyst layer at the bottom, 20 cm high, and a glass packing layer at the top, 100 cm high. The volume ratio of the catalyst layer to the glass packing layer in the distillation column is 0.2:1, and the long side particle size of the glass packing is 20 mm. The catalyst packed in the distillation column accounts for 50% of the total catalyst volume.

Claims

1. A composite material, characterized by, The composite material comprises porous carbon and cerium nitride within the porous carbon, wherein the cerium content is 1 wt.% or more based on the total weight of the elements within the porous carbon, preferably from 1 wt.% to 70 wt.%, more preferably from 5 wt.% to 68 wt.%, and even more preferably from 10 wt.% to 65 wt.%.

2. The composite material of claim 1, wherein, The cerium halide is at least one of cerium chloride and cerium bromide; and / or The cerium content based on the total weight of all elements within the porous carbon body is w1, and the cerium content based on the total weight of all elements on the outer surface of the porous carbon body is w2, where w1 > w2, preferably w1 ≥ 1.2 × w2, and more preferably w1 = (1.2 - 5) × w2.

3. The composite material according to claim 1 or 2, characterized in that, The composite material has an average pore size of 50 nm to 500 nm, preferably 50 nm to 300 nm. The specific surface area of the composite is 5 m 2 / g to 100 m 2 / g, preferably 10 m 2 / g to 60 m 2 / g, and / or The particle size of the composite material is 0.1 mm to 3 mm, preferably 0.3 mm to 2 mm.

4. The composite material according to any of the preceding claims, characterized in that, The porous carbon originates from the carbonization of halogenated alkylated resins, preferably from the carbonization of nitrogen-modified halogenated resins; and / or Based on the total weight of the composite material, the nitrogen content is 1 wt.% to 15 wt.%, preferably 3 wt.% to 10 wt.%.

5. A method for preparing the composite material according to any one of claims 1 to 4, comprising: 1) React haloalkylated resins with nitrogen-containing organic compounds to obtain nitrogen-modified halogenated resins; 2) Optionally, the nitrogen-modified halogenated resin is washed with a halide salt solution, and 3) Selectively wash the nitrogen-modified halogen-containing resin with a halide salt solution and mix it with a cerium precursor. Then, calcine the mixture under an inert gas atmosphere to obtain the composite material. Preferably, based on the total weight of the composite material, the content of cerium nitride is 3 wt.% to 85 wt.%, more preferably 5 wt.% to 70 wt.%, and more preferably 8 wt.% to 55 wt.%.

6. The method of claim 5, wherein, The halogenated alkylating resin is a chloroalkylating resin and / or a brominated alkylating resin, preferably a chloroalkylating resin, and / or the halogenated alkylating resin is a halogenated methyl resin; preferably, the halogenated alkylating resin is one or more of chloromethyl polystyrene, chloromethyl polyethylene, chloromethyl carboxyl resin and chloromethyl phenolic resin, preferably chloromethyl polystyrene. The particle size of the halogenated alkylated resin is 0.1 mm to 3 mm, preferably 0.3 mm to 2 mm; Based on the weight of the haloalkylated resin, the halogen content is greater than 1 wt.%, preferably 10 wt.% to 25 wt.%; and / or The halogenated alkylated resin is spherical.

7. The method according to claim 5 or 6, characterized in that, The reaction in step 1) is carried out in the presence of a first solvent, which is preferably one or more of toluene, methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, dichloromethane, chloroform, amides and ethers, more preferably alkylamides, and even more preferably N,N-dimethylformamide. The weight ratio of the haloalkylated resin to the first solvent is 1:1 to 1:10, preferably 1:3 to 1:10; The nitrogen-containing organic compound is selected from one or more of piperazine, amine, pyridine, imidazole, quinoline and pyrrole, preferably one or more of methylamine, ethylamine, piperazine, imidazole and pyridine, wherein the methylamine is preferably trimethylamine; The weight ratio of the nitrogen-containing organic compound to the haloalkylated resin is 0.5 to 5.0, preferably 0.8 to 2.0, and more preferably 0.8 to 1.

5. Step 1) The reaction is carried out at a temperature of 50°C to 150°C, preferably 70°C to 90°C, for a time of 1 hour to 24 hours, preferably 10 hours to 14 hours; and / or The halide solution is an aqueous solution of a metal salt containing fluoride, chloride, bromide and / or iodide ions, preferably an aqueous solution of one or more of sodium chloride, potassium chloride, zinc chloride, sodium bromide, potassium bromide and zinc bromide.

8. The method according to any one of claims 5 to 7, characterized in that, The mixing in step 3) is carried out in the presence of a second solvent, which is preferably at least one of water and alcohol, more preferably one or more of water, methanol, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, and pentanol, and even more preferably at least one of water, ethylene glycol, and glycerol. The weight ratio of the nitrogen-modified halogenated resin to the second solvent is 1:1 to 1:10, preferably 1:2 to 1:8; The mixing in step 3) is carried out under heating and stirring. Preferably, the heating and stirring is carried out at a temperature of 20°C to 90°C, more preferably 30°C to 70°C, at a rate of 50 rpm to 1000 rpm, more preferably 400 rpm to 600 rpm, for a time of 1 hour to 24 hours, more preferably 2 hours to 6 hours. The cerium precursor is a cerium salt, preferably cerium nitrate and / or cerium chloride; The weight ratio of the cerium precursor to the nitrogen-modified halogen-containing resin is 0.01 to 1.5, preferably 0.05 to 1.2, and more preferably 0.1 to 1.

2. In step 3), a drying step is also included before calcination, wherein the drying is preferably carried out at a temperature of 70°C to 150°C for a time of 2 to 48 hours; The inert gas is one or more of nitrogen, carbon dioxide, and argon, preferably nitrogen and / or argon; and / or The calcination is carried out at a temperature of 300°C to 1200°C for 1 hour to 48 hours, preferably at a temperature of 400°C to 900°C for 2 hours to 36 hours, and more preferably at a temperature of 600°C to 800°C for 4 hours to 10 hours.

9. A method for producing a carbonate ester by a transesterification reaction, comprising reacting a first carbonate ester with a hydroxyl group-containing compound in the presence of a catalyst to obtain a second carbonate ester, characterized in that, The catalyst is a composite material according to any one of claims 1 to 4 or a composite material prepared by the method according to any one of claims 5 to 8.

10. The method according to claim 9, characterized in that, The first carbonate is at least one of alkylene carbonate and dialkyl carbonate, preferably at least one of ethylene carbonate, propylene carbonate and dimethyl carbonate; The hydroxyl-containing compound is at least one of alkyl alcohols and alkoxy alcohols, preferably at least one of methanol, ethanol, and ethylene glycol monomethyl ether; and / or The second carbonate is at least one of dialkyl carbonate and di(alkoxyalkyl) carbonate, preferably at least one of dimethyl carbonate and di(2-methoxyethyl) carbonate.

11. The method of claim 10, wherein, The first carbonate is ethylene carbonate, the hydroxyl-containing compound is methanol, and the second carbonate is dimethyl carbonate; The first carbonate is propylene carbonate, the hydroxyl-containing compound is methanol, and the second carbonate is dimethyl carbonate; and / or The first carbonate is dimethyl carbonate, the hydroxyl-containing compound is ethylene glycol monomethyl ether, and the second carbonate is di(2-methoxyethyl) carbonate.

12. The method according to any one of claims 9 to 11, characterized in that, The transesterification reaction is carried out at a temperature of 70°C to 150°C, preferably 100°C to 120°C, for 1 hour to 15 hours, preferably 5 hours to 10 hours.

13. The method according to any one of claims 9 to 12, characterized in that, The molar ratio of the hydroxyl-containing compound to the first carbonate is (1-15):1, preferably (3-12):1; and / or The weight ratio of catalyst to first carbonate is (0.05-0.8):1, preferably (0.05-0.6):1, and more preferably (0.08-0.5):

1.

14. The method according to any one of claims 9 to 12, characterized in that, The molar ratio of the first carbonate to the hydroxyl-containing compound is (1-15):1, preferably (3-12):1; and / or The weight ratio of catalyst to hydroxyl-containing compound is (0.5-3):1, preferably (0.5-2):1, and more preferably (0.5-1):

1.

15. The method according to any one of claims 9 to 14, characterized in that, The transesterification reaction is carried out in a reactor equipped with a distillation unit, both of which contain a catalyst. Preferably, the catalyst loading in the distillation unit accounts for 30 wt.% to 70 wt.% of the total catalyst usage, more preferably 40 wt.% to 60 wt.%. Preferably, in the distillation apparatus, the catalyst is packed in the lower part and the inert packing is packed in the upper part, and the volume ratio of the catalyst to the inert packing is preferably (0.05-1):1, and more preferably (0.1-0.8):1; Preferably, the particle size of the inert filler is 1 mm to 30 mm; and / or, Preferably, the reflux ratio of the distillation apparatus is (1-3):1.

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