Process for the synthesis of oxazolidinones from carbon dioxide and an alcohol amine and catalysts
By using cerium-based composite oxides as solid catalysts, the problems of difficult catalyst separation and low selectivity were solved, and efficient and economical synthesis of oxazolidinone compounds from the reaction of carbon dioxide with alcoholamines was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2026-03-03
AI Technical Summary
In existing technologies, catalysts for the synthesis of oxazolidinone compounds from carbon dioxide and alcoholamines are difficult to separate from the reaction system, and the reaction selectivity is low, leading to increased costs and difficulty in removing byproducts.
Using cerium-based composite oxides as solid catalysts, carbon dioxide reacts with alcoholamines in the liquid phase through carboxylation and cyclization dehydration to generate oxazolidinone compounds. The catalyst exists in solid form both before and after the reaction, which facilitates separation and improves the selectivity of the reaction.
This approach achieves easy separation and high selectivity of the catalyst, high conversion rate of alkanolamines, reduced costs, and improved reaction efficiency.
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Abstract
Description
Technical Field
[0001] This application relates to the field of carbon dioxide catalytic conversion and utilization technology, and in particular to a method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alkanolamines, oxazolidinone compounds prepared based on carbon dioxide and alkanolamines, and the application of cerium-based composite oxides in the preparation of oxazolidinone compounds based on carbon dioxide and alkanolamines. Background Technology
[0002] The overuse and misuse of antibiotics have led to the rapid development of antibiotic- and antimicrobial-resistant bacteria, seriously threatening the lives and health of patients with infectious diseases. Oxazolidinone antibiotics (such as linezolid and radizolide) are a new class of chemically synthesized antimicrobials following sulfonamides and fluoroquinolones. They exert their antimicrobial effect by inhibiting bacterial protein synthesis, and their core unit is oxazolidinone. Preparing oxazolidinone antibiotics by reacting carbon dioxide with nitrogen-containing organic matter can not only eliminate the greenhouse effect caused by carbon dioxide but also convert it into high-value-added pharmaceuticals. Theoretically, the cyclization of amino alcohols and carbon dioxide is the simplest, green, and environmentally friendly route for converting carbon dioxide into oxazolidinone compounds. On the one hand, amino alcohols (derived from various amino acids) are readily available, inexpensive, and generally safe ideal chemicals; on the other hand, the cyclization of amino alcohols and carbon dioxide only produces water as a stoichiometric byproduct, making it an ideal green synthetic route. Homogeneous organometallic catalysts, such as electrophilic reagents like trialkylphosphine, high-energy phosphorus compounds, or strong bases like DBU (1,8-diazacyclo[5.4.0]undec-7-ene), trialkylamines, guanidines, and organotitanium complexes, can promote the synthesis of oxazolidinone compounds from carbon dioxide and alkanolamines. However, these methods use large amounts of condenser, leading to a significant increase in cost and generating substantial amounts of waste (such as alkylphosphine oxides), which are difficult to remove from the product. Therefore, there is an urgent need to develop reaction systems for the highly selective synthesis of oxazolidinone compounds that are easily separable. Summary of the Invention
[0003] Based on this, this application provides a method and catalyst for synthesizing oxazolidinone compounds based on carbon dioxide and alkanolamines, oxazolidinone compounds prepared based on carbon dioxide and alkanolamines, and the application of cerium-based composite oxides in the preparation of oxazolidinone compounds based on carbon dioxide and alkanolamines. This preparation method allows the catalyst to be easily separated and removed from the system after the reaction.
[0004] The first aspect of this application provides a method for synthesizing oxazolidinone compounds based on carbon dioxide and alcoholamines, comprising:
[0005] Using carbon dioxide and an alcoholic amine as raw materials, the alcoholic amine reacts with the carbon dioxide in the presence of a solid catalyst to generate the oxazolidinone compound; wherein the solid catalyst comprises a cerium-based composite oxide, and the reaction process includes liquid-phase carboxylation and cyclization dehydration.
[0006] In some embodiments of this application, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;
[0007] The first cerium-based composite oxide includes CeM1 x1 O y1 Wherein, M1 includes a first metal cation different from Ce, and the values of x1 and y1 make CeM1 x1 O y1 The algebraic sum of their valences is zero;
[0008] The second cerium-based composite oxide includes CeO2-M2 x2 O y2 Wherein, M2 includes a second metal cation different from Ce, and the values of x2 and y2 make M2 x2 O y2 The algebraic sum of their valences is zero;
[0009] The third cerium-based composite oxide includes M3'-CeM3 x3 O y3 Wherein, M3 includes a third metal cation different from Ce, M3' includes a fourth metal cation, and the values of x3 and y3 make CeM3 x3 O y3 The algebraic sum of their valences is zero;
[0010] Optionally, M1, M2, and M3 each independently include Zn. 2+ La 3+ In 3+ Al 3+ and Zr 4+ At least one of them;
[0011] Optionally, M3' includes Na + Li + Ba 2+ or Co x’+ At least one of them.
[0012] In some embodiments of this application, one or more of the following conditions are met:
[0013] (1) The CeO2-M2 x2 O y2In it, the molar ratio of Ce to M2 is denoted as Ce / M2, then 0 < Ce / M2 ≤ 1000, optionally 0 < Ce / M2 ≤ 10, and further optionally 0.25 < Ce / M2 ≤ 4;
[0014] (2) The M3’-CeM3 described above x3 O y3 In it, the molar ratio of M3’ to Ce is denoted as M3’ / Ce, then 0 < M3’ / Ce ≤ 1, optionally 0 < M3’ / Ce ≤ 0.5, and further optionally 0 < M3’ / Ce ≤ 0.1;
[0015] Optionally, the third cerium-based composite oxide is M3’-CeZr x3 O2. Among them, the molar ratio of Ce to Zr is denoted as Ce / Zr, then 0 < Ce / Zr ≤ 1000, optionally 0 < Ce / Zr ≤ 10, and further optionally 0.25 < Ce / Zr ≤ 4.
[0016] In some embodiments of the present application, one or more of the following conditions are satisfied:
[0017] (1) The first cerium-based composite oxide is CeZr x1 O2. Among them, the molar ratio of Ce to Zr is denoted as (Ce / Zr)’, then 0 < (Ce / Zr)’ ≤ 1000, optionally 0 < (Ce / Zr)’ ≤ 10, and further optionally 0.25 < (Ce / Zr)’ ≤ 4;
[0018] (2) The second cerium-based composite oxide includes one or more of CeO2-ZnO, CeO2-La2O3, CeO2-In2O3, and CeO2-Al2O3.
[0019] In some embodiments of the present application, the alkanolamine includes one or more of substituted or unsubstituted ethanolamine and substituted or unsubstituted propanolamine;
[0020] Optionally, the alkanolamine includes one or more of ethanolamine, 3-amino-1,2-propanediol, and propanolamine.
[0021] In some embodiments of the present application, the reaction is carried out in a solution of the alkanolamine;
[0022] Optionally, the solvent in the solution includes one or more of acetonitrile, water, 1,4-dioxane, and mesitylene, and further optionally acetonitrile.
[0023] In some embodiments of the present application, one or more of the following conditions are satisfied:
[0024] (1) The reaction temperature is 100℃~300℃, preferably 100℃~240℃, and further preferably 120℃~220℃;
[0025] (2) The reaction time is 0.5h to 100h, preferably 0.5h to 60h, and further preferably 0.5h to 48h;
[0026] (3) During the reaction process, the pressure of the carbon dioxide is 1 atm to 40 atm, which can be selected as 1 atm to 20 atm, and further can be selected as 2 atm to 16 atm;
[0027] (4) The reaction is carried out under stirring conditions, and the stirring speed is 200 rpm to 1500 rpm.
[0028] In some embodiments of this application, the ratio of the amount of the alkanolamine to the amount of the solid catalyst is (100~1500):(4~700), optionally (200~1300):(4~700), and further optionally (300~1300):(4~700);
[0029] Optionally, the amount of the alkanolamine used is 100mg~1500mg, optionally 200~1300mg, and further optionally 300mg~1300mg;
[0030] Optionally, the amount of the solid catalyst used is 4 mg to 700 mg, or optionally 34 mg to 684 mg.
[0031] The second aspect of this application provides an oxazolidinone compound prepared from carbon dioxide and an alcohol amine, obtained by the preparation method described in the first aspect of this application.
[0032] The third aspect of this application provides the application of a cerium-based composite oxide in the preparation of oxazolidinone compounds based on carbon dioxide and alkanolamines, wherein the cerium-based composite oxide is the same cerium-based composite oxide used in the preparation method described in the first aspect of this application.
[0033] The preparation method provided in this application uses a specific solid catalyst—cerium-based composite oxide. This catalyst can exist in solid form both before and after the reaction, and therefore, compared with traditional homogeneous organometallic catalysts, it is easy to separate and remove from the product after the reaction. At the same time, this catalyst also has high selectivity for the reaction of alkanolamines with carbon dioxide, thus enabling alkanolamines to have a high conversion rate. Detailed Implementation
[0034] To facilitate understanding of this application, a more complete description will be provided below. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.
[0035] For simplicity, this application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form a range not explicitly stated; and any lower limit can be combined with other lower limits to form a range not explicitly stated, just as any upper limit can be combined with any other upper limit to form a range not explicitly stated. Furthermore, although not explicitly stated, every point or individual value between the endpoints of the range is included within that range. Therefore, each point or individual value can be used as its own lower or upper limit and combined with any other point or individual value or with other lower or upper limits to form a range not explicitly stated.
[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. It should be noted that, unless otherwise stated, the term "and / or" as used herein includes any and all combinations of one or more of the associated listed items, "above," "below," includes the stated number, and "one or more" with "multiple" means two or more.
[0037] In this document, when referring to numerical intervals (i.e., numerical ranges), unless otherwise specified, the distribution of selectable values within a numerical interval is considered continuous, and includes the two endpoints (i.e., the minimum and maximum values) of the numerical interval, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, and other numerical interval types.
[0038] In this document, for methods involving multiple steps, unless otherwise explicitly stated herein, there is no strict order constraint on the execution of these steps; they may be executed in any order other than those described. Moreover, any step may include multiple sub-steps or multiple stages, which are not necessarily completed at the same time, but may be executed at different times, and their execution order is not necessarily sequential, but may be executed in turn, alternately, or simultaneously with other steps or parts of the sub-steps or stages of other steps.
[0039] The foregoing description of this application is not intended to describe every disclosed implementation or method. Instead, the following description provides more specific examples of exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments that can be used in various combinations. The examples listed are representative only and should not be construed as exhaustive.
[0040] Currently, in the reaction of amino alcohols and carbon dioxide with carboxyl cyclization to oxazolidinone compounds, commonly used catalysts are homogeneous organometallic catalysts such as trialkylphosphine, high-energy phosphorus compounds or strong bases such as DBU (1,8-diazacyclo[5.4.0]undec-7-ene), trialkylamines and guanidines, and organotitanium complexes. Although homogeneous organometallic catalysts can promote the synthesis of oxazolidinone compounds from carbon dioxide and alcoholamines, these catalysts and reactants are usually in the liquid phase. In liquid-phase reactions, they mix with reactants and products, and easily form a large number of byproducts (such as alkylphosphine oxides), making it difficult to remove the catalyst itself and byproducts from the products after the reaction. In view of this, the inventors have proposed the following technical solution.
[0041] In a first aspect, this application provides a method for synthesizing oxazolidinone compounds based on carbon dioxide and alcoholamines, which may include the following step S1:
[0042] S1: Using carbon dioxide and an alcohol amine as raw materials, the alcohol amine reacts with the carbon dioxide under the action of a solid catalyst to generate the oxazolidinone compound; wherein the solid catalyst includes a cerium-based composite oxide, and the reaction process includes liquid-phase carboxylation and cyclization dehydration.
[0043] The preparation method provided in this application employs a specific solid catalyst—cerium-based composite oxide. This catalyst exists in solid form both before and after the reaction, and therefore, compared to traditional homogeneous organometallic catalysts, it is easily separated and removed from the product after the reaction. At the same time, this catalyst also exhibits high selectivity for the reaction of alkanolamines with carbon dioxide, thus enabling alkanolamines to achieve a high conversion rate.
[0044] Therefore, this application utilizes a specific solid catalyst to convert alkanolamines into oxazolidinone compounds. This catalyst is inexpensive and readily available, and the catalyst and product are easily separated. Based on this, the method for preparing oxazolidinone compounds based on alkanolamines provided in this application has high research value and application prospects.
[0045] It should be noted that the "cerium-based composite oxide" mentioned in this application refers to a composite oxide formed by cerium as a base element and together with one or more other metallic elements.
[0046] In some embodiments, the cerium-based composite oxide includes one or more of a first cerium-based composite oxide, a second cerium-based composite oxide, and a third cerium-based composite oxide;
[0047] The first cerium-based composite oxide includes CeM1 x1 O y1 Wherein, M1 includes a first metal cation different from Ce, and the values of x1 and y1 make CeM1 x1 O y1 The algebraic sum of their valences is zero;
[0048] The second cerium-based composite oxide includes CeO2-M2 x2 O y2 Wherein, M2 includes a second metal cation different from Ce, and the values of x2 and y2 make M2 x2 O y2 The algebraic sum of their valences is zero;
[0049] The third cerium-based composite oxide includes M3'-CeM3 x3 O y3 Wherein, M3 includes a third metal cation different from Ce, M3' includes a fourth metal cation, and the values of x3 and y3 make CeM3 x3 O y3 The algebraic sum of their valences is zero.
[0050] It should be noted that "CeO2-M2" in this application x2 O y2 "" refers to CeO2 and M2 x2 O y2 Cerium-based composite oxides formed by chemical bonding between them; "M3"-CeM3 x3 O y3 "" refers to CeM3 x3 O y3 The cerium-based composite oxide is bonded to a third metal cation M3'.
[0051] In some embodiments, M1, M2, and M3 each independently include Zn.2+ , La 3+ , In 3+ , Al 3+ and Zr 4+ at least one of.
[0052] In some embodiments, the M3' includes Na + , Li + , Ba 2+ or Co x’+ at least one of.
[0053] In some embodiments, in the CeO2 - M2 x2 O y2 , if the molar ratio of Ce to M2 is denoted as Ce / M2, then 0 < Ce / M2 ≤ 1000. For example, Ce / M2 can be 0.5, 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 or within the range composed of any of the above values. Optionally, 0 < Ce / M2 ≤ 10, and further optionally, 0.25 < Ce / M2 ≤ 4. Thus, CeO2 - M2 x2 O y2 can have high selectivity and catalytic performance, and the alkanolamine can have a high conversion rate.
[0054] In some embodiments, in the M3' - CeM3 x3 O y3 , if the molar ratio of M3' to Ce is denoted as M3' / Ce, then 0 < M3' / Ce ≤ 1. For example, M3' / Ce can be 0.5%, 1%, 5%, 10%, 50%, 80%, 100% or within the range composed of any of the above values. Optionally, 0 < M3' / Ce ≤ 0.5, and further optionally, 0 < M3' / Ce ≤ 0.1. Thus, M3' - CeM3 x3 O y3 can have high selectivity and catalytic performance, and the alkanolamine can have a high conversion rate.
[0055] In some embodiments, the third cerium-based composite oxide is M3' - CeZr x3 O2, where, if the molar ratio of Ce to Zr is Ce / Zr, then 0 < Ce / Zr ≤ 1000. For example, Ce / Zr can be 0.5, 1, 3, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000 or within the range composed of any of the above values. Optionally, 0 < Ce / Zr ≤ 10, and further optionally, 0.25 < Ce / Zr ≤ 4, and particularly optionally 3. Thus, M3' - CeZr x3O2 has high selectivity and catalytic performance, which enables alkanolamines to have a high conversion rate.
[0056] In some embodiments, the first cerium-based composite oxide is CeZr. x1 O2, where the molar ratio of Ce to Zr is denoted as (Ce / Zr)', then 0 < (Ce / Zr)' ≤ 1000. For example, (Ce / Zr)' can be 0.5, 1, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, or any value within the range of these values. It is optional that 0 < (Ce / Zr)' ≤ 10, further optional that 0.25 < (Ce / Zr)' ≤ 4, and particularly optional that 3. This allows CeZr to... x1 O2 has high selectivity and catalytic performance, which enables alkanolamines to have a high conversion rate.
[0057] In some embodiments, the second cerium-based composite oxide includes one or more of CeO2-ZnO, CeO2-La2O3, CeO2-In2O3, and CeO2-Al2O3.
[0058] In some embodiments, the alkanolamine includes one or more of substituted or unsubstituted ethanolamines and substituted or unsubstituted propanolamines.
[0059] In some embodiments, the alkanolamine includes one or more of ethanolamine, 3-amino-1,2-propanediol, and propanolamine.
[0060] In some embodiments, the reaction is carried out in a solution of an alcoholamine.
[0061] In some embodiments, the solvent in the solution includes one or more of acetonitrile, water, 1,4-dioxane and mesitylene, with acetonitrile being an option.
[0062] In some embodiments, the reaction may include the following step S10:
[0063] S10: Add the alkanolamine, solvent and solid catalyst to the reactor and seal it. Replace the air in the reactor with high-purity CO2 to remove the residual air. After replacement, introduce high-purity CO2 into the reactor at room temperature, and then raise the temperature to the specified reaction temperature to carry out the reaction.
[0064] In some embodiments, the reactor may be a high-pressure autoclave reactor.
[0065] In some embodiments, the number of times high-purity CO2 is used for replacement can be 5 to 8 times.
[0066] In some embodiments, the reaction is carried out under stirring conditions, with the stirring speed ranging from 200 rpm to 1500 rpm. For example, this speed can be 400 rpm, 600 rpm, 800 rpm, 1000 rpm, 1200 rpm, 1500 rpm, or any range of the above values. Optionally, the speed is 1000 rpm.
[0067] In some embodiments, the ratio of the alkanolamine to the solid catalyst is (100-1500):(4-700). For example, this ratio can be 100:700, 305:684, 610:342, 1500:700, 750:171, 915:34, 100:4, 1220:17, 1500:4, or any range of the above values. Alternatively, it can be (200-1300):(34-684), and more preferably (300-1300):(34-684). This facilitates the catalytic performance of the solid catalyst, resulting in a higher conversion rate of the alkanolamine.
[0068] In some embodiments, the amount of the alkanolamine used is 100 mg to 1500 mg. For example, the amount of alkanolamine used can be 100 mg, 305 mg, 610 mg, 750 mg, 915 mg, 1220 mg, 1500 mg, or within any range of the above values. Optionally, it can be 200 to 1300 mg, and more preferably 300 mg to 1300 mg.
[0069] In some embodiments, the amount of the solid catalyst used is 4 mg to 700 mg. For example, the amount of solid catalyst can be 4 mg, 8 mg, 17 mg, 34 mg, 171 mg, 342 mg, 684 mg, 700 mg, or any range of the above values. 34 mg to 684 mg is an option. This facilitates the catalytic performance of the solid catalyst, resulting in a higher conversion rate of the alcoholamine.
[0070] In some embodiments, the reaction temperature is 100°C to 300°C. For example, this temperature can be 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, or any range thereof. 100°C to 240°C is optional, and more preferably 120°C to 220°C. This facilitates a higher conversion rate of the alkanolamine.
[0071] It should be noted that the temperature of the reaction refers to the real-time temperature of the reactor.
[0072] In some embodiments, the reaction time is 0.5 h to 100 h. For example, the reaction time can be 0.5 h, 1 h, 2 h, 4 h, 8 h, 12 h, 24 h, 48 h, or any range of the above values. It can be selected as 0.5 h to 60 h, and more preferably 0.5 h to 48 h. This is beneficial for achieving a higher conversion rate of the alcoholamine.
[0073] In some embodiments, the pressure of the carbon dioxide during the reaction is 1 atm to 40 atm. For example, the pressure of the carbon dioxide can be 1 atm, 2 atm, 4 atm, 6 atm, 8 atm, 10 atm, 12 atm, 14 atm, 16 atm, or any range of these values. It can be selected as 1 atm to 20 atm, more preferably 2 atm to 16 atm, and particularly preferably 8 atm. This is beneficial for achieving a higher conversion rate of the alcoholamine.
[0074] It should be noted that the cerium-based composite oxide described in this application can be a commercial product or a commercially available product, or it can be prepared by conventional or known methods.
[0075] In some embodiments, the preparation method of the cerium-based composite oxide includes co-precipitation, impregnation, etc. Optionally, the cerium-based composite oxide is prepared by co-precipitation.
[0076] In some embodiments, the step of preparing the first cerium-based composite oxide and / or the second cerium-based composite oxide by co-precipitation may include:
[0077] S20: After mixing the cerium salt solution and the non-cerium metal salt solution evenly, add an alkaline reagent dropwise with continuous stirring until the solution becomes alkaline and the precipitate is completely precipitated; after the precipitate is subjected to a first calcination treatment, a first cerium-based composite oxide and / or a second cerium-based composite oxide are obtained.
[0078] In some embodiments, before the precipitate is subjected to the first calcination treatment, the precipitate may be subjected to one or more of the following steps: settling and aging, filtration, washing, drying, etc.
[0079] In some embodiments, the alkaline reagent includes one or more of ammonia, NaOH, or KOH.
[0080] In some embodiments, the cerium source in the cerium salt solution includes one or more of cerium nitrate, cerium nitrate ammonium, and cerium chloride, with cerium nitrate ammonium being a possible alternative.
[0081] In some embodiments, the non-cerium metal source in the non-cerium metal salt solution includes one or more of the non-cerium metal nitrates, oxynitrates, and chlorides. In other embodiments, the non-cerium metal includes at least one of Zn, La, In, Al, and Zr, optionally Zr. For example, when the non-cerium metal is zirconium, the zirconium source includes zirconium oxynitrate and / or zirconium chloride, optionally zirconium oxynitrate.
[0082] It can be understood that in the above preparation step S20, by adjusting the ratio of the added cerium source and non-cerium metal source and the pH of the solution during preparation, first cerium-based composite oxides and / or second cerium-based composite oxides with different (Ce / non-cerium metal) molar ratios can be obtained.
[0083] In some embodiments, in the preparation step S20 described above, the mixed solution of cerium salt solution and non-cerium metal salt solution may be heated to promote the precipitation of the precipitate. Optionally, the heating temperature is 0~100℃, and the continuous stirring time is 1h~12h.
[0084] In some embodiments, the temperature for the first calcination treatment of the precipitate is 300°C to 1000°C. For example, the temperature for the first calcination treatment can be 300°C, 400°C, 600°C, 700°C, 750°C, 800°C, 850°C, 900°C, 1000°C, or any range thereof. 400°C to 900°C is optional, and more preferably 400°C to 850°C. This facilitates the preparation of cerium-based composite oxides with high selectivity and catalytic performance.
[0085] In some embodiments, based on step S20, the third cerium-based composite oxide M3'-CeZr x3 O2 can be prepared using the following steps:
[0086] S30: Impregnating a third metal cation M3' onto a first cerium-based composite oxide and / or a second cerium-based composite oxide, thereby binding and loading the third metal cation M3' onto the first cerium-based composite oxide and / or the second cerium-based composite oxide, and obtaining M3'-CeZr through steps such as drying and a second calcination treatment. x3 O2.
[0087] In some embodiments, the temperature of the second calcination treatment is 300°C to 1000°C. For example, the temperature of the second calcination treatment can be 300°C, 400°C, 600°C, 700°C, 750°C, 800°C, 850°C, 900°C, 1000°C, or any range of the above values. 400°C to 900°C is optional, and more preferably 400°C to 850°C. This is advantageous for producing cerium-based composite oxides with high selectivity and catalytic performance.
[0088] It can be understood that in step S30 above, by adjusting the molar concentration (molar percentage) of the third metal ion M3', different M3' / Ce molar ratios of the third cerium-based composite oxide M3'-CeZr can be obtained. x3 O2.
[0089] Secondly, this application provides an oxazolidinone compound prepared from carbon dioxide and an alcohol amine, obtained by the preparation method described in the first aspect of this application.
[0090] Thirdly, this application provides the application of a cerium-based composite oxide in the preparation of oxazolidinone compounds based on carbon dioxide and alkanolamines, wherein the cerium-based composite oxide is the cerium-based composite oxide used in the preparation method described in the first aspect of this application.
[0091] The following are specific embodiments, which describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations within the scope of the disclosure of this application will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following embodiments are based on weight, and all reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing, and the instruments used in the embodiments are commercially available.
[0092] Example 1
[0093] Preparation of cerium-based composite oxides
[0094] A 0.2 mol / L solution of cerium ammonium nitrate and a 0.2 mol / L solution of zirconium oxynitrate were mixed thoroughly at a Ce / Zr molar ratio of 3:1. Then, 1 mol / L ammonia solution was added dropwise until the solution pH reached 10. The mixture was stirred vigorously at room temperature for 1 h to obtain a hydroxide precipitate. After washing several times, the precipitate was dried at 110 °C for 12 h. Finally, the precipitate was calcined in a muffle furnace at 700 °C for 3 h to obtain a cerium-based composite oxide denoted as CeZrO2(3:1)-700, where 3:1 represents the Ce / Zr molar ratio of 3:1 and 700 represents the calcination temperature.
[0095] Preparation of oxazolidinone
[0096] The preparation of oxazolidinone compounds by reacting carbon dioxide with alcoholamines was carried out in a liquid-phase batch reactor. The specific procedure was as follows: 34 mg of the prepared CeZrO2(3:1)-700, 610 mg of ethanolamine, and 16.4 g of acetonitrile were added to a polytetrafluoroethylene liner and sealed. The reactor was then purged five times with 8 atm high-purity CO2 to remove residual air. After purging, 8 atm of high-purity CO2 was introduced into the reactor at room temperature, followed by heating to 140 °C and stirring at 1000 rpm for 2 h. The reaction products were detected by gas chromatography, and the results are shown in Table 1.
[0097] Examples 2-5
[0098] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 2-5 are basically the same as those in Example 1, except that the Ce / Zr molar ratios in the solutions in Examples 2-5 are 1:3, 1:1, 2:1, and 4:1, respectively. XRF (X-ray fluorescence spectroscopy) was used to determine the Ce / Zr molar ratios in the prepared cerium-based composite oxides to be 1:3, 1.06:1, 2.17:1, and 3.96:1, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 1.
[0099] Table 1. Effect of composition on the catalytic performance of the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinone
[0100]
[0101] It can be seen that by controlling the Ce / Zr molar ratio in the cerium-based composite oxide within a suitable range, ethanolamine can achieve a high conversion rate, and 2-oxazolidinone can achieve a high selectivity, meaning that the cerium-based composite oxide has high catalytic performance; and the catalytic performance is even better when the Ce / Zr molar ratio is (1~4):1.
[0102] Examples 6-12
[0103] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 6-12 were basically the same as those in Example 1, except that the calcination temperatures for preparing the cerium-based composite oxides in Examples 6-12 were 400 ℃, 500 ℃, 600 ℃, 750 ℃, 800 ℃, 850 ℃, and 900 ℃, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 2.
[0104] Table 2 Effect of calcination temperature on the catalytic performance of cerium-based composite oxide CeZrO2 (3:1)
[0105]
[0106] It can be seen that by controlling the calcination temperature during the preparation of cerium-based composite oxides within a suitable range, ethanolamine can achieve a high conversion rate, and 2-oxazolidinone can achieve a high selectivity, meaning that cerium-based composite oxides have high catalytic performance; and the catalytic performance is even better when the calcination temperature is between 500℃ and 900℃.
[0107] Examples 13-19
[0108] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 13-19 are basically the same as those in Example 9, except that the reaction times for the cerium-based composite oxide CeZrO2(3:1)-750 catalyzing the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinones in Examples 13-19 are 0.5 h, 1 h, 4 h, 8 h, 12 h, 24 h, and 48 h, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 3.
[0109] Table 3 Effect of reaction time on the catalytic performance of cerium-based composite oxide CeZrO2(3:1)-750
[0110]
[0111] It can be seen that by controlling the reaction time of cerium-based composite oxide CeZrO2(3:1)-750 catalyzing the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine within a suitable range, ethanolamine can achieve a high conversion rate and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxide has high catalytic performance; and the catalytic performance is better when the reaction time is 2h~48h.
[0112] Examples 20-23
[0113] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 20-23 were basically the same as those in Example 9, with the only difference being that the reaction temperatures for the preparation of 2-oxazolidinones from carbon dioxide and ethanolamine catalyzed by cerium-based composite oxide CeZrO2(3:1)-750 in Examples 20-23 were 120 °C, 160 °C, 180 °C, and 200 °C, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 4.
[0114] Table 4 Effect of reaction temperature on the catalytic performance of CeZrO2(3:1)-750
[0115]
[0116] It can be seen that by controlling the reaction temperature of cerium-based composite oxide CeZrO2(3:1)-750 catalyzing the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine within a suitable range, ethanolamine can achieve a high conversion rate and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxide has high catalytic performance; and the catalytic performance is better when the reaction temperature is 140℃~200℃.
[0117] Example 24
[0118] The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in Example 24 are basically the same as those in Example 21, except that the amount of cerium-based composite oxide CeZrO2(3:1)-750 added in Example 24 is 17 mg. The reaction products were detected by gas chromatography, and the results are shown in Table 5.
[0119] Example 25
[0120] The preparation method of cerium-based composite oxide and the preparation process of oxazolidinone in Example 25 are basically the same as those in Example 22, except that the amount of cerium-based composite oxide CeZrO2(3:1)-750 added in Example 25 is 8 mg. The reaction products were detected by gas chromatography, and the results are shown in Table 5.
[0121] Example 26
[0122] The preparation method of the cerium-based composite oxide and the preparation process of the oxazolidinone in Example 26 are basically the same as those in Example 23, except that the amount of cerium-based composite oxide CeZrO2(3:1)-750 added in Example 25 is 4 mg. The reaction products were detected by gas chromatography, and the results are shown in Table 5.
[0123] Table 5 Catalytic performance of CeZrO2(3:1)-750
[0124]
[0125] It can be seen that by controlling the ratio of alcohol amine to catalyst within a suitable range, ethanolamine can achieve a high conversion rate, and 2-oxazolidinone can achieve a high selectivity, meaning that cerium-based composite oxides have high catalytic performance.
[0126] Examples 27-31
[0127] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 27-31 are basically the same as those in Example 9, except that the CO2 reaction pressures for the cerium-based composite oxide CeZrO2(3:1)-750 catalyzing the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinones in Examples 27-31 are 2 atm, 4 atm, 6 atm, 10 atm, and 12 atm, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 6.
[0128] Table 6. Effect of carbon dioxide pressure on the catalytic performance of CeZrO2(3:1)-750
[0129]
[0130] It can be seen that by controlling the CO2 reaction pressure of cerium-based composite oxide CeZrO2(3:1)-750 catalyzing the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine within a suitable range, ethanolamine can achieve a high conversion rate and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxide has high catalytic performance; and the catalytic performance is better when the reaction pressure is 4 atm ~ 12 atm.
[0131] Examples 32-35
[0132] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 32-35 were basically the same as those in Example 14, except that the amount of ethanolamine added in the preparation of 2-oxazolidinones by catalyzing carbon dioxide and ethanolamine with cerium-based composite oxide CeZrO2(3:1)-750 in Examples 32-35 was 305 mg, 458 mg, 915 mg, and 1220 mg, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 7.
[0133] Table 7 Effect of ethanolamine addition on the catalytic performance of CeZrO2(3:1)-750
[0134]
[0135] It can be seen that by controlling the ratio of alcohol amine to catalyst within a suitable range, ethanolamine can achieve a high conversion rate, and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxides have high catalytic performance; and the catalytic performance is better when the ratio is (305~915):34.
[0136] Example 36
[0137] The preparation method of cerium-based composite oxide and the preparation process of oxazolidinone in Example 36 are basically the same as those in Example 17, except that in Example 36, the amount of ethanolamine added in the preparation of 2-oxazolidinone by catalyzing carbon dioxide and ethanolamine with cerium-based composite oxide CeZrO2(3:1)-750 is 305 mg, and the amount of cerium-based composite oxide added is 684 mg. The reaction products were detected by gas chromatography, and the results are shown in Table 8.
[0138] Example 37
[0139] The catalyst preparation method and oxazolidinone preparation process in Example 37 were basically the same as in Example 36, except that the CO2 reaction pressure in the preparation of 2-oxazolidinone from carbon dioxide and ethanolamine using the cerium-based composite oxide CeZrO2(3:1)-750 in Example 37 was 16 atm. The reaction products were detected by gas chromatography, and the results are shown in Table 8.
[0140] Example 38
[0141] The preparation method of cerium-based composite oxide and the preparation process of oxazolidinone in Example 38 are basically the same as those in Example 36, except that in Example 38, the amount of ethanolamine added in the preparation of 2-oxazolidinone by catalyzing carbon dioxide and ethanolamine with cerium-based composite oxide CeZrO2(3:1)-750 is 915 mg, and the amount of cerium-based composite oxide added is 342 mg. The reaction products were detected by gas chromatography, and the results are shown in Table 8.
[0142] Table 8 Catalytic performance of CeZrO2(3:1)-750
[0143]
[0144] Examples 39-41
[0145] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 39-41 are basically the same as those in Example 37, except that the reaction times for the preparation of 2-oxazolidinones from carbon dioxide and ethanolamine using cerium-based composite oxide CeZrO2(3:1)-750 in Examples 39-41 are 1 h, 2 h, and 4 h, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 9.
[0146] Table 9. Effect of reaction time on the catalytic performance of CeZrO2(3:1)-750
[0147]
[0148] Examples 42-43
[0149] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 42 and 43 are basically the same as those in Example 9, except that in Examples 42 and 43, the solvents used in the preparation of 2-oxazolidinones from carbon dioxide and ethanolamine catalyzed by the cerium-based composite oxide CeZrO2(3:1)-750 are 1,4-dioxane and mesitylene, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 10.
[0150] Table 10 Effect of solvent on the catalytic performance of CeZrO2(3:1)-750
[0151]
[0152] It can be seen that by choosing a suitable solvent, ethanolamine can achieve a high conversion rate and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxides have high catalytic performance.
[0153] Example 44
[0154] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 44 are basically the same as those in Example 9, except that in Example 44, the cerium-based composite oxide CeZrO2(3:1)-750 catalyzes the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinone, in which 610 mg of ethanolamine is converted into 750 mg of propanolamine. The reaction products were detected by gas chromatography, and the results are shown in Table 11.
[0155] Example 45
[0156] The preparation method of the cerium-based composite oxide and the preparation process of oxazolidinone in Example 45 are basically the same as those in Example 9, except that in Example 45, the cerium-based composite oxide CeZrO2(3:1)-750 catalyzes the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinone, in which 610 mg of ethanolamine is converted into 910 mg of 3-amino-1,2-propanediol. The reaction products were detected by gas chromatography, and the results are shown in Table 11.
[0157] Table 11 Effect of ethanolamine addition on the catalytic performance of CeZrO2(3:1)-750
[0158]
[0159] Example 46
[0160] Preparation of cerium-based composite oxides
[0161] A 0.2 mol / L solution of cerium ammonium nitrate and a 0.2 mol / L solution of zirconium oxide nitrate were mixed thoroughly at a Ce / Zr molar ratio of 3:1. Then, 1 mol / L ammonia solution was added dropwise until the solution pH reached 10. The mixture was stirred vigorously at room temperature for 1 h to obtain a hydroxide precipitate. After washing several times, the precipitate was dried at 110 °C for 12 h. Finally, the precipitate was calcined in a muffle furnace at 600 °C for 3 h. The resulting cerium-based composite oxide was designated CeZrO2(3:1)-600.
[0162] A 1 mol% sodium hydroxide solution (Na / Ce molar ratio = 0.01) was impregnated onto a CeZrO2(3:1)-600 catalyst and dried at 110 °C for 12 h. Finally, the catalyst was calcined in a muffle furnace at 600 °C for 3 h to obtain a cerium-based composite oxide, denoted as 1%Na-CeZrO2(3:1)-600.
[0163] The preparation process of oxazolidinone in Example 46 was basically the same as that in Example 9. The reaction products were detected by gas chromatography, and the results are shown in Table 12.
[0164] Examples 47-48
[0165] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 47 and 48 are basically the same as those in Example 46, except that the molar percentage of sodium hydroxide is adjusted in Examples 47 and 48 to make the Na / Ce ratios of the prepared cerium-based composite oxides 0.05 and 0.10, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 12.
[0166] Examples 49-51
[0167] The preparation methods of cerium-based composite oxides and oxazolidinones in Examples 49-51 are basically the same as those in Example 46, except that lithium hydroxide, barium chloride, and cobalt nitrate are used instead of sodium hydroxide in Examples 49-51, and their molar percentages are adjusted so that the prepared cerium-based composite oxides are 1%Li-CeZrO2(3:1)-600, 0.5%Ba-CeZrO2(3:1)-750, and 0.5%Co-CeZrO2(3:1)-750, respectively. The reaction products were detected by gas chromatography, and the results are shown in Table 12.
[0168] Table 12 Effect of additives on the catalytic performance of CeZrO2(3:1)-750
[0169]
[0170] It can be seen that by controlling the Na / Ce molar ratio within a suitable range, ethanolamine can achieve a high conversion rate, and 2-oxazolidinone can achieve a high selectivity, that is, cerium-based composite oxides have high catalytic performance; and the catalytic performance is even better when the Na / Ce molar ratio is (0.01~0.05):1.
[0171] Example 52
[0172] Preparation of cerium-based composite oxides
[0173] A 0.2 mol / L zinc nitrate solution and a 0.2 mol / L zirconium nitrate solution were mixed thoroughly at a Ce / Zn molar ratio of 3:1. Then, 1 mol / L ammonia solution was added dropwise until the solution pH reached 10. The mixture was stirred vigorously at room temperature for 1 h to obtain a hydroxide precipitate. After several washings, the precipitate was dried at 110 °C for 12 h. Finally, the precipitate was calcined in a muffle furnace at 600 °C for 3 h to obtain a cerium-based composite oxide, denoted as CeO2-ZnO(3:1)-600, where 3:1 represents the Ce / Zn molar ratio of 3:1, and 600 represents the calcination temperature.
[0174] The preparation process of oxazolidinone in Example 52 was basically the same as that in Example 1, except that CeO2-ZnO(3:1)-600 was used as the catalyst in Example 52. The reaction products were detected by gas chromatography, and the results are shown in Table 13.
[0175] Examples 53-55
[0176] The preparation process of oxazolidinone in Examples 53-55 was basically the same as that in Example 52, except that CeO2-La2O3(3:1)-600, CeO2-In2O3(3:1)-600, and CeO2-Al2O3(3:1)-600 were used as catalysts in Examples 53-55. The reaction products were detected by gas chromatography, and the results are shown in Table 13.
[0177] Table 13 CeO2-M x O y Catalytic performance of the reaction of carbon dioxide and ethanolamine to prepare 2-oxazolidinone
[0178]
[0179] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0180] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.
Claims
1. A method for synthesizing oxazolidinones based on carbon dioxide and alcohol amines, characterized by, Comprising: reacting an alcohol amine with carbon dioxide in the presence of a solid catalyst to form the oxazolidine compound; wherein the solid catalyst is selected from cerium-based composite oxides, and the reaction comprises liquid-phase carboxylation and cyclodehydration; the cerium-based composite oxide comprises one or more of a first cerium-based composite oxide and a third cerium-based composite oxide; said first cerium-based composite oxide comprises CeM1 x1 O y1 wherein M1 is selected from Zr 4+ x1 and y1 are such that the algebraic sum of the valencies of said CeM1 x1 O y1 is zero, and the molar ratio of Ce to Zr is denoted as (Ce / Zr)', then 0.25 < (Ce / Zr)' < 4. said third cerium-based composite oxide comprises M3'-CeM3 x3 O y3 wherein M3 is selected from Zr 4+ , M3' is selected from at least one of Na + , Li 2+ , Ba x3 , x3 and y3 have values such that the algebraic sum of the valencies of said CeM3 y3 O x3 is zero, the molar ratio of Ce to Zr being denoted by Ce / Zr, then 0.25 < Ce / Zr < 4. the alcohol amine is selected from one or more of ethanolamine, 3-amino-1,2-propanediol, and propanolamine.
2. The method of claim 1, wherein, M3'-CeM3 x3 O y3 In the intermediate, the molar ratio of M3' to Ce is denoted as M3' / Ce, and 0 < M3' / Ce≤ 1.
3. The method of claim 2, wherein, 0 < M3' / Ce ≤ 0.
5.
4. The method of claim 3, wherein, 0 < M3' / Ce ≤ 0.
1.
5. The method according to any one of claims 1 to 4, characterized in that, The first cerium-based composite oxide is CeZr x1 O2.
6. The method according to any one of claims 1 to 4, characterized in that, the reaction is carried out in a solution of the alcohol amine.
7. The method of claim 6, wherein, the solvent in the solution is selected from one or more of acetonitrile, water, 1,4-dioxane, and mesitylene.
8. The method of any one of claims 1-4, wherein, one or more of the following conditions are met: (1) the temperature of the reaction is 100°C to 300°C; (2) the time of the reaction is 0.5h to 100h; (3) during the reaction, the pressure of the carbon dioxide is 1atm to 40atm; (4) the reaction is carried out under stirring, and the stirring speed is 200rpm to 1500rpm.
9. The method of claim 8, wherein, one or more of the following conditions are met: (1) the temperature of the reaction is 100°C to 240°C; (2) the time of the reaction is 0.5h to 60h; (3) during the reaction, the pressure of the carbon dioxide is 1atm to 20atm.
10. The method of claim 9, wherein, one or more of the following conditions are met: (1) the temperature of the reaction is 120°C to 220°C; (2) the time of the reaction is 0.5h to 48h; (3) during the reaction, the pressure of the carbon dioxide is 2atm to 16atm.
11. The method of any one of claims 1-4, wherein, the ratio of the amount of the alcohol amine to the amount of the solid catalyst is (100-1500):(4-700).
12. The method of claim 11, wherein, the ratio of the amount of the alcohol amine to the amount of the solid catalyst is (200-1300):(4-700).
13. The method of claim 12, wherein, the ratio of the amount of the alcohol amine to the amount of the solid catalyst is (300-1300):(4-700).
14. The method of claim 11, wherein, one or more of the following conditions are met: (1) the amount of the alcohol amine is 100mg to 1500mg; (2) the amount of the solid catalyst is 4mg to 700mg.
15. The method of claim 14, wherein, one or more of the following conditions are met: (1) the amount of the alcohol amine is 200mg to 1300mg; (2) the amount of the solid catalyst is 34mg to 684mg.
16. The method of claim 15, wherein, the amount of the alcohol amine is 300mg to 1300mg.
17. Use of a cerium-based composite oxide in the preparation of oxazolidinones from carbon dioxide and an alcohol amine, characterized in that, the cerium-based composite oxide is the cerium-based composite oxide used in the method of any one of claims 1-16.