Preparation process of gamma-butyrolactone
The γ-endobutyl ester is prepared by the reaction of acetic anhydride and ethylene, and the oxidant is recovered by baking, which solves the problems of high raw material costs and short oxidant life in the prior art, and achieves efficient and economical preparation of γ-endobutyl ester and recycling of oxidant.
Patent Information
- Application Number
- CN202411660279.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-20
- Publication Date
- 2025-02-25
AI Technical Summary
The existing γ-butyrolactone synthesis methods have problems such as high raw material costs, high equipment corrosion, and short oxidant life, which leads to high production costs and is difficult to meet the market's demand for γ-butyrolactone and its downstream products.
Acetic anhydride and ethylene are used as the main raw materials, and the reaction is added and the reaction is heated up, and the reactant is obtained and filtered. The filtrate contains the target product γ-endobutyl ester. After calcination, the filter residue is recovered as an oxidant and reintroduced to realize the recycling of the oxidant.
This process has high selectivity, low raw material cost and mild reaction conditions, which can effectively reduce production costs, improve economic benefits, and realize the recycling of oxidants, which is suitable for industrial promotion.
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of chemical synthesis, and in particular to a preparation process of γ-butyl ester. Background Art
[0002] γ-Butyrolactone (GBL) is an important organic chemical raw material and fine chemical intermediate. It is also a high-boiling point solvent with good performance, strong solubility, good electrical properties, high stability, non-toxicity and safe use. γ-Butyrolactone is widely used in industrial fields such as petrochemicals, textiles, spices, pesticides and medicines. Its largest use is the production of methyl pyrrolidone and battery electrolytes.
[0003] The existing synthesis methods of γ-butyrolactone are classified according to the raw materials, mainly including the following three methods: furfural method, maleic anhydride hydrogenation method and 1,4-butanediol dehydrogenation method. However, the price and supply of raw materials for furfural production are uncertain, and this process is rarely used in the world. At present, the 1,4-butanediol gas phase dehydrogenation method is mainly used in industry, followed by the method of synthesizing γ-butyrolactone by gas phase hydrogenation of maleic anhydride. The cost of maleic anhydride gas phase hydrogenation raw materials is low, but due to the presence of acid in the by-product, it is highly corrosive to the equipment and has high material requirements. In addition, the oxidant has a short life and a high price. This has led to a significant increase in the actual investment cost of the process. The 1,4-butanediol dehydrogenation process is relatively simple, the crude product has low acidity, and the by-products are easy to separate, so the finished product has a higher quality, but the price of raw materials for the 1,4-butanediol dehydrogenation process is relatively high.
[0004] With the rapid development of the global lithium battery and new energy industries, and the strengthening of environmental protection has led to an increase in demand for biodegradable plastics, the market demand for γ-butyrolactone and its downstream products has grown rapidly. Although the maleic anhydride hydrogenation method and 1,4-butanediol dehydrogenation method are relatively mature, the production cost is high. The cost can be reduced to a certain extent by producing raw materials by ourselves, but this will inevitably increase investment significantly and reduce the return on investment. Therefore, it is necessary to develop a new method for the synthesis of γ-butyrolactone. Summary of the invention
[0005] The purpose of the present application is to provide a preparation process of γ-butyl ester, which has a simple process flow, is easy to operate, has high product selectivity, can reduce raw material costs, can bring higher economic benefits, and has production application value.
[0006] The technical solution of this application is as follows:
[0007] The present invention provides a process for preparing γ-butyl ester, which comprises the following steps:
[0008] S1: Add acetic anhydride and oxidant to the reaction vessel, introduce ethylene, and heat to react.
[0009] Obtaining reactants;
[0010] S2: filtering the reactants to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0011] S3: The filter residue is calcined and recovered, and then re-added to the above step S1 as an oxidant.
[0012] Furthermore, in some embodiments of the present application, in the above step S1, the ratio of the amount of acetic anhydride added to the amount of ethylene is (1-15):1.
[0013] Furthermore, in some embodiments of the present application, in the above step S1, the molar ratio of the oxidant used to ethylene is (0.1-3):1.
[0014] Furthermore, in some embodiments of the present application, the above-mentioned oxidant is any one or more of a manganese-based oxidant, a vanadium-based oxidant, and a copper-based oxidant.
[0015] Furthermore, in some embodiments of the present application, the manganese-based oxidant includes Mn(Ac)3, Mn2O3, MnO2; the vanadium-based oxidant includes V2O5; and the copper-based oxidant includes Cu(Ac)2.
[0016] Furthermore, in some embodiments of the present application, in the above step S1, ethylene or ethylene and protective gas are introduced to make the pressure reach 1 to 3 MPa, and then the temperature is increased to carry out the reaction.
[0017] Furthermore, in some embodiments of the present application, the protective gas is nitrogen.
[0018] Furthermore, in some embodiments of the present application, in the above step S1, the ethylene content in the gas environment of the reaction system is 50-100%.
[0019] Furthermore, in some embodiments of the present application, in the above step S1, the temperature is raised to 80-250° C. for reaction.
[0020] Furthermore, in some embodiments of the present application, in the above step S1, the reaction time is 1 to 6 hours.
[0021] Furthermore, in some embodiments of the present application, in the above step S2, the reactant is cooled and then filtered under reduced pressure to obtain a filtrate and a filter residue.
[0022] Furthermore, in some embodiments of the present application, in the above step S3, the filter residue is calcined at 300-500°C.
[0023] Furthermore, in some embodiments of the present application, in the above step S3, the atmosphere during calcination is air or oxygen.
[0024] The present application also provides a γ-butyl ester, which is prepared by the above-mentioned preparation process.
[0025] Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:
[0026] In view of the above aspects, the present application provides a preparation process of γ-butyl ester, which first adds acetic anhydride and an oxidant into a reaction container, then introduces ethylene and heats the reaction. The obtained reactants are filtered to obtain a filtrate and a filter residue, wherein the filter residue component is an oxidant and can be recovered in a subsequent step; the filtrate contains the target product γ-butyl ester, and the reaction equation is as follows.
[0027]
[0028] The filter residue can be recovered by roasting it and used as an oxidant and re-introduced into the above-mentioned S1 step, thereby realizing the recycling of the oxidant and further saving production costs.
[0029] The present application adopts acetic anhydride and ethylene as the main raw materials to prepare and produce γ-butyl ester. Its technical route has a high conversion rate and extremely high product selectivity, which can effectively reduce separation energy consumption and facilitate product separation and purification. In addition, its scheme has low raw material cost, can recycle and reuse the oxidant, and save resources; at the same time, the whole process reaction conditions are mild, the process is simple, and it is easy to operate, which can effectively reduce the whole process production cost and improve the process production economic benefits, and is suitable for industrial production promotion and application. DETAILED DESCRIPTION
[0030] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.
[0031] It should be noted that the term "include" or any other variation thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "include..." do not exclude the existence of other identical elements in the process, method, article or device including its elements.
[0032] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.
[0033] The features and performance of the present application are further described in detail below in conjunction with the embodiments.
[0034] Example 1
[0035] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0036] S1: Add 40g of acetic anhydride and 4g of V2O5 (oxidant) into a 100ml reactor, introduce ethylene until the pressure of the reactor reaches 1.0MPa, then heat to 150°C for 1h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 15:1; the molar ratio of the used oxidant to the ethylene is 0.8:1;
[0037] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0038] Example 2
[0039] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0040] S1: Add 40g of acetic anhydride and 4g of V2O5 (oxidant) into a 100ml reactor, introduce ethylene until the pressure of the reactor reaches 1.5MPa, then heat to 80°C and react for 6h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 10:1; the molar ratio of the used oxidant to the ethylene is 0.6:1;
[0041] S2: Cooling the reactant and filtering it under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0042] Example 3
[0043] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0044] S1: Add 10g of acetic anhydride and 4g of V2O5 (oxidant) into a 100ml reactor, introduce ethylene until the pressure of the reactor reaches 2.0MPa, then heat to 120°C and react for 3h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 1.3:1; the molar ratio of the used oxidant to the ethylene is 0.3:1;
[0045] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0046] Example 4
[0047] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0048] S1: Add 20g of acetic anhydride and 6.0g of Mn(Ac)3 (oxidant) into a 100ml reactor, introduce a mixed gas of ethylene and nitrogen (ethylene content in the system is 75%) until the pressure of the reactor reaches 1.0MPa, then heat to 250°C and react for 1h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 7.8:1; and the molar ratio of the used oxidant to the ethylene is 0.9:1;
[0049] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0050] Example 5
[0051] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0052] S1: Add 20g of acetic anhydride and 3.5g of Mn2O3 (oxidant) into a 100ml reactor, introduce ethylene until the pressure of the reactor reaches 1.0MPa, then heat to 120°C and react for 3h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 5.8:1; the molar ratio of the used oxidant to the ethylene is 0.7:1;
[0053] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0054] Example 6
[0055] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0056] S1: Add 40g of acetic anhydride and 6.7g of MnO2 (oxidant) into a 100ml reactor, introduce a mixed gas of ethylene and nitrogen (ethylene content in the system is 50%) until the pressure of the reactor reaches 2.0MPa, then heat to 120°C and react for 3h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 15:1; the molar ratio of the used oxidant to the ethylene is 3:1;
[0057] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0058] Example 7
[0059] This embodiment provides a γ-butyl ester, which is prepared by the following process:
[0060] S1: Add 40g of acetic anhydride, 1.3g of Mn(Ac)3·2H2O and 0.6g of Cu(Ac)·H2O (oxidant) into a 100ml reactor, introduce ethylene until the pressure of the reactor reaches 3.0MPa, then heat to 120°C and react for 3h to obtain a reactant; wherein the molar ratio of the added acetic anhydride to the ethylene is 5:1; the molar ratio of the used oxidant to the ethylene is 0.1:1;
[0061] S2: Cooling the reactants and filtering them under reduced pressure to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester;
[0062] Example 8
[0063] This embodiment is based on Embodiment 1, and differs from Embodiment 1 in that:
[0064] Further, step S3 is performed: the filter residue obtained in Example 1 is dried in an oven at 80° C. for 12 h, and then calcined in an air atmosphere at 500° C. for 6 h, the oxidant is recovered, and then used again in step S1;
[0065] The remaining steps and conditions are the same as in Example 1.
[0066] Example 9
[0067] This embodiment is based on Embodiment 5, and differs from Embodiment 5 in that:
[0068] Further, step S3 is performed: the filter residue obtained in Example 5 is dried in an oven at 80° C. for 12 h, and then calcined in an oxygen atmosphere at 300° C. for 6 h, and the oxidant is recovered and reused in step S1;
[0069] The remaining steps and conditions are the same as in Example 5.
[0070] Test example
[0071] The filtrate containing the target product γ-butyl ester obtained in Examples 1 to 9 was analyzed by gas chromatography, and its ethylene conversion rate and GBL liquid phase selectivity were calculated. The specific calculation formula is as follows:
[0072]
[0073]
[0074] Among them, A i and A GBL Respectively represent the peak areas of impurity i and product GBL in the gas chromatogram of the liquid product;
[0075] f i and f GBL represent the correction factors for impurity i and product GBL, respectively.
[0076] The results are shown in Table 1:
[0077] Table 1
[0078]
[0079]
[0080] The results show that γ-butyrolactone can be obtained by using one or two of V2O5, Mn(Ac)3, Mn2O3, MnO2, Cu(Ac)2 as catalysts and acetic anhydride and ethylene as raw materials. Among them, when V2O5 is used as an oxidant, the liquid phase selectivity of γ-butyrolactone is the highest, reaching 99.0%, and the ethylene selectivity is higher than 18%. The oxidant after the reaction can be recycled after oxidation treatment, and the performance remains unchanged.
[0081] In summary, the present application embodiment provides a preparation process of γ-butyl ester, which uses acetic anhydride and ethylene as the main raw materials to prepare and produce γ-butyl ester. Its technical route has a high conversion rate and extremely high product selectivity, which can effectively reduce separation energy consumption and facilitate product separation and purification. And its scheme has low raw material cost, can recycle and reuse the oxidant, and save resources; at the same time, the whole process reaction conditions are mild, the process is simple, and it is easy to operate, which can effectively reduce the whole process production cost, improve the process production economic benefits, and is suitable for industrial production promotion and application.
[0082] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.
Claims
1. A process for preparing γ-butyl ester, characterized in that: It includes the following steps: S1: Add acetic anhydride and an oxidant into a reaction container, introduce ethylene, and heat to react to obtain a reactant; S2: filtering the reactants to obtain a filtrate and a filter residue, wherein the filtrate contains the target product γ-butyl ester; S3: The filter residue is calcined and recovered, and then re-added to the S1 step as an oxidant.
2. The process for preparing γ-butyl ester according to claim 1, characterized in that: In the step S1, the molar ratio of the added acetic anhydride to ethylene is (1-15):
1.
3. The process for preparing γ-butyl ester according to claim 1, characterized in that: In the step S1, the molar ratio of the oxidant used to ethylene is (0.1-3):
1.
4. The process for preparing γ-butyl ester according to claim 1, characterized in that: The oxidant is any one or more of a manganese-based oxidant, a vanadium-based oxidant, and a copper-based oxidant.
5. The process for preparing γ-butyl ester according to claim 4, characterized in that: The manganese-based oxidant includes Mn(Ac)3, Mn2O3, and MnO2; the vanadium-based oxidant includes V2O5; and the copper-based oxidant includes Cu(Ac)2.
6. The process for preparing γ-butyl ester according to claim 1, characterized in that: In the step S1, ethylene or ethylene and protective gas are introduced to make the pressure reach 1-3 MPa, and then the temperature is increased to carry out the reaction.
7. The process for preparing γ-butyl ester according to claim 6, characterized in that: In the step S1, the ethylene content in the gas environment of the reaction system is 50-100%.
8. The process for preparing γ-butyl ester according to claim 1, characterized in that: In the step S1, the temperature is raised to 80-250° C. for reaction.
9. The process for preparing γ-butyl ester according to claim 1, characterized in that: In the step S3, the filter residue is calcined at 300-500°C.
10. A γ-butyl ester, characterized in that The method is prepared by the preparation process according to any one of claims 1 to 9.