WO2022258072A1 - 碳酸亚乙烯酯的制备方法 - Google Patents

碳酸亚乙烯酯的制备方法 Download PDF

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WO2022258072A1
WO2022258072A1 PCT/CN2022/098802 CN2022098802W WO2022258072A1 WO 2022258072 A1 WO2022258072 A1 WO 2022258072A1 CN 2022098802 W CN2022098802 W CN 2022098802W WO 2022258072 A1 WO2022258072 A1 WO 2022258072A1
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vinylene carbonate
preparation
reaction
yield
carbonate
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PCT/CN2022/098802
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English (en)
French (fr)
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朱振涛
贾国文
葛保超
武燕
马俊青
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山东海科创新研究院有限公司
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Priority to KR1020237032750A priority Critical patent/KR102677765B1/ko
Publication of WO2022258072A1 publication Critical patent/WO2022258072A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol

Definitions

  • the application belongs to the technical field of organic synthesis, in particular to a preparation method of vinylene carbonate.
  • Vinylene carbonate also known as 1,3-dioxol-2-one, has the property of being a colorless transparent liquid. It is a new type of organic film-forming additive and overcharge protection additive for lithium-ion batteries.
  • the present application proposes a method for preparing vinylene carbonate, aiming at at least one of the above technical problems in the existing preparation method of vinylene carbonate.
  • the preparation method of vinylene carbonate comprises the following steps:
  • the hydrogen acceptor is selected from any one of furfural or furan.
  • the supported copper-based catalyst is an acidic carrier, a basic carrier, or a mixture of an acidic carrier and a basic carrier.
  • the acidic carrier is selected from any one or more of aluminum oxide, zinc oxide, or iron oxide.
  • the basic carrier is selected from any one or both of lanthanum oxide and magnesium oxide.
  • the reaction device is a continuous fixed-bed reactor or a batch reactor.
  • the feed ratio of ethylene carbonate to hydrogen acceptor is (2:1)-(1:1).
  • furfuryl alcohol and tetrahydrofuran are also prepared by using the method for preparing vinylene carbonate.
  • the yield of furfuryl alcohol is 40-70%, and the yield of tetrahydrofuran is 20-40%.
  • the present application also proposes a vinylene carbonate, which is prepared by using the method for preparing vinylene carbonate described in any of the above technical solutions, and the yield of the vinylene carbonate is 75-90%.
  • the preparation method of vinylene carbonate proposed in the embodiments of the present application uses a supported copper-based catalyst, ethylene carbonate is used as a hydrogen donor, and furfural or furan is used as a hydrogen acceptor to carry out catalytic dehydrogenation-hydrogenation coupling
  • the target product vinylene carbonate is prepared by a one-step reaction method, which can increase the yield of vinylene carbonate, reduce the reaction temperature, and reduce the production cost of vinylene carbonate;
  • the preparation method of vinylene carbonate proposed in the embodiments of the present application in addition to being able to prepare vinylene carbonate, the method can also prepare two high value-added products of furfuryl alcohol and tetrahydrofuran;
  • the preparation method of vinylene carbonate proposed in the examples of this application has the characteristics of simple preparation process, short reaction time, no need to add toxic and harmful substances, and low cost.
  • the embodiment of the present application provides a kind of preparation method of vinylene carbonate, comprises the following steps:
  • the hydrogen acceptor is selected from any one of furfural or furan.
  • a new preparation method of vinylene carbonate which uses a supported copper-based catalyst, ethylene carbonate as a hydrogen donor, and adds a hydrogen acceptor to carry out catalytic dehydrogenation-hydrogenation
  • the target product vinylene carbonate is prepared by coupling reaction one-step method, and the method can increase the yield of vinylene carbonate, shorten the reaction time, lower the reaction temperature and reduce the production cost of vinylene carbonate.
  • furfural or furan as the hydrogen acceptor: these two raw materials can undergo reactions such as halogenation, sulfonation, and hydrogenation, and are often used in organic synthesis reactions, and they are used as hydrogen acceptors for synthesis The added value of furfural or furan is higher.
  • the catalyst used in the examples of the present application is a cheap and easy-to-obtain supported copper-based catalyst, and the dehydrogenation-hydrogenation coupling reaction is catalyzed by a continuous method or a batch method, which can ensure a high yield of the target product. Hydrogen is directly hydrogenated with another raw material to obtain high value-added products.
  • the supported copper-based catalyst is an acidic carrier, a basic carrier, or a mixture of an acidic carrier and a basic carrier.
  • the acidic carrier is selected from any one or more of aluminum oxide, zinc oxide or iron oxide.
  • the basic carrier is selected from any one or both of lanthanum oxide and magnesium oxide.
  • the reaction device is a continuous fixed-bed reactor or a batch reactor.
  • the feed ratio of ethylene carbonate to hydrogen acceptor is (2:1)-(1:1).
  • the reason for limiting the feed ratio of ethylene carbonate to hydrogen acceptor to (2:1)-(1:1): in order to ensure a higher yield of vinylene carbonate, to combine with the two A balance is achieved between the yields of high value-added products, so that the comprehensive yield of the above-mentioned products reaches an ideal state.
  • the ratio of ethylene carbonate to hydrogen acceptor is (2:1) -(1:1), it can well balance the yield of vinylene carbonate and the yield of two high value-added products.
  • furfuryl alcohol and tetrahydrofuran are also prepared by using the preparation method of vinylene carbonate.
  • the yield of furfuryl alcohol is 40-70%, and the yield of tetrahydrofuran is 20-40%.
  • the application also proposes a kind of vinylene carbonate, which is prepared by the preparation method of vinylene carbonate described in any of the above-mentioned embodiments, and the yield of said vinylene carbonate is 75-90%.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a continuous fixed-bed reactor is used for the catalytic reaction, 3g of Cu/Al 2 O 3 catalyst is packed in the reactor, nitrogen gas is introduced, the flow rate is 10L/h, and the molar ratio of ethylene carbonate and furfural is 1.2:1.
  • the raw material is added to the reactor with a flow rate of 20g/h, and the catalytic dehydrogenation-hydrogenation coupling reaction is carried out at a temperature of 260°C.
  • the material is taken every 2h and tested by gas chromatography to detect the content of vinylene carbonate and furfuryl alcohol. yield.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a reactor as a reactor to react, put 5g of Cu/ La2O3 catalyst at the bottom of the reactor, configure 100g of a mixture of ethylene carbonate and furfural with a molar ratio of 1.2:1, put it into the reactor, and seal the reactor OK, flush with nitrogen, replace 3 times, nitrogen pressure in the kettle is 0.1MPa, carry out catalytic dehydrogenation-hydrogenation coupling reaction at a reaction temperature of 220°C, the reaction time is 3h, the reaction is over, wait until the temperature of the kettle drops to At room temperature, gas chromatography was used to detect the yields of vinylene carbonate and furfuryl alcohol.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a fixed-bed reactor is used for catalytic reaction, 3g of Cu/La 2 O 3 is filled in the reactor, nitrogen gas is introduced, the flow rate is 10L/h, and the mixed raw material with ethylene carbonate and furfural molar ratio of 1.2:1 is configured, and the Into the reactor, the flow rate is 20g/h, and the catalytic dehydrogenation-hydrogenation coupling reaction is carried out at a temperature of 300°C. The material is taken every 2h, and the gas chromatography test is performed to detect the yield of vinylene carbonate and furfuryl alcohol.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a reactor as a reactor for the reaction, load 5g of Cu/Al 2 O 3 -La 2 O 3 catalyst at the bottom of the reactor, configure 100g of a mixture of ethylene carbonate and furan with a molar ratio of 1.6:1, and put it into the reactor
  • the kettle was sealed, flushed with nitrogen, and replaced 3 times.
  • the nitrogen pressure in the kettle was 0.1MPa, and the catalytic dehydrogenation-hydrogenation coupling reaction was carried out under the condition of a reaction temperature of 240°C.
  • the reaction time was 3h, and the reaction was completed. After the temperature of the kettle was lowered to room temperature, gas chromatography was used to detect the yields of vinylene carbonate and tetrahydrofuran.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a fixed bed reactor was used for catalytic reaction, 5g of Cu/Al 2 O 3 -La 2 O 3 was filled in the reactor, nitrogen gas was introduced, the flow rate was 3L/h, and the molar ratio of ethylene carbonate and furan was 1.8:1
  • the mixed raw materials are added to the reactor, the flow rate is 15g/h, and the catalytic dehydrogenation-hydrogenation coupling reaction is carried out under the condition of the reaction temperature of 300°C.
  • the material is taken every 2h, and the gas chromatography test is carried out to detect the carbon dioxide Yields of vinyl esters and tetrahydrofuran.
  • the present embodiment provides a kind of preparation method of vinylene carbonate, specifically:
  • a reactor as a reactor for the reaction, put 5g of Cu/Al 2 O 3 -La 2 O 3 at the bottom of the reactor, configure 120g of a mixture of ethylene carbonate and furan with a molar ratio of 2:1, and put it into the reactor , seal the kettle well, flush it with nitrogen, and replace it 3 times.
  • the nitrogen pressure in the kettle is 0.1MPa
  • the catalytic dehydrogenation-hydrogenation coupling reaction is carried out under the condition of a reaction temperature of 200°C.
  • the reaction time is 2 hours. Cool down to room temperature, and use gas chromatography to detect the yields of vinylene carbonate and tetrahydrofuran.
  • This comparative example provides a kind of preparation method of vinylene carbonate, specifically:
  • a reactor as a reactor for the reaction, load 5g of Cu/Al 2 O 3 -La 2 O 3 catalyst at the bottom of the reactor, configure 100g of a mixture of ethylene carbonate and furan with a molar ratio of 3:1, and put it into the reactor
  • the kettle was sealed, flushed with nitrogen, and replaced 3 times.
  • the nitrogen pressure in the kettle was 0.1MPa, and the catalytic dehydrogenation-hydrogenation coupling reaction was carried out under the condition of a reaction temperature of 240°C.
  • the reaction time was 3h, and the reaction was completed. After the temperature of the kettle was lowered to room temperature, gas chromatography was used to detect the yields of vinylene carbonate and tetrahydrofuran.
  • This comparative example provides a kind of preparation method of traditional vinylene carbonate, specifically:
  • This comparative example provides a kind of preparation method of vinylene carbonate, specifically:
  • the Al 2 O 3 carrier is crushed and sieved, and 20-40 mesh is selected. After activation at 500°C for 2 hours, the iron catalyst is loaded on the Al 2 O 3 carrier to obtain the mass ratio of Fe 2 O 3 to Al 2 O 3 1:4 catalyst.
  • ethylene carbonate is continuously fed into the micro-fixed-bed reactor with a micro-sampling pump at a space velocity of 2g/h mlcat., the reaction temperature is 360°C, and the reaction pressure is 0.2MPa. Nitrogen was introduced as carrier gas and protective gas to react, and the reaction product was collected by condensing device and analyzed by gas chromatography to detect the yield of vinylene carbonate.
  • Example 1 80% 47% - Example 2 90% 65% - Example 3 75% 43% - Example 4 85% - 20%
  • Example 5 80% - 30%
  • Example 6 75% - 32% Comparative example 1 60% - 45% Comparative example 2 70% - - Comparative example 3 65% - -
  • the preparation method provided in Comparative Example 1 has an unsatisfactory yield of vinylene carbonate due to the high molar ratio of ethylene carbonate and furan
  • the preparation method provided in Comparative Example 2 is a traditional two-step reaction, and In the preparation process, toxic and harmful substances such as chloroethylene carbonate are used, which have disadvantages such as long reaction time, easy to cause equipment corrosion, more solid waste, and difficult disposal, and the use of toxic substances does not conform to the current green chemistry.
  • the preparation method that comparative example 3 adopts is the reaction that ethylene carbonate one-step dehydrogenation prepares vinylene carbonate, although this reaction is one-step reaction, its required reaction temperature is higher (generally more than 300 °C), and carbonic acid
  • the yield of vinylidene is not high, but using the preparation method provided in the examples of this application, using a supported copper-based catalyst, ethylene carbonate as a hydrogen donor, furfural or furan as a hydrogen acceptor, to carry out catalytic dehydrogenation - One-step hydrogenation coupling reaction to prepare the target product vinylene carbonate.
  • This method can also prepare furfuryl alcohol and tetrahydrofuran while increasing the yield of vinylene carbonate, reducing the reaction temperature and reducing the production cost of vinylene carbonate. Two high value-added products. It can be seen that the preparation process provided by the present application has more advantages in terms of production cost and product performance.

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Abstract

本申请提出一种碳酸亚乙烯酯的制备方法，属于有机合成技术领域，能够解决现有的碳酸亚乙烯酯的制备方法存在的操作步骤复杂、反应时间长、易造成设备腐蚀、反应温度高、收率低等的技术问题。该技术方案包括：向反应装置中加入一定质量的负载型铜基催化剂、碳酸乙烯酯和氢受体，在氮气气氛中，于200-300℃条件下进行催化脱氢-加氢耦合反应，制备得到碳酸亚乙烯酯产品。本申请具有制备工艺简单、成本低廉、反应温度低且收率高等特点。本申请能够应用于碳酸亚乙烯酯制备方面。

Description

碳酸亚乙烯酯的制备方法
本申请要求在2021年11月23日提交中国专利局、申请号为202111389822.X、申请名称为“碳酸亚乙烯酯的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于有机合成技术领域，尤其涉及一种碳酸亚乙烯酯的制备方法。
背景技术
碳酸亚乙烯酯，又称1,3-二氧杂环戊烯-2-酮，具有呈无色透明液体的性质，是一种锂离子电池新型有机成膜添加剂与过充电保护添加剂。
目前，碳酸亚乙烯酯的制备方法主要有两种，一是碳酸乙烯酯通过光氯代反应生成一氯代碳酸乙烯酯(CEC)，然后在碱性环境条件，脱去氯化氢，生成碳酸亚乙烯酯的粗品，纯化得到商品化的碳酸亚乙烯酯(例如中国专利申请CN110483471A、CN108864031A、CN106632225A等)。该方法不仅涉及氯气、四氯化碳或黄酰氯等有毒有害物质，而且是两步反应，反应时间长，先引入氯原子，再脱除氯原子形成氯化氢，对设备腐蚀严重；二是采用催化脱氢的方法将碳酸乙烯酯一步脱氢制备碳酸亚乙烯酯(中国专利申请CN1789259A)，该反应需要在300℃以上，惰性气氛中进行，色谱收率最高只有60％，收率较低，这主要是因为碳-碳键脱氢需要的活化能较高，同时碳-碳双键会有脱出的氢再次反应又形成碳酸乙烯酯结构。
发明内容
本申请针对现有的碳酸亚乙烯酯的制备方法存在以上至少一个技术问题，提出一种碳酸亚乙烯酯的制备方法。
为了达到上述目的，本申请采用的技术方案为：
碳酸亚乙烯酯的制备方法，包括以下步骤：
向反应装置中加入一定质量的负载型铜基催化剂、碳酸乙烯酯和氢受体，在氮气气氛中，于200-300℃条件下进行催化脱氢-加氢耦合反应，制备得到碳酸亚乙烯酯产品；
所述氢受体选自糠醛或呋喃中的任意一种。
在本申请一些实施例中，所述负载型铜基催化剂为酸性载体、碱性载体或酸性载体与碱性载体混用。
在本申请一些实施例中，所述酸性载体选自三氧化二铝、氧化锌或氧化铁中的任意一种或几种。
在本申请一些实施例中，所述碱性载体选自氧化镧或氧化镁的任意一种或两种。
在本申请一些实施例中，所述反应装置为连续化固定床反应器或间歇法反应釜。
在本申请一些实施例中，所述碳酸乙烯酯与氢受体投料比为(2：1)-(1：1)。
在本申请一些实施例中，利用所述的碳酸亚乙烯酯的制备方法还制备得到糠醇和四氢呋喃。
在本申请一些实施例中，所述糠醇的收率为40-70％，四氢呋喃的收率为20-40％。
本申请还提出了一种碳酸亚乙烯酯，利用上述任一技术方案所述的碳酸亚乙烯酯的制备方法制备得到，所述碳酸亚乙烯酯的收率为75-90％。
与现有技术相比，本申请的优点和积极效果在于：
1、本申请实施例提出的碳酸亚乙烯酯的制备方法，该方法采用负载型铜基催化剂，碳酸乙烯酯作为氢供体，糠醛或是呋喃作为氢受体，进行催化脱氢-加氢耦合反应一步法制备得到目标产物碳酸亚乙烯酯，该方法能提高碳酸亚乙烯酯的收率、降低反应温度、降低碳酸亚乙烯酯的生产成本；
2、本申请实施例提出的碳酸亚乙烯酯的制备方法，该方法除了能制备得到碳酸亚乙烯酯外，还能制备得到糠醇和四氢呋喃两种高附加值的产品；
3、本申请实施例提出的碳酸亚乙烯酯的制备方法具有制备工艺简单、反应时间短、无需添加有毒有害物质、成本低廉等特点。
具体实施方式
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请实施例提供了一种碳酸亚乙烯酯的制备方法，包括以下步骤：
向反应装置中加入一定质量的负载型铜基催化剂、碳酸乙烯酯和氢受体，在氮气气氛中，于200-300℃条件下进行催化脱氢-加氢耦合反应，制备得到碳酸亚乙烯酯产品；
所述氢受体选自糠醛或呋喃中的任意一种。
在上述实施例中，提出了一种新的碳酸亚乙烯酯的制备方法，该方法采用负载型铜基催化剂，碳酸乙烯酯作为氢供体，并加入氢受体，进行催化脱氢-加氢耦合反应一步法制备得到目标产物碳酸亚乙烯酯，该方法能提高碳酸亚乙烯酯的收率、缩短反应时间、降低反应温度、降低碳酸亚乙烯酯的生产成本。
在上述实施例中，选择糠醛或呋喃作为氢受体的原因：这两种原料可以发生卤化、磺化、加氢等反应，常用于有机合成反应之中，将其作为氢受体用于合成糠醛或呋喃的附加价值较高。
此外，本申请实施例采用的催化剂为廉价易得的负载型铜基催化剂，采用连续法或是间歇法催化脱氢-加氢耦合反应，能够在确保目标产物较高收率条件下，脱出的氢直接与另一种原料发生加氢反应，从而获得高附加值的产品。
在一些实施例中，所述负载型铜基催化剂为酸性载体、碱性载体或酸性载体与碱性载体混用。
在一些实施例中，所述酸性载体选自三氧化二铝、氧化锌或氧化铁中的任意一种或几种。
在一些实施例中，所述碱性载体选自氧化镧或氧化镁的任意一种或两种。
在一些实施例中，所述反应装置为连续化固定床反应器或间歇法反应釜。
在一些实施例中，所述碳酸乙烯酯与氢受体投料比为(2：1)-(1：1)。
在上述实施例中，将碳酸乙烯酯与氢受体投料比限定为(2：1)-(1：1)的原因：为了在保证碳酸亚乙烯酯收率较高的基础上，与两种高附加值产品的收率之间取得平衡，使得上述产品的综合收率达到理想状态，本申请通过大量筛选实验验证后得知，当碳酸乙烯酯与氢受体投料比为(2：1)-(1：1)时，能够很好的平衡碳酸亚乙烯酯收率与两种高附加值产品收率。
在一些实施例中，利用碳酸亚乙烯酯的制备方法还制备得到糠醇和四氢呋喃。
在一些实施例中，所述糠醇的收率为40-70％，四氢呋喃的收率为20-40％。
本申请还提出了一种碳酸亚乙烯酯，其利用上述任一实施例所述的碳酸 亚乙烯酯的制备方法制备得到，所述碳酸亚乙烯酯的收率为75-90％。
为了更清楚详细地介绍本申请实施例所提供的碳酸亚乙烯酯的制备方法，下面将结合具体实施例进行描述。
实施例1
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：
配置1mol/L的硝酸铜水溶液，然后向其中加入500目的Al 2O 3粉体，搅拌均匀，制得A液；配置1mol/L的碳酸钠水溶液，制得B液，采用恒压滴液漏斗将B液加入A液中，待全部滴加完成，过滤获得沉淀，采用挤条器获得直径为5mm的催化剂前驱体；催化剂前驱体再经120℃烘干，然后经过500℃焙烧5h，在管式炉中，通入氮氢(氢气体积占5％)混合气，400℃还原3h，获得Cu/Al 2O 3催化剂，其中Cu负载量为10wt％。
(2)碳酸亚乙烯酯的制备：
采用连续化固定床反应器进行催化反应，将3g的Cu/Al 2O 3催化剂装填于反应器中，通入氮气，流量10L/h，配置碳酸乙烯酯和糠醛摩尔比为1.2:1的混合原料，添加到反应器中，流量为20g/h，于260℃温度条件下进行催化脱氢-加氢耦合反应，每隔2h取一次物料，进行气相色谱测试，检测碳酸亚乙烯酯和糠醇的收率。
实施例2
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：
配置1mol/L的硝酸铜水溶液，然后向其中加入500目的La 2O 3粉体，搅拌均匀，制得A液；配置1mol/L的碳酸钠水溶液，制得B液，采用恒压滴液 漏斗将B液加入A液中，待全部滴加完成，过滤获得沉淀，采用挤条器获得直径为5mm的催化剂前驱体；催化剂前驱体再经120℃烘干，然后经过500℃焙烧5h，在管式炉中，通入氮氢(氢气体积占5％)混合气，400℃还原3h，获得Cu/La 2O 3催化剂，其中Cu负载量为15wt％。
(2)碳酸亚乙烯酯的制备：
采用反应釜作为反应器进行反应，在釜底部装入5g的Cu/La 2O 3催化剂，配置碳酸乙烯酯和糠醛摩尔比为1.2:1的混合物料100g，放入反应釜中，将釜密封好，冲入氮气，置换3次，釜中氮气压力为0.1MPa，在反应温度为220℃的条件下进行催化脱氢-加氢耦合反应，反应时长为3h，反应结束，待釜温度降至室温，采用气相色谱测试，检测碳酸亚乙烯酯和糠醇的收率。
实施例3
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：制备方法同实施例2。
(2)碳酸亚乙烯酯的制备：
采用固定床反应器进行催化反应，将3g的Cu/La 2O 3装填在反应器中，通入氮气，流量10L/h，配置碳酸乙烯酯和糠醛摩尔比为1.2:1的混合原料，添加至反应器中，流量为20g/h，于300℃温度条件下进行催化脱氢-加氢耦合反应，每隔2h取一次物料，进行气相色谱测试，检测碳酸亚乙烯酯和糠醇的收率。
实施例4
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：
配置1mol/L的硝酸铜水溶液，之后向其中加入500目的La 2O 3和Al 2O 3 粉体，搅拌均匀，制得A液；配置1mol/L的碳酸钠水溶液，制得B液，采用恒压滴液漏斗将B液加入A液中，待全部滴加完成，过滤获得沉淀，采用挤条器获得直径为5mm的催化剂前驱体；催化剂前驱体再经120℃烘干，然后经过500℃焙烧5h，在管式炉中，通入氮氢(氢气体积占5％)混合气，400℃还原3h，获得Cu/Al 2O 3-La 2O 3催化剂，其中Cu负载量为5wt％。
(2)碳酸亚乙烯酯的制备：
采用反应釜作为反应器进行反应，在釜底部装入5g的Cu/Al 2O 3-La 2O 3催化剂，配置碳酸乙烯酯和呋喃摩尔比为1.6:1的混合物料100g，放入反应釜中，将釜密封好，冲入氮气，置换3次，釜中氮气压力为0.1MPa，在反应温度为240℃的条件下进行催化脱氢-加氢耦合反应，反应时长为3h，反应结束，待釜温度降至室温，采用气相色谱测试，检测碳酸亚乙烯酯和四氢呋喃的收率。
实施例5
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：制备方法同实施例4。
(2)碳酸亚乙烯酯的制备：
采用固定床反应器进行催化反应，将5g的Cu/Al 2O 3-La 2O 3装填在反应器中，通入氮气，流量3L/h，配置碳酸乙烯酯和呋喃摩尔比为1.8:1的混合原料，添加至反应器中，流量为15g/h，在反应温度为300℃的条件下进行催化脱氢-加氢耦合反应，每隔2h取一次物料，进行气相色谱测试，检测碳酸亚乙烯酯和四氢呋喃的收率。
实施例6
本实施例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：制备方法同实施例4。
(2)碳酸亚乙烯酯的制备：
采用反应釜作为反应器进行反应，在釜底部装入5g的Cu/Al 2O 3-La 2O 3，配置碳酸乙烯酯和呋喃摩尔比为2:1的混合物料120g，放入反应釜中，将釜密封好，冲入氮气，置换3次，釜中氮气压力为0.1MPa，在反应温度为200℃的条件下进行催化脱氢-加氢耦合反应，时间2h，反应结束，待釜温度降至室温，采用气相色谱测试，检测碳酸亚乙烯酯和四氢呋喃的收率。
对比例1
本对比例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)负载型铜基催化剂的制备：
配置1mol/L的硝酸铜水溶液，之后向其中加入500目的La 2O 3和Al 2O 3粉体，搅拌均匀，制得A液；配置1mol/L的碳酸钠水溶液，制得B液，采用恒压滴液漏斗将B液加入A液中，待全部滴加完成，过滤获得沉淀，采用挤条器获得直径为5mm的催化剂前驱体；催化剂前驱体再经120℃烘干，然后经过500℃焙烧5h，在管式炉中，通入氮氢(氢气体积占5％)混合气，400℃还原3h，获得Cu/Al 2O 3-La 2O 3催化剂，其中Cu负载量为5wt％。
(2)碳酸亚乙烯酯的制备：
采用反应釜作为反应器进行反应，在釜底部装入5g的Cu/Al 2O 3-La 2O 3催化剂，配置碳酸乙烯酯和呋喃摩尔比为3:1的混合物料100g，放入反应釜中，将釜密封好，冲入氮气，置换3次，釜中氮气压力为0.1MPa，在反应温度为240℃的条件下进行催化脱氢-加氢耦合反应，反应时长为3h，反应结束，待釜温度降至室温，采用气相色谱测试，检测碳酸亚乙烯酯和四氢呋喃的收率。
对比例2
本对比例提供了一种传统碳酸亚乙烯酯的制备方法，具体为：
在通风橱中准确称量氯代碳酸乙烯酯300g、碳酸二甲酯900g(水分＜500ppm)、阻聚剂BHT0.9g、三乙胺242g(水分＜500ppm)，先将氯代碳酸乙烯酯、碳酸二甲酯和阻聚剂依次加入2L带有机械搅拌和回流的三颈烧瓶中，烧瓶置于水浴中，待加热到反应温度时，将三乙胺通过恒压滴液漏斗滴入三颈烧瓶中(保持2-3滴/s，保证2个小时可以滴完)，待滴加完三乙胺，控制反应温度恒定在指定温度，保温2-3h，取样气相色谱中控检测。
对比例3
本对比例提供了一种碳酸亚乙烯酯的制备方法，具体为：
(1)催化剂的制备：
Al 2O 3载体经破碎过筛，选取20-40目，先在500℃下活化2h后，将铁催化剂负载在Al 2O 3载体上，得到Fe 2O 3与Al 2O 3的质量比为1∶4的催化剂。
(2)碳酸亚乙烯酯的制备：
将催化剂加入固定床反应器中，碳酸乙烯酯用微量进样泵以2g/h·mlcat.的空速持续通入微型固定床反应器中，反应温度为360℃，反应压力为0.2MPa，同时通入氮气作载气和保护气进行反应，反应产物用冷凝装置收集，并用气相色谱进行分析，检测碳酸亚乙烯酯的收率。
相关产品的收率测定
采用气相色谱分析法对上述各个实施例与对比例制备得到的碳酸亚乙烯酯、糠醇和四氢呋喃进行收率测定，具体结果如下：
表1实施例1-6及对比例1-3所得相关产品的收率测定结果
  碳酸亚乙烯酯收率(％) 糠醇收率(％) 四氢呋喃收率(％)
实施例1 80％ 47％ -
实施例2 90％ 65％ -
实施例3 75％ 43％ -
实施例4 85％ - 20％
实施例5 80％ - 30％
实施例6 75％ - 32％
对比例1 60％ - 45％
对比例2 70％ - -
对比例3 65％ - -
由上表可知，利用对比例1所提供的方法提高碳酸乙烯酯和呋喃的摩尔比制备得到的碳酸亚乙烯酯收率下降至60％，对比例2-3的方法制备碳酸亚乙烯酯产率不高而且在制备过程中并未产生糠醇、四氢呋喃等高附加值的产品，而利用本申请实施例所述的方法制备得到的碳酸亚乙烯酯收率高，最高可达90％，而且还能制得糠醇和四氢呋喃两种高附加值的产品。
进一步地，对比例1提供的制备方法由于碳酸乙烯酯和呋喃的摩尔比过高，导致制备的碳酸亚乙烯酯的收率不理想，对比例2提供的制备方法为传统的两步反应，且在制备过程中使用了氯代碳酸乙烯酯等有毒有害物质，存在反应耗时较长、易造成设备腐蚀、固废较多、不好处理等缺点，而且采用有毒物质也不符合当下绿色化学的要求，对比例3采用的制备方法是将碳酸乙烯酯一步脱氢制备碳酸亚乙烯酯的反应，虽然该反应为一步反应，但其所需反应温度较高(一般为300℃以上)，而且碳酸亚乙烯酯的收率并不高，而利用本申请实施例所提供的制备方法，采用负载型铜基催化剂，碳酸乙烯酯作为氢供体，糠醛或是呋喃作为氢受体，进行催化脱氢-加氢耦合反应一步法制备得到目标产物碳酸亚乙烯酯，该方法在提高碳酸亚乙烯酯的收率、降低 反应温度、降低碳酸亚乙烯酯的生产成本的同时，还能制备得到糠醇和四氢呋喃两种高附加值的产品。由此可见，本申请提供的制备工艺无论是生产成本方面、还是产品性能都更具优势。

Claims (8)

  1. 一种碳酸亚乙烯酯的制备方法，其特征在于，包括以下步骤：
    向反应装置中加入一定质量的负载型铜基催化剂、碳酸乙烯酯和氢受体，在氮气气氛中，于200-300℃条件下进行催化脱氢-加氢耦合反应，制备得到碳酸亚乙烯酯产品；
    所述氢受体选自糠醛或呋喃中的任意一种。
  2. 根据权利要求1所述的碳酸亚乙烯酯的制备方法，其特征在于，所述负载型铜基催化剂为酸性载体、碱性载体或酸性载体与碱性载体混用。
  3. 根据权利要求2所述的碳酸亚乙烯酯的制备方法，其特征在于，所述酸性载体选自三氧化二铝、氧化锌或氧化铁中的任意一种或几种。
  4. 根据权利要求2所述的碳酸亚乙烯酯的制备方法，其特征在于，所述碱性载体选自氧化镧或氧化镁的任意一种或两种。
  5. 根据权利要求1所述的碳酸亚乙烯酯的制备方法，其特征在于，所述反应装置为连续化固定床反应器或间歇法反应釜。
  6. 根据权利要求1所述的碳酸亚乙烯酯的制备方法，其特征在于，所述碳酸乙烯酯与氢受体投料比为(2：1)-(1：1)。
  7. 根据权利要求1所述的碳酸亚乙烯酯的制备方法，其特征在于，还制备得到糠醇和四氢呋喃。
  8. 根据权利要求7所述的碳酸亚乙烯酯的制备方法，其特征在于，所述糠醇的收率为40-70％，四氢呋喃的收率为20-40％。
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