CN103772344B - Photochemical synthesis method of monochloroethylene carbonate and photochemical reactor - Google Patents
Photochemical synthesis method of monochloroethylene carbonate and photochemical reactor Download PDFInfo
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- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000001308 synthesis method Methods 0.000 title description 2
- 230000005587 bubbling Effects 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 26
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 2
- 238000002386 leaching Methods 0.000 claims 2
- 229910052596 spinel Inorganic materials 0.000 claims 2
- 239000011029 spinel Substances 0.000 claims 2
- 239000002826 coolant Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 abstract description 51
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011261 inert gas Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000001174 ascending effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 24
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229950011008 tetrachloroethylene Drugs 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000010002 alcoholic liver cirrhosis Diseases 0.000 description 1
- ZBEBOOQVKXZARN-UHFFFAOYSA-N carbonochloridic acid;ethene Chemical compound C=C.OC(Cl)=O ZBEBOOQVKXZARN-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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- 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
- C07D317/42—Halogen atoms or nitro radicals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
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Abstract
本发明涉及光化学合成一氯代碳酸乙烯酯的方法及光化学反应器。本发明利用一种在内浸式光反应器中设置有一个夹套式的沉阱、在夹套式的沉阱中安装有高压汞灯的内浸上行鼓泡式光化学反应器进行光化学合成一氯代碳酸乙烯酯；在惰性气体的保护下，特别是剔除了传统的剧毒性的反应溶剂，使原料碳酸乙烯酯与氯气直接接触反应，反应不需要反应溶剂。所述的反应采取内浸式的光照方式，利用上行、鼓泡的方法来完成反应。用本发明方法制备一氯代碳酸乙烯酯的收率高达90%，产物易于分离提纯，纯度达到98.5%以上。本发明的方法由于不涉及传统使用的剧毒性的溶剂，反应速度快，安全系数高，对设备要求低，非常有利于大规模的工业化生产。
The invention relates to a method for photochemically synthesizing monochloroethylene carbonate and a photochemical reactor. The present invention utilizes an internal immersion ascending bubbling photochemical reactor in which a jacketed sinker is arranged in the jacketed sinker and a high-pressure mercury lamp is installed in the jacketed sinker to carry out photochemical synthesis. Chloroethylene carbonate: Under the protection of inert gas, especially the traditional highly toxic reaction solvent is eliminated, the raw material ethylene carbonate and chlorine gas are directly contacted and reacted, and the reaction does not require a reaction solvent. The described reaction adopts an in-immersion lighting method, and utilizes the method of ascending and bubbling to complete the reaction. The yield of the monochloroethylene carbonate prepared by the method of the invention is as high as 90%, the product is easy to separate and purify, and the purity reaches more than 98.5%. Since the method of the invention does not involve traditionally used highly toxic solvents, the reaction speed is fast, the safety factor is high, and the requirement for equipment is low, which is very beneficial to large-scale industrial production.
Description
技术领域technical field
本发明属于有机光化学合成技术领域，特别涉及利用光能引发自由基反应进行光化学合成一氯代碳酸乙烯酯的方法，以及适用于该方法的光化学反应器。The invention belongs to the technical field of organic photochemical synthesis, and in particular relates to a method for photochemically synthesizing monochloroethylene carbonate by using light energy to initiate free radical reaction, and a photochemical reactor suitable for the method.
背景技术Background technique
锂离子电池是上个世纪90年代发展起来的绿色新能源，这类电池因其高能量密度、高循环性能已占据了目前电池市场的主导地位。高纯度的一氯代碳酸乙烯酯用于大功率锂离子电池的电解液中，能够有效的改善电池的循环性能，大幅度的延长电池的寿命。此外，由一氯代碳酸乙烯酯制备的碳酸亚乙烯酯是目前效果最理想的锂离子电池的有机成膜添加剂。Lithium-ion battery is a green new energy developed in the 1990s. This type of battery has occupied a dominant position in the current battery market due to its high energy density and high cycle performance. High-purity monochloroethylene carbonate is used in the electrolyte of high-power lithium-ion batteries, which can effectively improve the cycle performance of the battery and greatly extend the life of the battery. In addition, vinylene carbonate prepared from monochloroethylene carbonate is currently the most effective organic film-forming additive for lithium-ion batteries.
目前报道的一氯代碳酸乙烯酯的合成方法主要有两种：一是以碳酸乙烯酯为原料，四氯化碳为溶剂，氯气为氯化剂在弱紫外光作用下生成目标产物一氯代碳酸乙烯酯[《化学试剂》，“碳酸亚乙烯酯合成方法的改进”，苑克国等，2006，701]；二是碳酸乙烯酯与磺酰氯、亚硫酰氯或者光气等氯代物在引发剂的作用下生成目标产物[《石油化工》，“碳酸亚乙烯酯的合成”，孙浩等，2005，977]。The synthetic method of monochloroethylene carbonate reported at present mainly contains two kinds: the one is to be raw material with ethylene carbonate, carbon tetrachloride is solvent, and chlorine is chlorination agent and generates target product monochloride under the action of weak ultraviolet light. Ethylene carbonate ["Chemical Reagents", "Improvement of Vinylene Carbonate Synthesis Method", Yuan Keguo et al., 2006, 701]; the second is that ethylene carbonate and chlorinated substances such as sulfonyl chloride, thionyl chloride or phosgene are triggered The target product is generated under the action of the agent ["Petrochemical Industry", "Synthesis of Vinylene Carbonate", Sun Hao et al., 2005, 977].
上述方法二中采用磺酰氯、亚硫酰氯或者光气等氯代物作为氯化剂，其一氯碳酸乙烯酯的收率仅为70%左右，产率过低。上述方法一中，报道的文献和专利多数是以四氯化碳为反应溶剂。四氯化碳是一种强挥发性的溶剂，遇火或者炽热物会分解出氯化氢、光气和氯气等剧毒气体，人体长期反复接触四氯化碳会出现多处组织功能异常，严重者甚至发展为门脉性肝硬化。目前四氯化碳已经逐步从工业上和试验室中被淘汰。针对四氯化碳的毒性问题比亚迪先雪峰等人利用四氯乙烯取代了四氯化碳[CN1958554A]。但实验表明在光照条件下氯气先于碳酸乙烯酯和四氯乙烯反应，其主要产物为固态的六氯乙烷，因此四氯乙烯不适合用作光氯代反应的溶剂。In the above method two, chlorinated compounds such as sulfuryl chloride, thionyl chloride or phosgene are used as chlorination agents, and the yield of chloroethylene carbonate is only about 70%, which is too low. In the above-mentioned method one, the document and the patent majority of report are with carbon tetrachloride as reaction solvent. Carbon tetrachloride is a highly volatile solvent. It will decompose highly toxic gases such as hydrogen chloride, phosgene and chlorine in case of fire or hot objects. The human body will experience abnormal tissue function in many places after repeated exposure to carbon tetrachloride for a long time. Even develop into portal cirrhosis. At present, carbon tetrachloride has been gradually phased out from industry and laboratories. Aiming at the toxicity problem of carbon tetrachloride, BYD Xianxuefeng and others replaced carbon tetrachloride with tetrachloroethylene [CN1958554A]. However, experiments have shown that chlorine reacts before ethylene carbonate and tetrachloroethylene under light conditions, and its main product is solid hexachloroethane, so tetrachloroethylene is not suitable for use as a solvent for photochlorination reactions.
综上所述，开发一种低毒、高效、工艺简单、适合工业化生产的一氯碳酸乙烯酯的合成方法是本领域迫切需要解决的问题。In summary, it is an urgent problem to be solved in this field to develop a low-toxicity, high-efficiency, simple process and suitable synthetic method for industrialized production of chloroethylene carbonate.
发明内容Contents of the invention
本发明的目的之一是针对上述问题，利用一种内浸上行鼓泡式光化学反应器（如图1所示），从而提供一种剔除剧毒反应溶剂、抑制光化学反应副产物、提高目标产物的产率、实现快速高效且适合大规模工业化生产的光化学合成一氯代碳酸乙烯酯的方法。One of the purposes of the present invention is to address the above problems, using an internal immersion upward bubbling photochemical reactor (as shown in Figure 1), thereby providing a method for removing highly toxic reaction solvents, suppressing photochemical reaction by-products, and improving the target product. The method for photochemically synthesizing monochloroethylene carbonate fast and efficient and suitable for large-scale industrial production.
本发明的目的之二是提供一种适用于目的一方法的一种内浸上行鼓泡式光化学反应器。The second object of the present invention is to provide an internal immersion upward bubbling photochemical reactor suitable for the first method.
本发明的光化学合成一氯代碳酸乙烯酯的方法中，用碳酸乙烯酯合成碳酸亚乙烯酯的关键步骤是光化学合成一氯代碳酸乙烯酯，其合成路线如式（I）所示的碳酸乙烯酯光氯代反应合成碳酸亚乙烯酯。In the method for photochemically synthesizing monochloroethylene carbonate of the present invention, the key step of synthesizing vinylene carbonate with ethylene carbonate is photochemically synthesizing monochloroethylene carbonate, and its synthetic route is as shown in formula (I) ethylene carbonate Photochlorination of esters to synthesize vinylene carbonate.
式（I）Formula (I)
从（式I）可看出碳酸乙烯酯的过度光照，会生成众多副产物。碳酸乙烯酯与氯气光照反应首先生成一氯代碳酸乙烯酯，一氯代碳酸乙烯酯在光照条件下继续与氯气反应生成二氯代产物，继而生成三氯代产物。动力学研究表明，生成一氯代碳酸乙烯酯的产率控制在73%~90%为宜。It can be seen from (Formula I) that the excessive light of ethylene carbonate will generate many by-products. The photoreaction of ethylene carbonate with chlorine gas first generates monochloroethylene carbonate, and monochloroethylene carbonate continues to react with chlorine gas under light conditions to generate dichlorinated products, and then trichlorinated products. Kinetic studies show that the yield of chloroethylene carbonate is preferably controlled at 73%~90%.
本发明的光化学合成一氯代碳酸乙烯酯的方法中采用了一种内浸上行鼓泡式光化学反应器，其光化学合成一氯代碳酸乙烯酯的方法为：直接将原料碳酸乙烯酯加热溶化，使液态的碳酸乙烯酯由所述的内浸上行鼓泡式光化学反应器的反应液的入口泵入所述的内浸上行鼓泡式光化学反应器中的内浸式光反应器中，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氯气（氯气的流量控制在3g～8g/min之间）和惰性气体（如氮气）进行鼓泡，调节惰性气体（如氮气）的流量使鼓泡均匀；开启浸入在所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中的夹套式的沉阱中的高压汞灯进行光化学氯代反应，控制液态的碳酸乙烯酯反应液的温度在37～50℃之间，连续进行光照，并控制光照反应使原料碳酸乙烯酯光氯代反应的转化率在90～95%之间，得到含有一氯代碳酸乙烯酯的反应液；此时一氯代碳酸乙烯酯的收率最优，为73%～90%。In the method for photochemically synthesizing monochloroethylene carbonate of the present invention, a kind of inner immersion upward bubbling photochemical reactor is adopted, and the method for photochemically synthesizing monochloroethylene carbonate is: directly raw material ethylene carbonate is heated and melted, Liquid ethylene carbonate is pumped from the entrance of the reaction solution of the internal immersion upward bubbling photochemical reactor into the internal immersion photoreactor in the internal immersion upward bubbling photochemical reactor. Inlet chlorine gas (the flow rate of chlorine gas is controlled between 3g and 8g/min) and inert gas (such as nitrogen) into the liquid ethylene carbonate in the inner immersion photoreactor for bubbling, Adjust the flow of inert gas (such as nitrogen) to make the bubbling uniform; turn on the high-pressure mercury lamp immersed in the jacketed trap in the liquid ethylene carbonate in the internal immersion photoreactor to carry out Photochemical chlorination reaction, control the temperature of the liquid ethylene carbonate reaction solution between 37 and 50°C, continuously illuminate, and control the light reaction so that the conversion rate of the raw material ethylene carbonate photochlorination reaction is between 90 and 95%. , to obtain a reaction solution containing chloroethylene carbonate; at this time, the yield of chloroethylene carbonate is optimal, which is 73% to 90%.
所述的光照的时间优选为30～80分钟。The time of the light irradiation is preferably 30-80 minutes.
本发明提供的光化学合成一氯代碳酸乙烯酯的方法中还包括对光照后的含有一氯代碳酸乙烯酯的反应液进行分离提纯。其分离提纯的方案是：将光照后的含有一氯代碳酸乙烯酯的反应液全部转移至储罐中（光照后的含有一氯代碳酸乙烯酯的反应液中存在极少量的原料碳酸乙烯酯（沸点243-244℃，740mm汞柱）、少量的副产物二氯代碳酸乙烯酯（65℃，3mm汞柱）和目标产物一氯代碳酸乙烯酯（90℃，3mm汞柱）），按照化合物的沸点相差较大，可以用蒸馏的方式进行分离提纯，提纯后的一氯代碳酸乙烯酯的纯度大于98.5%。The method for photochemically synthesizing monochloroethylene carbonate provided by the present invention also includes separating and purifying the reaction solution containing monochloroethylene carbonate after irradiation. The scheme for its separation and purification is: transfer all the reaction solution containing chloroethylene carbonate after light to the storage tank (there is a very small amount of raw material ethylene carbonate in the reaction solution containing chloroethylene carbonate after light). (boiling point 243-244°C, 740mmHg), a small amount of by-product dichloroethylene carbonate (65°C, 3mmHg) and target product monochloroethylene carbonate (90°C, 3mmHg)), according to The boiling points of the compounds are quite different, so they can be separated and purified by distillation, and the purity of the purified monochloroethylene carbonate is greater than 98.5%.
本发明使用高压汞灯作为内浸上行鼓泡式光化学反应器的光源，利用内浸、上行鼓泡的方式替代传统外置光源。所述的高压汞灯是500瓦或1千瓦的高压汞灯。The invention uses a high-pressure mercury lamp as the light source of the internal immersion upward bubbling photochemical reactor, and uses the internal immersion and upward bubbling mode to replace the traditional external light source. The high-pressure mercury lamp is a 500W or 1KW high-pressure mercury lamp.
为了能够更好的实现本发明的光化学合成一氯代碳酸乙烯酯的方法，本发明还提供了一种如图1所示的内浸上行鼓泡式光化学反应器。In order to better realize the method for photochemically synthesizing monochloroethylene carbonate of the present invention, the present invention also provides an internal immersion upward bubbling photochemical reactor as shown in FIG. 1 .
所述的内浸上行鼓泡式光化学反应器的结构是在内浸式的光反应器（由高硼硅玻璃制成）中设置有一个夹套式的沉阱，在所述的夹套式的沉阱中安装有高压汞灯(500瓦或1千瓦的高压汞灯)，所述的夹套设置有冷却水的进出口（夹套内可通冷却水），所述的沉阱兼有冷却所述的高压汞灯散发的热量和滤光两个作用。在所述的内浸式光反应器的下部连通一带有气液混合阀的管道，在所述的气液混合阀上方的所述的管道上设置有气体（如惰性气体（如氮气），氯气）进口，在所述的气液混合阀下方的所述的管道上设置有反应液的入口；在所述的内浸式光反应器的上方设置有反应液的出口，该反应液的出口可通过管路与储罐相连通。The structure of the internal immersion upward bubbling photochemical reactor is that a jacketed sinker is arranged in the internal immersion photoreactor (made of high borosilicate glass), and in the jacketed A high-pressure mercury lamp (500 watt or 1 kW high-pressure mercury lamp) is installed in the sinker, and the jacket is provided with a cooling water inlet and outlet (cooling water can pass through the jacket), and the sinker has both It has two functions of cooling the heat emitted by the high-pressure mercury lamp and filtering light. A pipeline with a gas-liquid mixing valve is connected to the lower part of the in-immersion photoreactor, and gas (such as inert gas (such as nitrogen), chlorine gas, etc.) is arranged on the pipeline above the gas-liquid mixing valve. ) inlet, the inlet of the reaction liquid is arranged on the pipeline below the gas-liquid mixing valve; Connected to the storage tank through the pipeline.
所述的内浸式光反应器中装载有反应液，沉阱直接浸入内浸式光反应器中的反应液中。The in-immersion photoreactor is loaded with reaction solution, and the sinker is directly immersed in the reaction solution in the in-immersion photoreactor.
在所述的内浸上行鼓泡式光化学反应器中，反应液可接受波长长于300nm的光进行氯代反应（如式（I）所示）生成一氯代碳酸乙烯酯。所述的内浸上行鼓泡式光化学反应器的沉阱能透过波长长于300nm的光，由可滤除波长短于300nm的光的玻璃制成。In the internal immersion upward bubbling photochemical reactor, the reaction solution can accept light with a wavelength longer than 300nm for chlorination reaction (as shown in formula (I)) to generate monochloroethylene carbonate. The sinker of the internal immersion upward bubbling photochemical reactor can transmit light with a wavelength longer than 300nm, and is made of glass that can filter out light with a wavelength shorter than 300nm.
本发明利用内浸上行鼓泡式光化学反应器，在惰性气体的保护下，特别是剔除了传统的剧毒性的反应溶剂，使原料碳酸乙烯酯与氯气直接接触反应，反应不需要反应溶剂。所述的反应采取内浸式的光照方式，利用上行、鼓泡的方法来完成反应。用本发明提供的方法制备一氯代碳酸乙烯酯的收率高达90%，产物易于分离提纯，纯度达到98.5%以上。本发明的方法由于不涉及传统使用的剧毒性的溶剂，反应速度快，安全系数高，对设备要求低，非常有利于大规模的工业化生产。The invention utilizes an internal immersion upward bubbling photochemical reactor, under the protection of an inert gas, especially eliminates the traditional highly toxic reaction solvent, and makes the raw material ethylene carbonate and chlorine directly contact and react without a reaction solvent. The described reaction adopts the method of immersion illumination, and utilizes the method of ascending and bubbling to complete the reaction. The yield of monochloroethylene carbonate prepared by the method provided by the invention is as high as 90%, the product is easy to separate and purify, and the purity reaches more than 98.5%. Since the method of the invention does not involve traditionally used highly toxic solvents, the reaction speed is fast, the safety factor is high, and the requirement for equipment is low, which is very beneficial to large-scale industrial production.
附图说明Description of drawings
图1.本发明的内浸上行鼓泡式光化学反应器的结构示意图。Fig. 1. Schematic diagram of the structure of the internal immersion upward bubbling photochemical reactor of the present invention.
附图标记reference sign
1.内浸式光反应器 2.夹套式的沉阱 3.高压汞灯 4.气液混合阀1. Immersion photoreactor 2. Jacketed sinker 3. High pressure mercury lamp 4. Gas-liquid mixing valve
5.气体进口 6.反应液的入口 7.反应液的出口5. Gas inlet 6. Reaction liquid inlet 7. Reaction liquid outlet
具体实施方式Detailed ways
实施例1Example 1
请参见图1所示的内浸上行鼓泡式光化学反应器，在一由高硼硅玻璃制成的内浸式光反应器1中设置有一个由可滤除波长短于300nm的光的玻璃制成的夹套式的沉阱2，在所述的夹套式的沉阱中安装有500瓦或1千瓦的高压汞灯3，所述的夹套设置有冷却水的进出口；在所述的内浸式光反应器的下部连通一带有气液混合阀4的管道，在所述的气液混合阀上方的所述的管道上设置有气体进口5，在所述的气液混合阀下方的所述的管道上设置有反应液的入口6；在所述的内浸式光反应器的上方设置有反应液的出口7。Please refer to the inner immersion upward bubbling photochemical reactor shown in Fig. 1, in an inner immersion photoreactor 1 made of high borosilicate glass, a glass with a wavelength shorter than 300nm is arranged. The jacketed sinker 2 of making, the high-pressure mercury lamp 3 of 500 watts or 1 kilowatt is installed in the jacketed sinker of described jacket, and described jacket is provided with the import and export of cooling water; The bottom part of the immersion photoreactor communicates with a pipeline with a gas-liquid mixing valve 4, and a gas inlet 5 is arranged on the pipeline above the gas-liquid mixing valve. The inlet 6 of the reaction liquid is arranged on the lower pipe; the outlet 7 of the reaction liquid is arranged above the immersed photoreactor.
采用上述的内浸上行鼓泡式光化学反应器进行光化学合成一氯代碳酸乙烯酯。The photochemical synthesis of monochloroethylene carbonate is carried out by using the above-mentioned internal immersion upward bubbling photochemical reactor.
直接将176g的固态碳酸乙烯酯加热溶化，使液态的碳酸乙烯酯由所述的内浸上行鼓泡式光化学反应器的反应液的入口泵入所述的内浸上行鼓泡式光化学反应器中的内浸式光反应器中，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氮气，然后开启氯气阀门，以4g/min的流量，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氯气，调整氮气的流量使鼓泡均匀；开启浸入在所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中的夹套式的沉阱中的500瓦的高压汞灯进行光化学氯代反应，控制液态的碳酸乙烯酯反应液的温度在37℃，连续进行光照50分钟后，停止通入氯气，关闭高压汞灯，得到含有一氯代碳酸乙烯酯的反应液249g，碳酸乙烯酯的转化率为91.5%。The solid ethylene carbonate of 176g is directly heated and melted, and the liquid ethylene carbonate is pumped into the described inner immersion upward bubbling photochemical reactor from the inlet of the reaction solution of the inner immersion upward bubbling photochemical reactor In the in-immersion photoreactor, feed nitrogen into the described liquid ethylene carbonate in the in-in-immersion photoreactor from the gas inlet, then open the chlorine valve, with the flow rate of 4g/min, by The gas inlet feeds chlorine gas into the liquid ethylene carbonate in the immersion photoreactor, adjusts the flow of nitrogen to make the bubbling uniform; The 500-watt high-pressure mercury lamp in the jacketed sinker in the liquid ethylene carbonate carries out the photochemical chlorination reaction, and the temperature of the liquid ethylene carbonate reaction solution is controlled at 37° C., and after 50 minutes of continuous illumination , stop feeding chlorine gas, turn off the high-pressure mercury lamp, obtain 249g of reaction solution containing chloroethylene carbonate, and the transformation rate of ethylene carbonate is 91.5%.
将上述含有一氯代碳酸乙烯酯的光反应液249g转至500mL的单口烧瓶中进行减压蒸馏，真空度为3mm汞柱，收集86-92℃馏分232g。将所得232g馏分进行二次蒸馏，真空度3mm汞柱，收集90-91℃馏分223g。一氯碳酸乙烯酯的收率为90%，GC纯度为99.4%。Transfer 249 g of the photoreaction solution containing monochloroethylene carbonate to a 500 mL single-necked flask for vacuum distillation with a vacuum of 3 mm Hg, and collect 232 g of fractions at 86-92°C. The obtained 232g fraction was subjected to secondary distillation, and the vacuum degree was 3mm Hg, and 223g of 90-91°C fraction was collected. The yield of chloroethylene carbonate was 90%, and the GC purity was 99.4%.
所得产物一氯代碳酸乙烯酯用色谱进行检测和表征，一氯代碳酸乙烯酯的色谱纯度为99.4%。色谱仪的型号为岛津GC2014。色谱的测试参数为：The obtained product monochloroethylene carbonate is detected and characterized by chromatography, and the chromatographic purity of monochloroethylene carbonate is 99.4%. The model of the chromatograph is Shimadzu GC2014. The test parameters of the chromatography are:
毛细管柱：HP-5MSCapillary column: HP-5MS
升温程序：初始温度70℃，维持1分钟，然后以10℃/min的速度升至200℃，维持2分钟Heating program: the initial temperature is 70°C, maintained for 1 minute, then raised to 200°C at a speed of 10°C/min, maintained for 2 minutes
载气：氮气Carrier gas: nitrogen
气化室温度：210℃Gasification chamber temperature: 210°C
检测器温度：210℃Detector temperature: 210°C
进样量：0.2μLInjection volume: 0.2μL
分流比：30:1Split ratio: 30:1
实施例2Example 2
采用实施例1的内浸上行鼓泡式光化学反应器进行光化学合成一氯代碳酸乙烯酯。The photochemical synthesis of monochloroethylene carbonate was carried out using the internal immersion upward bubbling photochemical reactor of Example 1.
直接将176g的固态碳酸乙烯酯加热溶化，使液态的碳酸乙烯酯由所述的内浸上行鼓泡式光化学反应器的反应液的入口泵入所述的内浸上行鼓泡式光化学反应器中的内浸式光反应器中，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氮气，然后开启氯气阀门，以3g/min的流量，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氯气，调整氮气的流量使鼓泡均匀；开启浸入在所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中的夹套式的沉阱中的500瓦的高压汞灯进行光化学氯代反应，控制液态的碳酸乙烯酯反应液的温度在50℃，连续进行光照80分钟后，停止通入氯气，关闭高压汞灯，得到含有一氯代碳酸乙烯酯的反应液263g，碳酸乙烯酯的转化率为95%。The solid ethylene carbonate of 176g is directly heated and melted, and the liquid ethylene carbonate is pumped into the described inner immersion upward bubbling photochemical reactor from the inlet of the reaction solution of the inner immersion upward bubbling photochemical reactor In the in-immersion photoreactor, feed nitrogen into the described liquid ethylene carbonate in the in-in-immersion photoreactor from the gas inlet, then open the chlorine valve, with the flow rate of 3g/min, by The gas inlet feeds chlorine gas into the liquid ethylene carbonate in the immersion photoreactor, adjusts the flow of nitrogen to make the bubbling uniform; The 500-watt high-pressure mercury lamp in the jacketed sinker in the liquid ethylene carbonate carries out photochemical chlorination reaction, and the temperature of the liquid ethylene carbonate reaction solution is controlled at 50° C., and after 80 minutes of continuous illumination , stop feeding chlorine, turn off the high-pressure mercury lamp, obtain the reaction solution 263g that contains monochloroethylene carbonate, and the transformation rate of ethylene carbonate is 95%.
将上述含有一氯代碳酸乙烯酯的光反应液263g转至500mL的单口烧瓶中进行减压蒸馏，真空度为3mm汞柱，收集86-92℃馏分184g。将所得184g馏分进行二次蒸馏，真空度3mm汞柱，收集90-91℃馏分179g。一氯碳酸乙烯酯的收率为73%，GC纯度为98.8%。Transfer 263 g of the photoreaction solution containing monochloroethylene carbonate to a 500 mL single-necked flask for vacuum distillation at a vacuum of 3 mm Hg, and collect 184 g of fractions at 86-92°C. The resulting 184g fraction was subjected to secondary distillation with a vacuum of 3mm Hg, and 179g of fractions at 90-91°C were collected. The yield of ethylene monochlorocarbonate was 73%, and the GC purity was 98.8%.
所得产物一氯代碳酸乙烯酯用色谱进行检测和表征，一氯代碳酸乙烯酯的色谱纯度为98.8%。色谱仪的型号为岛津GC2014。色谱的测试参数同实施例1。The obtained product monochloroethylene carbonate is detected and characterized by chromatography, and the chromatographic purity of monochloroethylene carbonate is 98.8%. The model of the chromatograph is Shimadzu GC2014. The test parameters of the chromatogram are the same as in Example 1.
实施例3Example 3
采用实施例1的内浸上行鼓泡式光化学反应器进行光化学合成一氯代碳酸乙烯酯。The photochemical synthesis of monochloroethylene carbonate was carried out using the internal immersion upward bubbling photochemical reactor of Example 1.
直接将176g的固态碳酸乙烯酯加热溶化，使液态的碳酸乙烯酯由所述的内浸上行鼓泡式光化学反应器的反应液的入口泵入所述的内浸上行鼓泡式光化学反应器中的内浸式光反应器中，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氮气，然后开启氯气阀门，以4g/min的流量，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氯气，调整氮气的流量使鼓泡均匀；开启浸入在所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中的夹套式的沉阱中的500瓦的高压汞灯进行光化学氯代反应，控制液态的碳酸乙烯酯反应液的温度在40℃，连续进行光照40分钟后，停止通入氯气，关闭高压汞灯，得到含有一氯代碳酸乙烯酯的反应液236g，碳酸乙烯酯的转化率为90%。The solid ethylene carbonate of 176g is directly heated and melted, and the liquid ethylene carbonate is pumped into the described inner immersion upward bubbling photochemical reactor from the inlet of the reaction solution of the inner immersion upward bubbling photochemical reactor In the in-immersion photoreactor, feed nitrogen into the described liquid ethylene carbonate in the in-in-immersion photoreactor from the gas inlet, then open the chlorine valve, with the flow rate of 4g/min, by The gas inlet feeds chlorine gas into the liquid ethylene carbonate in the immersion photoreactor, adjusts the flow of nitrogen to make the bubbling uniform; The 500-watt high-pressure mercury lamp in the jacketed sinker in the liquid ethylene carbonate carries out photochemical chlorination reaction, and the temperature of the liquid ethylene carbonate reaction solution is controlled at 40° C., and after 40 minutes of continuous illumination , stop feeding chlorine, turn off the high-pressure mercury lamp, obtain the reaction solution 236g that contains monochloroethylene carbonate, and the transformation rate of ethylene carbonate is 90%.
将上述含有一氯代碳酸乙烯酯的光反应液236g转至500mL的单口烧瓶中进行减压蒸馏，真空度为3mm汞柱，收集86-92℃馏分212g。将所得212g馏分进行二次蒸馏，真空度3mm汞柱，收集90-91℃馏分208g。一氯碳酸乙烯酯的收率为85%，GC纯度为99.0%。Transfer 236 g of the photoreaction solution containing monochloroethylene carbonate to a 500 mL single-necked flask for vacuum distillation at a vacuum of 3 mm Hg, and collect 212 g of fractions at 86-92°C. The obtained 212g fraction was subjected to secondary distillation, the vacuum degree was 3mm Hg, and 208g of 90-91°C fraction was collected. The yield of chloroethylene carbonate was 85%, and the GC purity was 99.0%.
所得产物一氯代碳酸乙烯酯用色谱进行检测和表征，一氯代碳酸乙烯酯的色谱纯度为99.0%。色谱仪的型号为岛津GC2014。色谱的测试参数同实施例1。The obtained product monochloroethylene carbonate is detected and characterized by chromatography, and the chromatographic purity of monochloroethylene carbonate is 99.0%. The model of the chromatograph is Shimadzu GC2014. The test parameters of the chromatogram are the same as in Example 1.
实施例4Example 4
采用实施例1的内浸上行鼓泡式光化学反应器进行光化学合成一氯代碳酸乙烯酯。The photochemical synthesis of monochloroethylene carbonate was carried out using the internal immersion upward bubbling photochemical reactor of Example 1.
直接将176g的固态碳酸乙烯酯加热溶化，使液态的碳酸乙烯酯由所述的内浸上行鼓泡式光化学反应器的反应液的入口泵入所述的内浸上行鼓泡式光化学反应器中的内浸式光反应器中，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氮气，然后开启氯气阀门，以8g/min的流量，由气体进口向所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中通入氯气，调整氮气的流量使鼓泡均匀；开启浸入在所述的内浸式光反应器中的所述的液态的碳酸乙烯酯中的夹套式的沉阱中的1000瓦的高压汞灯进行光化学氯代反应，控制液态的碳酸乙烯酯反应液的温度在45℃，连续进行光照30分钟后，停止通入氯气，关闭高压汞灯，得到含有一氯代碳酸乙烯酯的反应液253g，碳酸乙烯酯的转化率为92.6%。The solid ethylene carbonate of 176g is directly heated and melted, and the liquid ethylene carbonate is pumped into the described inner immersion upward bubbling photochemical reactor from the inlet of the reaction solution of the inner immersion upward bubbling photochemical reactor In the in-immersion photoreactor, feed nitrogen into the described liquid ethylene carbonate in the in-in-immersion photoreactor from the gas inlet, then open the chlorine valve, with the flow rate of 8g/min, by The gas inlet feeds chlorine gas into the liquid ethylene carbonate in the immersion photoreactor, adjusts the flow of nitrogen to make the bubbling uniform; The 1000-watt high-pressure mercury lamp in the jacketed sinker in the liquid ethylene carbonate carries out the photochemical chlorination reaction, and the temperature of the liquid ethylene carbonate reaction solution is controlled at 45°C, and after 30 minutes of continuous illumination , stop feeding chlorine, turn off the high-pressure mercury lamp, obtain the reaction solution 253g that contains monochloroethylene carbonate, and the transformation rate of ethylene carbonate is 92.6%.
将上述含有一氯代碳酸乙烯酯的光反应液253g转至500mL的单口烧瓶中进行减压蒸馏，真空度为3mm汞柱，收集86-92℃馏分218g。将所得218g馏分进行二次蒸馏，真空度3mm汞柱，收集90-91℃馏分215g。一氯碳酸乙烯酯的收率为87%，GC纯度为98.5%。Transfer 253 g of the photoreaction solution containing monochloroethylene carbonate to a 500 mL single-necked flask for vacuum distillation at a vacuum of 3 mm Hg, and collect 218 g of fractions at 86-92°C. The obtained 218g fraction was subjected to secondary distillation, the vacuum degree was 3mm Hg, and 215g of 90-91°C fraction was collected. The yield of chloroethylene carbonate was 87%, and the GC purity was 98.5%.
所得产物一氯代碳酸乙烯酯用色谱进行检测和表征，一氯代碳酸乙烯酯的色谱纯度为98.5%。色谱仪的型号为岛津GC2014。色谱的测试参数同实施例1。The obtained product monochloroethylene carbonate is detected and characterized by chromatography, and the chromatographic purity of monochloroethylene carbonate is 98.5%. The model of the chromatograph is Shimadzu GC2014. The test parameters of the chromatogram are the same as in Example 1.
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| CN105859677B (en) * | 2016-04-20 | 2018-05-18 | 唐山汉伯化工有限公司 | A kind of preparation method of monochloroethylene carbonate |
| CN106632227A (en) * | 2016-12-08 | 2017-05-10 | 江苏理文化工有限公司 | Method for preparing chloroethylene carbonate |
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| CN114192078A (en) * | 2021-11-26 | 2022-03-18 | 江苏理文化工有限公司 | Bubbling reaction device and method for continuously producing chlorinated ethylene carbonate |
| CN115286612A (en) * | 2022-07-27 | 2022-11-04 | 珠海正杏新材料科技有限公司 | A kind of production method of chloroethylene carbonate |
| CN115043813A (en) * | 2022-08-02 | 2022-09-13 | 中楚鑫新材料科技(荆州)有限公司 | High-conversion-rate preparation method of chloroethylene carbonate |
| CN116370993A (en) * | 2023-02-21 | 2023-07-04 | 山东孚日新能源材料有限公司 | Purification method of chloroethylene carbonate |
| CN116715651A (en) * | 2023-06-16 | 2023-09-08 | 四川鸿鹏新材料有限公司 | Halogen-containing ester additive, preparation method thereof and lithium battery electrolyte containing halogen-containing ester additive |
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