WO2022052222A1 - 一种草酸酯加氢制备乙醇酸酯的反应系统及方法 - Google Patents

一种草酸酯加氢制备乙醇酸酯的反应系统及方法 Download PDF

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WO2022052222A1
WO2022052222A1 PCT/CN2020/122812 CN2020122812W WO2022052222A1 WO 2022052222 A1 WO2022052222 A1 WO 2022052222A1 CN 2020122812 W CN2020122812 W CN 2020122812W WO 2022052222 A1 WO2022052222 A1 WO 2022052222A1
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micro
hydrogenation
reaction
hydrogen
oxalate
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PCT/CN2020/122812
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English (en)
French (fr)
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张志炳
周政
刘甲
张锋
李磊
孟为民
王宝荣
杨高东
罗华勋
杨国强
田洪舟
曹宇
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南京延长反应技术研究院有限公司
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Publication of WO2022052222A1 publication Critical patent/WO2022052222A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form

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  • the invention relates to the field of glycolate preparation, in particular to a reaction system and method for preparing glycolate by hydrogenation of oxalate.
  • Glycolic acid ester is an important chemical product, which is widely used in many fields such as chemical industry, medicine, pesticide, feed, dye and fragrance. Such as improved solvents for fibers, resins and rubber; hydrogenation to produce ethylene glycol, carbonylation to produce malonate, aminolysis to produce glycine, hydrolysis to produce glycolic acid, etc.
  • foreign technologies mainly use the formaldehyde carbonylation route to prepare glycolate, but the formaldehyde carbonylation technology requires high pressure conditions, and it will bring huge corrosion, high equipment requirements, large investment, and difficult industrial production.
  • the first object of the present invention is to provide a reaction system for preparing glycolic acid ester by hydrogenating oxalate.
  • the reaction system is configured with a micro-interface unit inside the hydrogenation reactor, so that hydrogen and dimethyl oxalate are subjected to hydrogenation reaction Before breaking the hydrogen into microbubbles, the mass transfer area of the phase boundary between the hydrogen and dimethyl oxalate was increased, thereby solving the problem of the reaction pressure caused by the fact that the hydrogen and the dimethyl oxalate could not be fully mixed in the reactor in the prior art. High, high hydrogen ester ratio, low liquid hourly space velocity.
  • the second object of the present invention is to provide a reaction method for preparing glycolic acid ester by using a reaction system, the glycolic acid ester obtained by the reaction has high purity, is widely used, improves the applicability of glycolic acid ester itself, and is worthy of widespread application.
  • the invention provides a reaction system for preparing glycolate by hydrogenating oxalate, comprising a hydrogenation reactor and a hydrogen feed pipeline;
  • the side wall of the hydrogenation reactor is provided with an oxalate feed pipeline, and a micro-interface unit is arranged in the hydrogenation reactor, and the micro-interface unit is formed by a plurality of micro-interface generators arranged in sequence from top to bottom ;
  • the hydrogen feed pipeline enters the inside of the micro-interface unit through the side wall of the hydrogenation reactor, so as to realize that the hydrogen is broken into micro-level micro-bubbles in the micro-interface unit in advance before the hydrogenation reaction ;
  • the reaction product after the hydrogenation reaction in the hydrogenation reactor enters a light removal tower to remove light components, and then enters a rectification tower for rectification to obtain glycolic acid ester.
  • the glycolic ester reaction system of the present invention is provided with a micro-interface unit inside the hydrogenation reactor, so that the hydrogen entering the reactor can be dispersed and broken into micro-bubbles, thereby improving the mass transfer effect.
  • the oxalate introduced into the interface unit is mainly to cooperate with the dispersion and crushing of the gas, which is equivalent to the role of the medium.
  • the micro-interface unit includes three micro-interface generators, and a set of liquid reciprocal channels are arranged between adjacent micro-interface generators, and the liquid reciprocal channels realize gas-liquid circulation in the micro-interface generators .
  • the hydrogen feed pipeline is connected with a gas source external channel to provide a gas source for hydrogen to enter the micro-interface unit.
  • the oxalate feed pipeline is connected with an oxalate storage tank to provide a raw material source for the oxalate entering the hydrogenation reactor.
  • the micro-interface unit of the present invention is arranged inside the hydrogenation reactor and arranged in sequence from top to bottom.
  • the oxalate enters the hydrogenation reactor from the oxalate storage tank through the oxalate feed pipeline. After entering, it can be in close contact with the incoming hydrogen as a medium, so as to ensure that the hydrogen can be fully dispersed and broken in the micro-interface unit, and it is equivalent to forming a micro-interface system in each micro-interface generator to achieve
  • the gas phase is fully dispersed and broken inside the micro-interface generator under the premise of using the liquid phase as the medium.
  • the micro-interface generator at the bottom is the closest to the gas-phase feed port, so it is used as the main dispersed and broken micro-interface system.
  • the two micro-interface generators formed by the two micro-interface generators form a secondary micro-interface system and a tertiary micro-interface system, which also has the effect of strengthening the hydrogenation reaction.
  • the present invention also sets liquid reciprocal channels between adjacent micro-interface generators.
  • there are two liquid reciprocal channels which are arranged symmetrically on the left and right, because the mutual circulation of liquid between the micro-interface generators , which can improve the fragmentation of the gas phase, because the fragmentation requires power.
  • the liquid reciprocal channels also provide power correspondingly. The best way is to use two liquids.
  • the liquid phase flow directions of the reciprocal channels are just opposite, so that convection can also be generated between the various micro-interface generators to improve the crushing effect.
  • the micro-interface generator in the hydrogenation reactor breaks the hydrogen into micro-sized micro-bubbles, and releases the micro-bubbles into the reactor to increase the amount of hydrogen and oxalic acid during the hydrogenation reaction.
  • the mass transfer area of the phase boundary between the dimethyl esters makes the hydrogen fully contact with the dimethyl oxalate in the state of microbubbles, and the hydrogenation reaction is carried out.
  • micro-interface generator used in the present invention has been embodied in the inventor's prior patents, such as application numbers CN201610641119. Patents of CN205833127U and CN207581700U. In the previous patent CN201610641119.6, the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator) were introduced in detail.
  • the body is provided with an inlet communicating with the cavity, the opposite first and second ends of the cavity are open, wherein the cross-sectional area of the cavity is from the middle of the cavity to the first and second ends of the cavity.
  • the second end is reduced; the secondary crushing piece is arranged at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is arranged in the cavity, and both ends of the secondary crushing piece and the cavity are open An annular channel is formed between the through holes of the micro-bubble generator.
  • the micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe.” From the specific structure disclosed in the application document, we can know that its specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe.
  • the micro-bubble generator in this patent belongs to the pneumatic micro-interface generation. device.
  • the previous patent 201610641251.7 records that the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed port with the gas-liquid mixture outlet, indicating that the bubble breaker is both It needs to be mixed with gas and liquid.
  • the primary bubble breaker mainly uses circulating liquid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is a gas-liquid breaker. The mixture is simultaneously fed into the elliptical rotating ball for rotation, so that the bubbles are broken during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage type micro-interface generator.
  • both hydraulic micro-interface generators and gas-liquid linkage micro-interface generators belong to a specific form of micro-interface generators.
  • the micro-interface generators used in the present invention are not limited to the above-mentioned forms.
  • the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can take.
  • the previous patent 201710766435.0 recorded that "the principle of the bubble breaker is to achieve high-speed jets to achieve gas collision", and also stated that it can be used in micro-interface enhanced reactors to verify the relationship between the bubble breaker and the micro-interface generator.
  • the top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet.
  • the liquid phase entering from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the accompanying drawings.
  • the bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.
  • micro-interface generator Since the micro-interface generator was just developed in the early stage of the previous patent application, it was named as micro-bubble generator (CN201610641119.6), bubble breaker (201710766435.0), etc., and later changed its name to micro-interface generator with continuous technological improvement.
  • the micro-interface generator in the present invention is equivalent to the previous micro-bubble generator, bubble breaker, etc., but the names are different.
  • the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some belong to the type of hydraulic bubble breakers, and some belong to the type of gas bubble breakers.
  • the type of liquid-linked bubble breaker but the difference between the types is mainly selected according to the specific working conditions.
  • the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and connection position depends on the micro-interface generator. It depends on the structure of the interface generator, which is not limited.
  • the top of the light-removing tower is provided with a light component outlet for discharging the light components of methanol, methyl formate, ethylene glycol and dimethyl carbonate
  • the bottom of the light-removing tower is provided with a reorganization A branch outlet, the heavy component outlet communicates with the side wall of the rectification column for further rectification of glycolate.
  • a raw material circulation outlet is provided at the bottom of the rectification column, and the oxalate is returned to the hydrogenation reactor from the raw material circulation outlet to realize the recycling of the raw material.
  • an overhead condenser is provided on the top of the rectification column, and a part of the substances condensed from the column overhead condenser is returned to the rectification column, and the other part goes to the glycol ester storage tank.
  • the reaction product that has been reacted in the hydrogenation reactor is transported to the inside of the light-removing tower, and the light components such as methanol, methyl formate, ethylene glycol and dimethyl carbonate are distilled from the top of the column, and the obtained heavy components are transported to the follow-up. in the distillation column.
  • the rectification tower performs rectification treatment on the heavy components in the light removal tower, and the dimethyl oxalate left at the bottom of the rectification tower is recycled to the interior of the hydrogenation reactor, and used again for the dimethyl oxalate in the hydrogenation reactor.
  • the hydrogenation reaction a part of the substances passing through the top condenser at the top of the rectification column are returned to the rectification column, and a part of the glycolic acid ester distilled is transported to the glycolic acid ester storage tank.
  • the present invention also provides a reaction method for preparing glycolic acid ester by hydrogenation of oxalate, comprising the following steps:
  • the mixed micro-interface of oxalate and hydrogen is dispersed and broken, and then hydrogenated, and then dehydrogenated and rectified to obtain glycolic acid ester for collection.
  • the temperature of the hydrogenation reaction is 200-300° C.
  • the pressure of the carboxylation reaction is 0.1-2 MPa.
  • a micro-interface generator connected to the hydrogen feed pipeline is arranged inside the hydrogenation reactor, so that before the hydrogen and dimethyl oxalate undergo hydrogenation reaction, the micro-interface generator breaks the hydrogen into a diameter of Micro-bubbles greater than or equal to 1 ⁇ m and less than 1 mm make hydrogen contact with dimethyl oxalate in the state of micro-bubbles, so as to increase the phase boundary mass transfer area between hydrogen and dimethyl oxalate during the hydrogenation reaction, and carry out sufficient
  • the hydrogenation reaction is carried out after mixing, thereby solving the problems of high reaction pressure, large hydrogen ester ratio and low liquid hourly space velocity because hydrogen and dimethyl oxalate cannot be fully mixed in the reactor in the prior art.
  • the glycolate product obtained by the reaction method of the present invention has good quality and high yield.
  • the preparation method itself has low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, which is equivalent to increasing the production capacity.
  • the reaction system for preparing glycolate by hydrogenation of oxalate of the present invention is by arranging a micro-interface unit inside the hydrogenation reactor, so that hydrogen is broken into microbubbles before hydrogen and dimethyl oxalate carry out hydrogenation reaction, Improve the phase boundary mass transfer area between hydrogen and dimethyl oxalate, thereby solving the problem that in the prior art, hydrogen and dimethyl oxalate cannot be fully mixed inside the reactor, resulting in high reaction pressure, large hydrogen-to-ester ratio, and high liquid-to-liquid ratio.
  • the reaction method of the present invention is easy to operate, the glycolate obtained by the reaction has high purity, and is widely used, which improves the applicability of the glycolate itself, and is worthy of widespread application.
  • FIG. 1 is a schematic structural diagram of a reaction system for preparing glycolate from oxalate according to an embodiment of the present invention.
  • the terms “installed”, “connected” and “connected” should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • installed should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • FIG. 1 it is a reaction system for preparing glycolate by hydrogenation of oxalate according to the embodiment of the present invention, which mainly includes a hydrogenation reactor 13 and a hydrogen feed pipeline, and 1kg of hydrogenation catalyst is pre-filled into the hydrogenation catalyst.
  • an oxalate feed pipeline is also arranged on the side wall of the hydrogenation reactor 13 and a micro-interface unit is arranged in the hydrogenation reactor 13, and the micro-interface unit is composed of a plurality of micro-interface generators 131.
  • the micro-interface generators 131 are preferably three micro-interface generators 131 arranged in sequence from top to bottom, and a set of liquid reciprocal channels 132 are arranged between adjacent micro-interface generators 131, and the liquid reciprocal channels 132 realize the micro-interface generators 131.
  • the hydrogen feed pipeline is connected with a gas source external channel 12 to provide a gas source for the entry of hydrogen into the micro-interface unit, and the oxalate feed pipeline is connected with an oxalate storage tank 11 to achieve a gas source entering the hydrogenation reactor 13.
  • Oxalate provides a source of raw materials, 50kg of dimethyl oxalate is pre-filled into the oxalate storage tank 11, and is transported to the interior of the hydrogenation reactor 13 through the first delivery pump 17, and the external channel 12 of the gas source is connected with enough hydrogen gas.
  • the source is connected, the system is started, the temperature of the hydrogenation reactor 13 is set to 200 ° C, the pressure is set to 1.0 MPa, and the dimethyl oxalate is transported to the interior of the hydrogenation reactor 13, and at the same time, the hydrogen is transported to the hydrogenation reactor 13 through the hydrogen feed pipeline.
  • the pressure is set to 1.0 MPa
  • the dimethyl oxalate is transported to the interior of the hydrogenation reactor 13, and at the same time, the hydrogen is transported to the hydrogenation reactor 13 through the hydrogen feed pipeline.
  • the micro-interface generator 131 breaks the hydrogen into micro-bubbles with a micron scale, and releases the micro-bubbles into the interior of the reactor, so that the hydrogen is fully contacted with dimethyl oxalate in the state of micro-bubbles, and the dimethyl oxalate is in the hydrogenation process. Under the catalysis of the catalyst, it reacts with hydrogen to generate glycolate, and at the same time, it also generates by-products such as methanol, methyl formate, ethylene glycol and dimethyl carbonate.
  • the hydrogenated reaction product is transported to the light removal tower 14 to remove the light components, the light components and the heavy components are separated and processed, and the light components such as methanol and methyl formate are distilled from the light component outlet 141 at the top of the tower.
  • the heavy components such as dimethyl oxalate and glycolate remain at the bottom of the column, and the heavy components are transported to the rectifying column 15 from the heavy component outlet 142, and the dimethyl oxalate is left at the bottom of the rectifying column 15, from the setting
  • the raw material circulation outlet 152 at the bottom of the rectifying column 15 goes out, and is transported back to the hydrogenation reactor 13 by the second delivery pump 18 to realize re-circulation.
  • the top condenser 151 is refluxed, and the other part is directly extracted and sent to the glycol ester storage tank 16 for storage.
  • the micro-interface generator 131 converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the bubbles and transfers them to the bubbles, so that the bubbles are broken into micron-level micrometers with a diameter greater than or equal to 1 ⁇ m and less than 1 mm.
  • Bubble according to the energy input method or gas-liquid ratio, is divided into pneumatic micro-interface generator 131, hydraulic micro-interface generator 131 and gas-liquid linkage micro-interface generator 131, wherein the pneumatic micro-interface generator 131 is driven by gas, and the input gas volume is much larger than that of liquid.
  • the hydraulic micro-interface generator 131 is driven by liquid, and the input gas volume is generally less than the liquid volume; the gas-liquid linkage micro-interface generator 131 is driven by gas and liquid simultaneously, and the input gas volume is close to the liquid volume.
  • the micro-interface generator 131 is selected from one or more of the pneumatic micro-interface generator 131 , the hydraulic micro-interface generator 131 and the gas-liquid linkage type micro-interface generator 131 .
  • micro-interface generators 131 can also be added.
  • the installation position is not limited. It can be installed externally or built-in. When built-in, it can also be installed on the side wall of the kettle. , so as to realize the hedging of the micro-bubbles coming out of the outlet of the micro-interface generator 131 .
  • the reaction system of the present invention has fewer equipment components, small footprint, low energy consumption, low cost, high safety and controllable reaction. , the raw material conversion rate is high, which is equivalent to providing a reaction system with stronger operability in the field of glycolate preparation, which is worthy of widespread application.

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Abstract

提供了一种草酸酯加氢制备乙醇酸酯的反应系统及方法，所述反应系统包括：加氢反应器，氢气进料管道；加氢反应器的侧壁设置有草酸酯进料管道，加氢反应器内设置有微界面机组，微界面机组由多个微界面发生器从上至下依次排列形成；氢气进料管道穿过加氢反应器的侧壁进入到所述微界面机组内部，以实现在加氢反应之前氢气预先在所述微界面机组内部破碎成微米级别的微气泡；从加氢反应器加氢反应后的反应产物进入脱轻塔脱除轻组分，再进入精馏塔精馏处理后，得到乙醇酸酯。反应系统通过在加氢反应器内部设置微界面机组，使得在氢气与草酸二甲酯进行加氢反应之前将氢气破碎为微气泡，提高氢气与草酸二甲酯之间的相界传质面积。

Description

一种草酸酯加氢制备乙醇酸酯的反应系统及方法 技术领域
本发明涉及乙醇酸酯制备领域，具体而言，涉及一种草酸酯加氢制备乙醇酸酯的反应系统及方法。
背景技术
乙醇酸酯是一种重要的化工产品，广泛应用于化工、医药、农药、饲料、染料和香料等诸多领域。如纤维、树脂和橡胶的改良溶剂；加氢制备乙二醇，羰化制丙二酸酯，氨解制甘氨酸，水解制乙醇酸等。目前国外技术主要采用甲醛羰化路线来制备乙醇酸酯，但甲醛羰化技术要求在高压条件下进行，且会带来巨大腐蚀，对设备要求高，投入大，工业化生产困难。而国内则是沿用氯乙酸和苛性钠溶液混合反应再酯化的工艺路线，但该法以乙酸为原料，氯法生产，腐蚀严重，污染大，成本高，也不能大规模生产。
因此，亟需改进乙酸乙酯的生产工艺路线。通过草酸酯加氢制备乙醇酸酯，进而开发下游产品，形成良好的产业链，是目前化工企业十分看好的前景。草酸酯加氢制备乙醇酸酯的反应是放热反应，随着反应的进行催化剂床层温度会随之升高，而过高的局部温升必然加速催化剂的失活，影响催化剂性能。
此外，在加氢反应过程中，氢气和草酸二甲酯无法得到充分的混合，从而导致反应需要在较高氢酯比(氢酯比＞30:1)和高氢气压力(＞2.0MPa)下进行，限制了反应器的生产能力(液时空速＜1.0h -1)。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种草酸酯加氢制备乙醇酸酯的反应系统，该反应系统通过在加氢反应器内部设置微界面机组，使得在氢气与草酸二甲酯进行加氢反应之前将氢气破碎为微气泡，提高氢气与草酸二甲酯之间的相界传质面积，从而解决了现有技术中由于氢气和草酸二甲酯在反应器内部无法得到充分混合，导致反应压力高、氢酯比大、液时空速低的问题。
本发明的第二目的在于提供一种采用反应系统制备乙醇酸酯的反应方法，反应得到的乙醇酸酯纯度高，应用广泛，提高了乙醇酸酯本身的适用面，值得广泛推广应用。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种草酸酯加氢制备乙醇酸酯的反应系统，包括加氢反应器，氢气进料管道；
所述加氢反应器的侧壁设置有草酸酯进料管道，所述加氢反应器内设置有微界面机组，所述微界面机组由多个微界面发生器从上至下依次排列形成；所述氢气进料管道穿过所述加氢反应器的侧壁进入到所述微界面机组内部，以实现在加氢反应之前氢气预先在所述微界面机组内部破碎成微米级别的微气泡；
从所述加氢反应器加氢反应后的反应产物进入脱轻塔脱除轻组分，再进入精馏塔精馏处理后，得到乙醇酸酯。
本发明的乙醇酸酯的反应系统，通过在加氢反应器的内部设置有微界面机组，从而实现了将进入反应器内的氢气进行分散破碎成微气泡，从而提高传质效果，此外在微界面机组内部通入的草酸酯主要是为了配合气体的分散破碎，相当于介质的作用。
优选地，所述微界面机组包括3个微界面发生器，相邻所述微界面发生器之间设置有一组液体互逆通道，所述液体互逆通道实现微界面发生器内气液的流通。
优选地，所述氢气进料管道连接有气源外接通道以实现为氢气进入到微界 面机组提供气源。
优选地，所述草酸酯进料管道连接有草酸酯存储罐以实现为进入到加氢反应器内的草酸酯提供原料来源。
本发明的微界面机组设置在了加氢反应器的内部，按照从上至下依次排布的方式设置，草酸酯从草酸酯存储罐通过草酸酯进料管道进入到加氢反应器的内部，进入之后作为介质与进入的氢气能够发生密切的接触，从而保证了氢气能够在微界面机组中充分分散破碎，且相当于在每个微界面发生器均形成一次微界面体系，以实现气相在以液相为介质的前提下在微界面发生器内部得到充分的分散破碎，最底部的微界面发生器离气相进料口最为接近，所以其作为主要分散破碎的微界面体系，然后上部的两个微界面发生器形成二次微界面体系以及三次微界面体系，也起到加强加氢反应的效果。
此外，本发明在相邻的微界面发生器之间还设置了液体互逆通道，液体互逆通道最好为两条，左右对称设置，因为在各个微界面发生器之间通过液体的互相流通，从而更能够提高气相的破碎，因为破碎是需要动力的，除了微界面发生器内部的微孔结构提供动力以外，液体互逆通道也相应的配合提供了动力，最好的方式是两个液体互逆通道的液相流向是正好相反的，从而在各个微界面发生器之间也能产生对流，提高破碎的效果。
所述加氢反应器中的微界面发生器将氢气打碎成微米尺度的微气泡，并将微气泡释放到所述反应器内部，以增大加氢反应过程中所述氢气与所述草酸二甲酯之间的相界传质面积，使得氢气以微气泡的状态与草酸二甲酯充分接触，并进行加氢反应。
本领域所属技术人员可以理解的是，本发明所采用的微界面发生器在本发明人在先专利中已有体现，如申请号CN201610641119.6、201610641251.7、CN201710766435.0、CN106187660、CN105903425A、CN109437390A、CN205833127U及CN207581700U的专利。在先专利CN201610641119.6中详细介绍了微米气泡发生器(即微界面发生器)的具体产品结构和工作原理，该 申请文件中记载了“微米气泡发生器包括本体和二次破碎件、本体内具有空腔，本体上设有与空腔连通的进口，空腔的相对的第一端和第二端均敞开，其中空腔的横截面积从空腔的中部向空腔的第一端和第二端减小；二次破碎件设在空腔的第一端和第二端中的至少一个处，二次破碎件的一部分设在空腔内，二次破碎件与空腔两端敞开的通孔之间形成一个环形通道。微米气泡发生器还包括进气管和进液管。”从该申请文件中公开的具体结构可以知晓其具体工作原理为：液体通过进液管切向进入微米气泡发生器内，超高速旋转并切割气体，使气体气泡破碎成微米级别的微气泡，从而提高液相与气相之间的传质面积，而且该专利中的微米气泡发生器属于气动式微界面发生器。
另外，在先专利201610641251.7中有记载一次气泡破碎器具有循环液进口、循环气进口和气液混合物出口，二次气泡破碎器则是将进料口与气液混合物出口连通，说明气泡破碎器都是需要气液混合进入，另外从后面的附图中可知，一次气泡破碎器主要是利用循环液作为动力，所以其实一次气泡破碎器属于液动式微界面发生器，二次气泡破碎器是将气液混合物同时通入到椭圆形的旋转球中进行旋转，从而在旋转的过程中实现气泡破碎，所以二次气泡破碎器实际上是属于气液联动式微界面发生器。其实，无论是液动式微界面发生器，还是气液联动式微界面发生器，都属于微界面发生器的一种具体形式，然而本发明所采用的微界面发生器并不局限于上述几种形式，在先专利中所记载的气泡破碎器的具体结构只是本发明微界面发生器可采用的其中一种形式而已。此外，在先专利201710766435.0中记载到“气泡破碎器的原理就是高速射流以达到气体相互碰撞”，并且也阐述了其可以用于微界面强化反应器，验证本身气泡破碎器与微界面发生器之间的关联性；而且在先专利CN106187660中对于气泡破碎器的具体结构也有相关的记载，具体见说明书中第[0031]-[0041]段，以及附图部分，其对气泡破碎器S-2的具体工作原理有详细的阐述，气泡破碎器顶部是液相进口，侧面是气相进口，通过从顶部进来的液相提供卷吸动力，从而达到粉碎成超细气泡的效果，附图中也可见气泡破碎器呈锥形的结构， 上部的直径比下部的直径要大，也是为了液相能够更好的提供卷吸动力。由于在先专利申请的初期，微界面发生器才刚研发出来，所以早期命名为微米气泡发生器(CN201610641119.6)、气泡破碎器(201710766435.0)等，随着不断技术改进，后期更名为微界面发生器，现在本发明中的微界面发生器相当于之前的微米气泡发生器、气泡破碎器等，只是名称不一样。
综上所述，本发明的微界面发生器属于现有技术，虽然有的气泡破碎器属于气动式气泡破碎器类型，有的气泡破碎器属于液动式气泡破碎器类型，还有的属于气液联动式气泡破碎器类型，但是类型之间的差别主要是根据具体工况的不同进行选择，另外关于微界面发生器与反应器、以及其他设备的连接，包括连接结构、连接位置，根据微界面发生器的结构而定，此不作限定。
优选地，所述脱轻塔的顶部设置有轻组分出口，以用于甲醇、甲酸甲酯、乙二醇和碳酸二甲酯的轻组分的排出，所述脱轻塔的底部设置有重组分出口，所述重组分出口与所述精馏塔的侧壁相通以用于将乙醇酸酯进行进一步的精馏。
优选地，所述精馏塔的底部设置有原料循环出口，所述草酸酯从所述原料循环出口返回到所述加氢反应器以实现的原料的循环利用。
优选地，所述精馏塔的顶部设置有塔顶冷凝器，从所述塔顶冷凝器冷凝下来的物质一部分返回到所述精馏塔，另外一部分去往乙醇酸酯存储罐。
将加氢反应器内部反应完毕的反应产物输送至脱轻塔内部，甲醇、甲酸甲酯、乙二醇和碳酸二甲酯等轻组分从塔顶馏出，将得到的重组分输送至后续的精馏塔中。
精馏塔对脱轻塔中的重组分进行精馏处理，将留在精馏塔底部的草酸二甲酯循环至加氢反应器的内部，再次用于加氢反应器内的草酸二甲酯加氢反应，将精馏塔顶部经过塔顶冷凝器的物质，一部分返回到所述精馏塔，一部分馏出的乙醇酸酯输送至乙醇酸酯存储罐。
本发明还提供了一种草酸酯加氢制备乙醇酸酯的反应方法，包括如下步 骤：
将草酸酯与氢气混合微界面分散破碎后进行加氢反应，再经过脱氢、精馏得到乙醇酸酯进行收集。
优选地，加氢反应的温度200-300℃，所述羧化反应的压力为0.1-2MPa。
具体地，该制备方法通过在加氢反应器内部设置与氢气进料管道连接的微界面发生器，使得在氢气与草酸二甲酯进行加氢反应之前，微界面发生器将氢气破碎成直径为大于等于1μm、小于1mm的微气泡，使得氢气以微气泡的状态与草酸二甲酯接触，以增大加氢反应过程中氢气与草酸二甲酯之间的相界传质面积，并进行充分混合再进行加氢反应，从而解决了现有技术中由于氢气和草酸二甲酯在反应器内部无法得到充分混合，导致反应压力高、氢酯比大、液时空速低的问题。
采用本发明的反应方法得到的乙醇酸酯产品品质好、收率高。且该制备方法本身反应温度低、压力大幅度下降，液时空速高，相当于提高了产能。
与现有技术相比，本发明的有益效果在于：
(1)本发明的草酸酯加氢制备乙醇酸酯的反应系统通过在加氢反应器内部设置微界面机组，使得在氢气与草酸二甲酯进行加氢反应之前将氢气破碎为微气泡，提高氢气与草酸二甲酯之间的相界传质面积，从而解决了现有技术中由于氢气和草酸二甲酯在反应器内部无法得到充分混合，导致反应压力高、氢酯比大、液时空速低的问题；
(2)本发明的反应方法操作简便，反应得到的乙醇酸酯纯度高，应用广泛，提高了乙醇酸酯本身的适用面，值得广泛推广应用。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并 不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例提供的草酸酯制备乙醇酸酯的反应系统结构示意图。
附图说明：
11-草酸酯存储罐；               12-气源外接通道；
13-加氢反应器；                 131-微界面发生器；
132-液体互逆通道；              14-脱轻塔；
141-轻组分出口；                142-重组分出口；
15-精馏塔；                     151-塔顶冷凝器；
152-原料循环出口；              16-乙醇酸酯存储罐；
17-第一输送泵；                 18-第二输送泵。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，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，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为 对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
为了更加清晰的对本发明中的技术方案进行阐述，下面以具体实施例的形式进行说明。
实施例
参阅图1所示，为本发明实施例的草酸酯加氢制备乙醇酸酯的反应系统，其主要包括加氢反应器13以及氢气进料管道，将1kg的加氢催化剂预先填入到加氢反应器13中，在加氢反应器13的侧壁上还设置有草酸酯进料管道，在加氢反应器13内设置有微界面机组，微界面机组由多个微界面发生器131从上至下依次排列形成，优选地为3个微界面发生器131，且相邻的微界面发生器131之间设置有一组液体互逆通道132，液体互逆通道132实现微界面发生器131内气液的流通。这样一来，氢气进料管道穿过所述加氢反应器13的侧壁进入到所述微界面机组内部，以实现在加氢反应之前氢气预先在所述微界面机组内部破碎成微米级别的微气泡。
氢气进料管道连接有气源外接通道12以实现为氢气进入到微界面机组提供气源，草酸酯进料管道连接有草酸酯存储罐11以实现为进入到加氢反应器13内的草酸酯提供原料来源，将50kg的草酸二甲酯预先填入草酸酯存储罐11内部，通过第一输送泵17输送到加氢反应器13内部，气源外接通道12与足够的氢气气源连接，启动系统，加氢反应器13的温度设置为200℃，压力设置 为1.0MPa，将草酸二甲酯输送至加氢反应器13的内部，同时，将氢气通过氢气进料管道输送至微界面机组的每个微界面发生器131内部。
微界面发生器131将氢气打碎成微米级尺度的微气泡，并将微气泡释放到反应器的内部，使得氢气以微气泡的状态与草酸二甲酯充分接触，草酸二甲酯在加氢催化剂的催化下与氢气反应生成乙醇酸酯，同时，也生成甲醇、甲酸甲酯、乙二醇和碳酸二甲酯等副产物。
将加氢完的反应产物输送至脱轻塔14脱除轻组分，对轻组分与重组分进行分离处理，甲醇、甲酸甲酯等轻组分从塔顶的轻组分出口141馏出，草酸二甲酯和乙醇酸酯等重组分留在塔底，并将重组分从重组分出口142出去输送至精馏塔15，草酸二甲酯留在精馏塔15的塔底，从设置在精馏塔15底部的原料循环出口152出去，通过第二输送泵18输送回加氢反应器13中以实现重新的循环利用，乙醇酸酯从精馏塔15的塔顶馏出，一部分经过塔顶冷凝器151回流，另一部分则直接采出去往乙醇酸酯存储罐16进行存储。
在上述实施例中，微界面发生器131通过将气体的压力能和/或液体的动能转变为气泡表面能并传递给气泡，使气泡破碎成直径为大于等于1μm、小于1mm的微米级别的微气泡，根据能量输入方式或气液比分为气动式微界面发生器131、液动式微界面发生器131和气液联动式微界面发生器131，其中气动式微界面发生器131采用气体驱动，输入气量远大于液体量；液动式微界面发生器131采用液体驱动，输入气量一般小于液体量；气液联动式微界面发生器131采用气液同时驱动，输入气量接近于液体量。微界面发生器131选用气动式微界面发生器131、液动式微界面发生器131以及气液联动式微界面发生器131中的一种或几种。
为了增加分散、传质效果，也可以多增设额外的微界面发生器131，安装位置其实也是不限的，可以外置也可以内置，内置时还可以采用安装在釜内的侧壁上相对设置，以实现从微界面发生器131的出口出来的微气泡发生对冲。
在上述实施例中，泵体的个数并没有具体要求，可根据需要在相应的位置 设置。
在上述实施例中，其他操作条件不变，当加氢反应温度设置为220℃，压力设置为0.5MPa。
在上述实施例中，其他操作条件不变，当加氢反应温度设置为260℃，压力设置为1MPa。
在上述实施例中，其他操作条件不变，当加氢反应温度设置为300℃，压力设置为0.1MPa。
总之，与现有技术的草酸酯加氢制备乙醇酸酯的反应系统相比，本发明的反应系统设备组件少、占地面积小、能耗低、成本低、安全性高、反应可控，原料转化率高，相当于为乙醇酸酯制备领域提供了一种操作性更强的反应系统，值得广泛推广应用。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (9)

  1. 一种草酸酯加氢制备乙醇酸酯的反应系统，其特征在于，包括：加氢反应器，氢气进料管道；
    所述加氢反应器的侧壁设置有草酸酯进料管道，所述加氢反应器内设置有微界面机组，所述微界面机组由多个微界面发生器从上至下依次排列形成；所述氢气进料管道穿过所述加氢反应器的侧壁进入到所述微界面机组内部，以实现在加氢反应之前氢气预先在所述微界面机组内部破碎成微米级别的微气泡；
    从所述加氢反应器加氢反应后的反应产物进入脱轻塔脱除轻组分，再进入精馏塔精馏处理后，得到乙醇酸酯。
  2. 根据权利要求1所述的反应系统，其特征在于，所述微界面机组包括3个微界面发生器，相邻所述微界面发生器之间设置有一组液体互逆通道，所述液体互逆通道实现微界面发生器内气液的流通。
  3. 根据权利要求1所述的反应系统，其特征在于，所述氢气进料管道连接有气源外接通道以实现为氢气进入到微界面机组提供气源。
  4. 根据权利要求1所述的反应系统，其特征在于，所述草酸酯进料管道连接有草酸酯存储罐以实现为进入到加氢反应器内的草酸酯提供原料来源。
  5. 根据权利要求1-4任一项所述的反应系统，其特征在于，所述脱轻塔的顶部设置有轻组分出口，以用于甲醇、甲酸甲酯、乙二醇和碳酸二甲酯的轻组分的排出，所述脱轻塔的底部设置有重组分出口，所述重组分出口与所述精馏塔的侧壁相通以用于将乙醇酸酯进行进一步的精馏。
  6. 根据权利要求1-4任一项所述的反应系统，其特征在于，所述精馏塔的底部设置有原料循环出口，所述草酸酯从所述原料循环出口返回到所述加氢反应器以实现的原料的循环利用。
  7. 根据权利要求1-4任一项所述的反应系统，其特征在于，所述精馏塔的顶部设置有塔顶冷凝器，从所述塔顶冷凝器冷凝下来的物质一部分返回到所述精馏塔，另外一部分去往乙醇酸酯存储罐。
  8. 采用权利要求1-7任一项所述的草酸酯加氢制备乙醇酸酯的反应系统的反应方法，其特征在于，包括如下步骤：
    将草酸酯与氢气混合微界面分散破碎后进行加氢反应，再经过脱氢、精馏得到乙醇酸酯进行收集。
  9. 根据权利要求8所述的反应方法，其特征在于，所述加氢反应的温度200-300℃，所述羧化反应的压力为0.1-2MPa。
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