CN110698333A - Method for continuously synthesizing o-phthalaldehyde by using microchannel reaction device - Google Patents

Method for continuously synthesizing o-phthalaldehyde by using microchannel reaction device Download PDF

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CN110698333A
CN110698333A CN201911057986.5A CN201911057986A CN110698333A CN 110698333 A CN110698333 A CN 110698333A CN 201911057986 A CN201911057986 A CN 201911057986A CN 110698333 A CN110698333 A CN 110698333A
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phthalaldehyde
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唐璇
王诗雨
成西涛
薛姗
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Xian Shiyou University
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Abstract

本发明公开了一种微通道反应器连续合成邻苯二甲醛的方法,以1,3-二氢异苯并呋喃及硝酸为原料,采用微通道反应装置进行邻苯二甲醛连续合成,产物经萃取、蒸馏及干燥等工艺步骤得到邻苯二甲醛产品。与现有技术相比,本发明的工艺反应充分利用了微通道反应器对传热及传质的强化及可实现精确控制的特点,克服了现有间歇反应器生产邻苯二甲醛存在的反应时间长、不能连续生产、安全性能低,且反应中需加入大量的酸性抑制剂、污染较大等问题,可实现连续生产和工艺的自控,生产高效安全,并且反应条件温和、反应时间短、产品纯度高、收率高,能耗小、绿色经济,有利于邻苯二甲醛在化工及医疗等行业的推广使用。

Figure 201911057986

The invention discloses a method for continuously synthesizing o-phthalaldehyde in a micro-channel reactor. Using 1,3-dihydroisobenzofuran and nitric acid as raw materials, a micro-channel reaction device is used to continuously synthesize o-phthalaldehyde. Process steps such as extraction, distillation and drying to obtain ortho-phthalaldehyde product. Compared with the prior art, the process reaction of the present invention makes full use of the characteristics of the micro-channel reactor to strengthen heat transfer and mass transfer and can realize precise control, and overcomes the existing reaction of the existing batch reactor to produce o-phthalaldehyde. It takes a long time, cannot be continuously produced, has low safety performance, and needs to add a large amount of acid inhibitors in the reaction, causing large pollution and other problems. It can realize continuous production and automatic control of the process, and the production is efficient and safe. The product has high purity, high yield, low energy consumption and green economy, which is conducive to the promotion and use of ortho-phthalaldehyde in chemical and medical industries.

Figure 201911057986

Description

一种微通道反应装置连续合成邻苯二甲醛的方法A kind of method for continuously synthesizing ortho-phthalaldehyde by microchannel reaction device

技术领域technical field

本发明内容属于化学合成工艺技术领域,涉及一种微通道反应装置连续合成邻苯二甲醛的方法。The content of the invention belongs to the technical field of chemical synthesis technology, and relates to a method for continuously synthesizing o-phthalaldehyde in a microchannel reaction device.

背景技术Background technique

邻苯二甲醛(O-phthalaldehyde OPA)作为重要的医药化工中间体,以往被广泛应用于胺类生物碱、荧光计组胺测定及医药检验方面,经研究者长期对其消毒性能的多方面研究,现已将其开发为新一代高效的医用消毒剂。与传统戊二醛消毒剂相比,邻苯二甲醛具有用时较短、杀菌性能优异等特点,可广泛应用于医药及医疗器械的消毒。O-phthalaldehyde (OPA), as an important pharmaceutical and chemical intermediate, has been widely used in amine alkaloids, fluorometer histamine determination and medical inspection in the past. , which has now been developed into a new generation of efficient medical disinfectants. Compared with traditional glutaraldehyde disinfectants, phthalaldehyde has the characteristics of shorter duration and excellent bactericidal performance, and can be widely used in the disinfection of medicine and medical equipment.

目前本领域有关邻苯二甲醛的合成路线的报道较多,主要有:邻二甲苯溴化水解法、邻二甲苯氯化水解法、硝酸直接氧化法、萘臭氧化加氢法及高温氧化法等。其中:邻二甲苯溴化水解法由于需用溴作原料,成本较高;邻二甲苯氯化水解法由于氯代反应在结构上易受到空间阻碍,单程收率较低,并且损耗较大;硝酸直接氧化法由于反应放热剧烈,氧化深度难以控制,导致反应的转化率不高(低于70%),兼之反应中需加入大量乙酸作为有机酸生成的抑制剂,不仅造成浪费,同时酸气污染较为严重;萘臭氧化加氢法存在着反应以贵金属作为催化剂,反应后产品不易分离且工艺条件难以控制,产品纯度较低,催化剂不方便回收利用,反应的设备投资过高等问题,要实现工业化生产比较困难;而高温氧化法的反应条件较为苛刻,且操作不便,不易控制,产品选择性差。There are many reports about the synthetic route of o-phthalaldehyde in this area at present, mainly including: o-xylene bromination hydrolysis method, o-xylene chlorinated hydrolysis method, nitric acid direct oxidation method, naphthalene ozonation hydrogenation method and high temperature oxidation method Wait. Wherein: the ortho-xylene brominated hydrolysis method needs to use bromine as the raw material, and the cost is higher; the ortho-xylene chlorinated hydrolysis method is easily sterically hindered due to the chlorination reaction in structure, the single-pass yield is low, and the loss is relatively large; The direct oxidation method of nitric acid is due to the severe exothermic reaction, and the depth of oxidation is difficult to control, resulting in a low conversion rate (less than 70%) of the reaction. In addition, a large amount of acetic acid needs to be added in the reaction as an inhibitor for organic acid generation, which not only causes waste, but also causes acid. The gas pollution is more serious; the ozonation and hydrogenation of naphthalene has problems such as the use of precious metals as catalysts in the reaction, the products after the reaction are not easy to separate and the process conditions are difficult to control, the product purity is low, the catalyst is inconvenient to recycle, and the investment in the reaction equipment is too high. It is difficult to realize industrialized production; while the reaction conditions of the high-temperature oxidation method are relatively harsh, and the operation is inconvenient, difficult to control, and the product selectivity is poor.

另外,现有的上述各合成方法均采用传统的反应釜(瓶)进行制备,相应都存在有选择性及收率低、成本较高、生产过程反应放热较为剧烈、工艺操作不易控制、不安全、设备及自控水平低、不能连续生产及生产操作繁琐等缺点,这些缺点也在很大程度上限制了邻苯二甲醛作为新一代高效消毒剂在诸多行业的推广使用。In addition, the existing above-mentioned synthetic methods all adopt traditional reaction kettles (bottles) to prepare, correspondingly all have low selectivity and yield, relatively high cost, relatively violent reaction exotherm in the production process, difficult control of technological operation, and inconvenience. The disadvantages of safety, low level of equipment and self-control, inability to continuous production, and cumbersome production operations also greatly limit the promotion and use of ortho-phthalaldehyde as a new generation of high-efficiency disinfectants in many industries.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于克服现有技术存在的不足,提供一种采用较为易得的1,3-二氢异苯并呋喃为起始原料的微通道反应装置连续合成邻苯二甲醛的方法,本发明所述的合成方法具有工艺具有反应条件温和、反应周期短、反应中不用加入有机酸抑制剂、后处理工艺简单、能耗小、可减少对环境的污染、转化率及产品纯度高等特点,有利于邻苯二甲醛在化工及医疗等行业的推广使用。The object of the present invention is to overcome the deficiencies existing in the prior art, and to provide a method for the continuous synthesis of o-phthalaldehyde in a microchannel reaction device that adopts relatively easy-to-obtain 1,3-dihydroisobenzofuran as starting material. The synthesis method of the invention has the characteristics of mild reaction conditions, short reaction period, no need to add organic acid inhibitors in the reaction, simple post-treatment process, low energy consumption, reduced environmental pollution, high conversion rate and product purity, etc. It is beneficial to the promotion and use of phthalaldehyde in chemical and medical industries.

为实现以上发明目的而采用的技术方案如下所述。The technical solutions adopted to achieve the above purpose of the invention are as follows.

一种微通道反应装置连续合成邻苯二甲醛的方法,包括下述的合成步骤:A method for the continuous synthesis of o-phthalaldehyde by a microchannel reaction device, comprising the following synthesis steps:

a、构建配置微通道反应装置,所述的微通道反应装置由导热油加热炉、两个油浴原料储罐、两个过滤器、两个柱塞式计量泵、微混合器、微通道反应器、恒温油浴槽、冷却槽、产物储槽、尾气吸收装置、氮气瓶组成,微混合器和微通道反应器设置于控温在30~80℃的恒温油浴槽内,导热油加热炉的热源输出端分别通过其上装有球阀的连接管路与第一油浴原料储罐及第二油浴原料储罐连接,第一油浴原料储罐的出口端经第一过滤器接至第一柱塞式计量泵的入口端,第二油浴原料储罐的出口端经第二过滤器接至第二柱塞式计量泵的入口端,第一柱塞式计量泵和第二柱塞式计量泵的出口端并联后进入恒温油浴槽再接至微混合器的入口端,微混合器的出口端经微通道反应器接至内充有自来水或盐水的冷却槽的入口端,冷却槽的出口端以及氮气瓶的出口端均通过一支其上装有球阀的管路进入产物储槽中,产物储槽的副产物尾气出口端通过其上装有球阀的管路接至尾气吸收装置内;a. Build and configure a microchannel reaction device, which consists of a heat-conducting oil heating furnace, two oil bath raw material storage tanks, two filters, two plunger metering pumps, a micromixer, and a microchannel reaction device. It consists of a thermostatic oil bath, a constant temperature oil bath, a cooling tank, a product storage tank, a tail gas absorption device, and a nitrogen bottle. The micro mixer and the micro channel reactor are set in a constant temperature oil bath with a temperature control of 30 to 80 ° C. The heat source of the heat transfer oil heating furnace The output ends are respectively connected with the first oil bath raw material storage tank and the second oil bath raw material storage tank through connecting pipelines with ball valves on them, and the outlet end of the first oil bath raw material storage tank is connected to the first column through the first filter The inlet end of the plunger metering pump, the outlet end of the second oil bath raw material storage tank is connected to the inlet end of the second plunger metering pump through the second filter, the first plunger metering pump and the second plunger metering The outlet end of the pump is connected in parallel and then enters the constant temperature oil bath and then connects to the inlet end of the micro mixer. The outlet end of the micro mixer is connected to the inlet end of the cooling tank filled with tap water or salt water through the micro channel reactor, and the outlet end of the cooling tank Both the end and the outlet end of the nitrogen cylinder enter the product storage tank through a pipeline equipped with a ball valve, and the by-product tail gas outlet end of the product storage tank is connected to the exhaust gas absorption device through a pipeline equipped with a ball valve;

b、将原料1,3-二氢异苯并呋喃及硝酸分别置入在两个油浴原料储罐中,通过导热油加热炉为原料预热至30~80℃;b. The raw materials 1,3-dihydroisobenzofuran and nitric acid are placed in two oil bath raw material storage tanks respectively, and the raw materials are preheated to 30-80 ℃ through a heat-conducting oil heating furnace;

c、将预热后的1,3-二氢异苯并呋喃及硝酸按照流量体积比1:0.5~4分别通过第一柱塞式计量泵和第二柱塞式计量泵进入微混合器中进行混合,进一步再通入微通道反应器内停留5~30min进行氧化反应合成邻苯二甲醛产物混合液,之后使其进至产物储槽中;c. Enter the preheated 1,3-dihydroisobenzofuran and nitric acid into the micro-mixer through the first plunger metering pump and the second plunger metering pump respectively according to the flow volume ratio of 1:0.5 to 4. Carry out mixing, further pass into the microchannel reactor and stay for 5-30min to carry out oxidation reaction to synthesize the o-phthalaldehyde product mixed solution, and then make it enter the product storage tank;

d、通过氮气瓶经氮气管路向产物储槽中以1~10mL/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置中,氮氧化物副产在pH值为1~3的硝酸催化下与浓度为5%~10%的尿素发生氧化还原反应,使其还原为氮气;向经氮气吹扫后的反应产物加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;d. Bubble nitrogen into the product storage tank at 1-10mL/min through a nitrogen bottle through a nitrogen pipeline, and purge the generated nitrogen oxide by-product into the tail gas absorption device. The nitrogen oxide by-product is at a pH value of 1- Under the catalysis of 3% nitric acid, a redox reaction occurs with urea with a concentration of 5% to 10% to reduce it to nitrogen; to the reaction product purged with nitrogen, add twice the volume of deionized water, stir for 30min, and cool to room temperature Then, stand to separate out the water phase, extract 3 times with equal volume of ethyl acetate, combine the extracts, and recover ethyl acetate by distillation to obtain o-phthalaldehyde;

e、将经蒸馏后的邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品。e. Place the distilled ortho-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50°C for 4 hours to obtain the ortho-phthalaldehyde product.

本发明进一步的技术解决方案还包括:步骤a中所述微通道反应器的管径为0.1~5mm。A further technical solution of the present invention further includes: the pipe diameter of the microchannel reactor in step a is 0.1-5 mm.

本发明进一步的技术解决方案还包括:步骤b中所述硝酸浓度为30%~98%,优选浓度为50%~69%;所述的原料预热温度优选为60~80℃。Further technical solutions of the present invention further include: the concentration of nitric acid in step b is 30%-98%, preferably 50%-69%; the raw material preheating temperature is preferably 60-80°C.

本发明进一步的技术解决方案还包括:步骤c中所述1,3-二氢异苯并呋喃与硝酸的流量体积比优选为1:1~2,混合液在微通道反应器内的优选停留时间为10~20min。Further technical solutions of the present invention also include: the flow volume ratio of 1,3-dihydroisobenzofuran and nitric acid described in step c is preferably 1:1 to 2, and the preferred residence time of the mixed solution in the microchannel reactor is The time is 10 to 20 minutes.

综上所述,本发明设计了以1,3-二氢异苯并呋喃(C8H8O)和硝酸为原料,采用微通道反应装置进行邻苯二甲醛连续合成的方法。与现有技术相比,本发明的工艺反应充分利用了微通道反应器对传热及传质的强化及可实现精确控制的特点,克服了现有间歇反应器生产邻苯二甲醛存在的反应时间长、不能连续生产、安全性能低,且反应中需加入大量的酸性抑制剂、污染较大等问题,可实现连续生产和工艺的自控,生产高效安全,并且反应条件温和、反应时间短、产品纯度高、收率高,能耗小、绿色经济,有利于邻苯二甲醛在化工及医疗等行业的推广使用。To sum up, the present invention designs a method for continuously synthesizing o-phthalaldehyde by using 1,3-dihydroisobenzofuran (C 8 H 8 O) and nitric acid as raw materials and using a microchannel reaction device. Compared with the prior art, the process reaction of the present invention makes full use of the characteristics of the micro-channel reactor to strengthen heat transfer and mass transfer and can realize precise control, and overcomes the existing reaction of the existing batch reactor to produce o-phthalaldehyde. It takes a long time, cannot be continuously produced, has low safety performance, and needs to add a large amount of acid inhibitors in the reaction, causing large pollution and other problems. It can realize continuous production and automatic control of the process, and the production is efficient and safe. The product has high purity, high yield, low energy consumption and green economy, which is conducive to the promotion and use of ortho-phthalaldehyde in chemical and medical industries.

附图说明Description of drawings

图1为本发明中所用微通道反应装置的结构示意图,亦为本发明的反应路线示意图。FIG. 1 is a schematic structural diagram of a microchannel reaction device used in the present invention, and is also a schematic diagram of a reaction route of the present invention.

图2是本发明一个实施例(实施例1)制备邻苯二甲醛的IR图。Figure 2 is an IR diagram of the preparation of ortho-phthalaldehyde in one embodiment of the present invention (Example 1).

图3是图2所示(实施例1)制备邻苯二甲醛的1HNMR图。Fig. 3 is a 1 HNMR chart of the preparation of ortho-phthalaldehyde shown in Fig. 2 (Example 1).

图4是图2所示(实施例1)制备的邻苯二甲醛的GC图。Fig. 4 is the GC chart of the ortho-phthalaldehyde prepared as shown in Fig. 2 (Example 1).

附图中各数字标号的名称分别是:1-第一油浴原料储罐,2-球阀,3-第一过滤器,4-第一柱塞式计量泵,5-第二油浴原料储罐,6-球阀,7-第二过滤器,8-第一柱塞式计量泵,9-导热油加热炉,10-球阀,11-第一高温油泵,12-球阀,13-恒温油浴槽,14-微混合器,15-微通道反应器,16-冷却槽,17-球阀,18-产物储槽,19-球阀,20-尾气吸收装置,21-球阀,22-氮气瓶,23-(恒温油浴槽用)导热油加热炉,24-球阀,25-球阀,26-第二高温油泵。The names of the numbers in the drawings are: 1- the first oil bath raw material storage tank, 2- ball valve, 3- the first filter, 4- the first plunger metering pump, 5- the second oil bath raw material storage tank Tank, 6-ball valve, 7-second filter, 8-first plunger metering pump, 9-heating oil heating furnace, 10-ball valve, 11-first high-temperature oil pump, 12-ball valve, 13-thermostatic oil bath , 14-micro mixer, 15-microchannel reactor, 16-cooling tank, 17-ball valve, 18-product storage tank, 19-ball valve, 20-exhaust gas absorption device, 21-ball valve, 22-nitrogen cylinder, 23- (For constant temperature oil bath) heat transfer oil heating furnace, 24-ball valve, 25-ball valve, 26-second high temperature oil pump.

具体实施方式Detailed ways

以下将结合附图对本发明内容做进一步说明。The content of the present invention will be further described below with reference to the accompanying drawings.

参见附图,本发明的合成工艺步骤如下所述。Referring to the accompanying drawings, the synthesis process steps of the present invention are as follows.

一、构建配置微通道反应装置,该微通道反应装置如图1所示,由通过相应管路连接的导热油加热炉9、第一油浴原料储罐1、第二油浴原料储罐5、第一过滤器3、第二过滤器7、第一柱塞式计量泵4、第二柱塞式计量泵8、微混合器14、微通道反应器15、恒温油浴槽13、冷却槽16、产物储槽18、尾气吸收装置20、氮气瓶22、第一高温油泵11、第二高温油泵26以及多个分装在各连接管路上的球阀(2、6、10、12、17、19、21、24、25)等组成。具体实施结构中,导热油加热炉9具有两路热源输出端,其一路热源输出端通过装有球阀12的连接管路与第一油浴原料储罐1连接,为第一油浴原料储罐1中的原料进行预热,另一路热源输出端通过装有球阀10和第一高温油泵的连接管路与第二油浴原料储罐5连接,为第二油浴原料储罐5中的原料预热;第一油浴原料储罐1的出口端通过装有球阀2的管路经第一过滤器3接至第一柱塞式计量泵4的入口端,第二油浴原料储罐5的出口端通过装有球阀6的管路经第二过滤器7接至第二柱塞式计量泵8的入口端,第一柱塞式计量泵4和第二柱塞式计量泵8的出口端并联后进入恒温油浴槽13中,再接至微混合器14的入口端,微混合器14的出口端再经微通道反应器15接至内充有自来水或盐水的冷却槽16的入口端,冷却槽16的出口端通过一支其上装有球阀17的管路进入产物储槽18中,产物储槽18的副产物尾气出口端通过其上装有球阀19的管路接至尾气吸收装置20内。此外氮气瓶22的出口端也通过一支其上装有球阀21的管路进入产物储槽18中,工作时通过氮气瓶22可向产物储槽18中以1~10mL/min鼓入氮气,氮氧化物副产在pH值为1~3的硝酸催化下与浓度为5%~10%的尿素发生氧化还原反应,使其还原为氮气。本发明中微通道反应器15的管径为0.1~5mm,微混合器14和微通道反应器15设置于恒温油浴槽13内,浸在导热油中,油温控制在30~80℃,图1中恒温油浴槽13用的导热油加热炉23通过球阀24、第二高温油泵26及球阀25与恒温油浴槽13相连通,用于控制原料反应温度。1. Construction and configuration of a microchannel reaction device. As shown in Figure 1, the microchannel reaction device consists of a heat transfer oil heating furnace 9, a first oil bath raw material storage tank 1, and a second oil bath raw material storage tank 5 connected by corresponding pipelines. , the first filter 3, the second filter 7, the first plunger metering pump 4, the second plunger metering pump 8, the micro mixer 14, the microchannel reactor 15, the constant temperature oil bath 13, the cooling tank 16 , product storage tank 18, tail gas absorption device 20, nitrogen cylinder 22, first high temperature oil pump 11, second high temperature oil pump 26 and a plurality of ball valves (2, 6, 10, 12, 17, 19) mounted on each connecting pipeline , 21, 24, 25) etc. In the specific implementation structure, the heat transfer oil heating furnace 9 has two heat source output ends, and one heat source output end is connected to the first oil bath raw material storage tank 1 through a connecting pipeline equipped with a ball valve 12, which is the first oil bath raw material storage tank. The raw material in 1 is preheated, and the output end of the other heat source is connected to the second oil bath raw material storage tank 5 through the connecting pipeline equipped with the ball valve 10 and the first high temperature oil pump, which is the raw material in the second oil bath raw material storage tank 5. Preheating; the outlet end of the first oil bath raw material storage tank 1 is connected to the inlet end of the first plunger metering pump 4 through the pipeline equipped with the ball valve 2 through the first filter 3, and the second oil bath raw material storage tank 5 The outlet end is connected to the inlet end of the second plunger metering pump 8 through the pipeline equipped with the ball valve 6 through the second filter 7, and the outlet of the first plunger metering pump 4 and the second plunger metering pump 8 After the ends are connected in parallel, they enter the constant temperature oil bath tank 13, and then connect to the inlet end of the micro-mixer 14. The outlet end of the micro-mixer 14 is connected to the inlet end of the cooling tank 16 filled with tap water or salt water through the micro-channel reactor 15. , the outlet end of the cooling tank 16 enters the product storage tank 18 through a pipeline equipped with a ball valve 17, and the by-product tail gas outlet end of the product storage tank 18 is connected to the exhaust gas absorption device 20 through a pipeline equipped with a ball valve 19. Inside. In addition, the outlet end of the nitrogen cylinder 22 also enters the product storage tank 18 through a pipeline with a ball valve 21 on it. During operation, nitrogen gas can be blown into the product storage tank 18 through the nitrogen cylinder 22 at 1-10 mL/min. Oxide by-products undergo a redox reaction with urea with a concentration of 5% to 10% under the catalysis of nitric acid with a pH value of 1 to 3 to reduce it to nitrogen. In the present invention, the diameter of the micro-channel reactor 15 is 0.1-5 mm, the micro-mixer 14 and the micro-channel reactor 15 are arranged in the constant temperature oil bath 13, immersed in heat-conducting oil, and the oil temperature is controlled at 30-80° C. The heat transfer oil heating furnace 23 used in the constant temperature oil bath 13 in 1 is communicated with the constant temperature oil bath 13 through the ball valve 24, the second high temperature oil pump 26 and the ball valve 25, and is used to control the reaction temperature of the raw materials.

二、将原料1,3-二氢异苯并呋喃及浓度为30%~98%(优选浓度为50%~69%)的硝酸分别置入在两个原料储罐中,通过导热油加热炉为原料预热至30~80℃,优选为60~80℃。2. Put the raw material 1,3-dihydroisobenzofuran and the nitric acid with a concentration of 30% to 98% (preferably a concentration of 50% to 69%) into two raw material storage tanks, respectively, and pass the heat transfer oil heating furnace The raw material is preheated to 30-80°C, preferably 60-80°C.

三、将预热后的1,3-二氢异苯并呋喃及硝酸按照流量体积比1:0.5~4(优选为1:1~2)分别通过第一柱塞式计量泵4和第二柱塞式计量泵8进入微混合器中14进行混合,进一步再通入微通道反应器15内停留5~30min(优选停留时间为10~20min)进行氧化反应合成邻苯二甲醛产物混合液,之后使其进至产物储槽中。3. Pass the preheated 1,3-dihydroisobenzofuran and nitric acid respectively through the first plunger metering pump 4 and the second according to the flow volume ratio of 1:0.5-4 (preferably 1:1-2) The plunger-type metering pump 8 enters the micro-mixer 14 for mixing, and further passes into the micro-channel reactor 15 to stay for 5 to 30 minutes (preferably the residence time is 10 to 20 minutes) for oxidation reaction to synthesize the o-phthalaldehyde product mixture, and then It goes to the product storage tank.

四、通过氮气瓶经氮气管路向产物储槽18中以1~10mL/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为1~3的硝酸催化下与浓度为5%~10%的尿素发生氧化还原反应,使其还原为氮气;向经氮气吹扫后的反应产物加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛。4. Bubble nitrogen into the product storage tank 18 through the nitrogen gas pipeline at a rate of 1-10 mL/min, and purge the generated nitrogen oxide by-product into the tail gas absorption device 20. Under catalysis, a redox reaction occurs with urea with a concentration of 5% to 10% to reduce it to nitrogen; add twice the volume of deionized water to the reaction product after nitrogen purging, stir for 30min, cool to room temperature, The aqueous phase was separated, extracted three times with an equal volume of ethyl acetate, the extracts were combined, and the ethyl acetate was recovered by distillation to obtain o-phthalaldehyde.

五、将经蒸馏后的邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品。5. Place the distilled ortho-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 °C for 4 hours to obtain the ortho-phthalaldehyde product.

实施例1Example 1

将原料1,3-二氢异苯并呋喃及98%硝酸预热至30℃,将预热后的1,3-二氢异苯并呋喃及98%硝酸按照流量体积比1:0.5分别泵入微混合器中进行混合,进一步再经过微通道反应器,微通道反应器的管径为0.3mm,在30℃温度停留反应时间10min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以5ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为2的硝酸催化下与浓度为5%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量95.5%,收率69.7%。本实施例的制备邻苯二甲醛的IR图、1HNMR图和GC图分别见图2、图3、图4.The raw materials 1,3-dihydroisobenzofuran and 98% nitric acid are preheated to 30°C, and the preheated 1,3-dihydroisobenzofuran and 98% nitric acid are pumped respectively according to the flow volume ratio of 1:0.5 Put into a micro-mixer for mixing, and then pass through a micro-channel reactor with a diameter of 0.3 mm, and stay at 30°C for a reaction time of 10 minutes to obtain the target product mixture of o-phthalaldehyde, and make it into the product Tank 18. Nitrogen gas is blown into the product storage tank 18 at a rate of 5 ml/min through the nitrogen cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 2 and a concentration of 5% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with an equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 ° C and dry for 4 hours to obtain o-phthalaldehyde product with a content of 95.5% and a yield of 69.7 %. The IR chart, 1 HNMR chart and GC chart of the preparation of o-phthalaldehyde in this example are shown in Figure 2, Figure 3, and Figure 4, respectively.

实施例2Example 2

将原料1,3-二氢异苯并呋喃及硝酸预热至50℃。将预热后的1,3-二氢异苯并呋喃及50%硝酸按照流量体积比1:2分别泵入微混合器中进行混合,进一步在经过微通道反应器,微通道及反应器的管径为0.3mm,在50℃温度停留反应时间10min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以5ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为2.5的硝酸催化下与浓度为10%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量96.1%,收率81.6%。The raw material 1,3-dihydroisobenzofuran and nitric acid were preheated to 50°C. The preheated 1,3-dihydroisobenzofuran and 50% nitric acid were respectively pumped into the micro-mixer according to the flow volume ratio of 1:2 for mixing, and further passed through the micro-channel reactor, the micro-channel and the tube of the reactor. The diameter is 0.3 mm, and the reaction time is 10 min at a temperature of 50° C. to obtain a mixed solution of the o-phthalaldehyde target product, which is fed into the product storage tank 18 . Nitrogen gas is blown into the product storage tank 18 at 5 ml/min through the nitrogen gas cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 2.5 and a concentration of 10% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with an equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 ° C and dry for 4 hours to obtain o-phthalaldehyde product with a content of 96.1% and a yield of 81.6 %.

实施例3Example 3

将原料1,3-二氢异苯并呋喃及硝酸预热至40℃。将预热后的1,3-二氢异苯并呋喃及60%硝酸按照流量体积比1:1.3分别泵入微混合器中进行混合,进一步在经过微通道反应器,微通道及反应器的管径为0.5mm,在40℃温度停留反应时间20min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以3ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为3的硝酸催化下与浓度为10%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量96.4%,收率70.4%。The raw material 1,3-dihydroisobenzofuran and nitric acid were preheated to 40°C. The preheated 1,3-dihydroisobenzofuran and 60% nitric acid were respectively pumped into the micro-mixer according to the flow volume ratio of 1:1.3 for mixing, and further passed through the micro-channel reactor, the micro-channel and the tube of the reactor. The diameter is 0.5 mm, and the reaction time is kept at 40° C. for 20 minutes to obtain the o-phthalaldehyde target product mixed solution, which is fed into the product storage tank 18 . Nitrogen gas is blown into the product storage tank 18 at 3 ml/min through the nitrogen gas cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 3 and a concentration of 10% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with an equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 °C for 4 hours to obtain o-phthalaldehyde product, with a content of 96.4% and a yield of 70.4 %.

实施例4Example 4

将原料1,3-二氢异苯并呋喃及硝酸预热至60℃。将预热后的1,3-二氢异苯并呋喃及68%硝酸按照流量体积比1:1.5分别泵入微混合器中进行混合,进一步在经过微通道反应器,微通道及反应器的管径为0.5mm,在60℃温度停留反应时间15min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以10ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为2.5的硝酸催化下与浓度为8%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量99.2%,收率88.4%。The raw material 1,3-dihydroisobenzofuran and nitric acid were preheated to 60°C. The preheated 1,3-dihydroisobenzofuran and 68% nitric acid were respectively pumped into the micro-mixer according to the flow volume ratio of 1:1.5 for mixing, and further passed through the micro-channel reactor, the micro-channel and the tube of the reactor. The diameter is 0.5 mm, and the reaction time is kept at 60° C. for 15 minutes to obtain the o-phthalaldehyde target product mixed solution, which is fed into the product storage tank 18 . Nitrogen gas is blown into the product storage tank 18 at 10 ml/min through the nitrogen gas cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 2.5 and a concentration of 8% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 °C for 4 hours to obtain o-phthalaldehyde product, with a content of 99.2% and a yield of 88.4 %.

实施例5Example 5

将原料1,3-二氢异苯并呋喃及硝酸预热至80℃。将预热后的1,3-二氢异苯并呋喃及30%硝酸按照流量体积比1:4分别泵入微混合器中进行混合,进一步在经过微通道反应器,微通道及反应器的管径为2mm,在80℃温度停留反应时间25min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以5ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为1.5的硝酸催化下与浓度为10%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量99.5%,收率84.7%。The raw material 1,3-dihydroisobenzofuran and nitric acid were preheated to 80°C. The preheated 1,3-dihydroisobenzofuran and 30% nitric acid were respectively pumped into the micro-mixer according to the flow volume ratio of 1:4 for mixing, and further passed through the micro-channel reactor, the micro-channel and the tube of the reactor. The diameter is 2 mm, and the reaction time is held at 80° C. for 25 min to obtain the o-phthalaldehyde target product mixed solution, which is fed into the product storage tank 18 . Nitrogen gas is blown into the product storage tank 18 at 5 ml/min through the nitrogen gas cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 1.5 and a concentration of 10% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with an equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 ° C and dry for 4 hours to obtain o-phthalaldehyde product with a content of 99.5% and a yield of 84.7 %.

实施例6Example 6

将原料1,3-二氢异苯并呋喃及硝酸预热至70℃。将预热后的1,3-二氢异苯并呋喃及40%硝酸按照流量体积比1:3.5分别泵入微混合器中进行混合,进一步在经过微通道反应器,微通道及反应器的管径为2mm,在70℃温度,停留反应时间30min,得到邻苯二甲醛目标产物混合液,使其进至产物储槽18。通过氮气瓶22经氮气管路向产物储槽18中以10ml/min鼓入氮气,将生成的氮氧化物副产吹扫至尾气吸收装置20中,在pH值为3的硝酸催化下与浓度为5%的尿素发生氧化还原反应,使其还原为氮气。氮气吹扫后,向反应产物混合液加入两倍体积的去离子水,搅拌30min,冷却至室温后,静置分离出水相,使用等体积的乙酸乙酯萃取3次,合并萃取液,蒸馏回收乙酸乙酯,得邻苯二甲醛;将邻苯二甲醛放置于真空度为50~60Pa、温度为50℃的真空干燥箱中干燥4h,得邻苯二甲醛产品,含量97.8%,收率79.3%。The raw material 1,3-dihydroisobenzofuran and nitric acid were preheated to 70°C. The preheated 1,3-dihydroisobenzofuran and 40% nitric acid were respectively pumped into the micro-mixer according to the flow volume ratio of 1:3.5 for mixing, and further passed through the micro-channel reactor, the micro-channel and the reactor tube. The diameter is 2 mm, and the reaction time is 30 min at a temperature of 70° C. to obtain a mixed solution of the o-phthalaldehyde target product, which is made to enter the product storage tank 18 . Nitrogen gas is blown into the product storage tank 18 at 10 ml/min through the nitrogen gas cylinder 22 through the nitrogen pipeline, and the generated nitrogen oxide by-product is swept into the tail gas absorption device 20. Under the catalysis of nitric acid with a pH value of 3 and a concentration of 5% of urea undergoes a redox reaction, reducing it to nitrogen. After nitrogen purging, add twice the volume of deionized water to the reaction product mixture, stir for 30 min, cool to room temperature, stand to separate out the water phase, extract three times with an equal volume of ethyl acetate, combine the extracts, and recover by distillation Ethyl acetate to obtain o-phthalaldehyde; place o-phthalaldehyde in a vacuum drying oven with a vacuum degree of 50-60 Pa and a temperature of 50 ° C and dry for 4 hours to obtain o-phthalaldehyde product with a content of 97.8% and a yield of 79.3 %.

Claims (4)

1. A method for continuously synthesizing o-phthalaldehyde by a microchannel reaction device is characterized by comprising the following synthesis steps:
a. the method comprises the steps of constructing and configuring a microchannel reaction device, wherein the microchannel reaction device comprises a heat-conducting oil heating furnace (9), two oil bath raw material storage tanks (1, 5), two filters (3, 7), two plunger type metering pumps (4, 8), a micro mixer (14), a microchannel reactor (15), a constant-temperature oil bath (13), a cooling tank (16), a product storage tank (18), a tail gas absorption device (20) and a nitrogen bottle (22), wherein the micro mixer (14) and the microchannel reactor (15) are arranged in the constant-temperature oil bath (13) with the temperature controlled at 30-80 ℃, a heat source output end of the heat-conducting oil heating furnace (9) is respectively connected with a first oil bath raw material storage tank (1) and a second oil bath raw material storage tank (5) through a connecting pipeline with ball valves arranged on the heat source output end, an outlet end of the first oil bath raw material storage tank (1) is connected to an inlet end of the first plunger type metering pump (4) through the first filter, the outlet end of a second oil bath raw material storage tank (5) is connected to the inlet end of a second plunger type metering pump (8) through a second filter (7), the outlet ends of the first plunger type metering pump (4) and the second plunger type metering pump (8) are connected in parallel and then enter a constant temperature oil bath groove (13) and then are connected to the inlet end of a micro mixer (14), the outlet end of the micro mixer (14) is connected to the inlet end of a cooling groove (16) filled with tap water or saline water through a micro channel reactor (15), the outlet end of the cooling groove (16) and the outlet end of a nitrogen bottle (22) both enter a product storage tank (18) through a pipeline provided with a ball valve, and the byproduct tail gas outlet end of the product storage tank (18) is connected to a tail gas absorption device (20) through a pipeline provided with a;
b. respectively putting raw materials 1, 3-dihydroisobenzofuran and nitric acid into two oil bath raw material storage tanks (1, 5), and preheating the raw materials to 30-80 ℃ by using a heat conduction oil heating furnace (9);
c. the preheated 1, 3-dihydroisobenzofuran and nitric acid respectively enter a micro mixer (14) through a first plunger type metering pump (4) and a second plunger type metering pump (8) according to the flow volume ratio of 1: 0.5-4 for mixing, and further enter a microchannel reactor (15) for staying for 5-30 min for oxidation reaction to synthesize a phthalic dicarboxaldehyde product mixed solution, and then the phthalic dicarboxaldehyde product mixed solution enters a product storage tank (18);
d. blowing nitrogen into the product storage tank (18) through a nitrogen bottle (22) through a nitrogen pipeline at a rate of 1-10 mL/min, blowing the generated nitrogen oxide byproduct into a tail gas absorption device (20), and carrying out an oxidation-reduction reaction on the nitrogen oxide byproduct and urea with the concentration of 5-10% under the catalysis of nitric acid with the pH value of 1-3 to reduce the nitrogen oxide byproduct into nitrogen; adding deionized water with the volume twice that of the reaction product subjected to nitrogen purging, stirring for 30min, cooling to room temperature, standing to separate out a water phase, extracting for 3 times by using ethyl acetate with the same volume, combining extract liquor, and distilling to recover ethyl acetate to obtain o-phthalaldehyde;
e. and (3) drying the distilled o-phthalaldehyde in a vacuum drying oven with the vacuum degree of 50-60 Pa and the temperature of 50 ℃ for 4 hours to obtain an o-phthalaldehyde product.
2. The method for continuously synthesizing o-phthalaldehyde by using the microchannel reaction device according to claim 1, wherein the method comprises the following steps: in the step a, the pipe diameter of the microchannel reactor (15) is 0.1-5 mm.
3. The method for continuously synthesizing o-phthalaldehyde by using the microchannel reaction device according to claim 1, wherein the method comprises the following steps: in the step b, the concentration of the nitric acid is 30-98%, and the preferable concentration is 50-69%; the preheating temperature of the raw materials is preferably 60-80 ℃.
4. The method for continuously synthesizing o-phthalaldehyde by using the microchannel reaction device according to claim 1, wherein the method comprises the following steps: the flow volume ratio of the 1, 3-dihydroisobenzofuran to the nitric acid in the step c is preferably 1: 1-2, and the preferable retention time of the mixed solution in the microchannel reactor (15) is 10-20 min.
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