CN111333559A - A kind of method for continuous flow rapid preparation of peracetic acid - Google Patents
A kind of method for continuous flow rapid preparation of peracetic acid Download PDFInfo
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Abstract
本发明提供了一种连续流快速制备过氧乙酸的方法,利用连续流微通道反应器进行反应,包括以下步骤,1)将醋酸、过氧化氢溶液、催化剂和稳定剂混合后一起通入微通道反应预热模块;2)使步骤1)预热后混合物连续进入微通道反应模块,反应温度范围80~150℃,压力维持0.5~2.0MPa,停留时间为10~200秒;3)使步骤2)微通道反应模块出口得到的产物进入冷却模块。本发明利用微通道反应器的特性,可以实现连续流快速制备过氧乙酸,相较于传统工艺,本发明极大地缩短了反应时间、提高了生产效率、有效降低了安全风险,易于进行工业化放大和生产。
The invention provides a continuous flow method for rapidly preparing peracetic acid. The continuous flow microchannel reactor is used to carry out the reaction, and the reaction includes the following steps: 1) acetic acid, hydrogen peroxide solution, catalyst and stabilizer are mixed and passed into the microchannel together Reaction preheating module; 2) Make the preheated mixture in step 1) continuously enter the microchannel reaction module, the reaction temperature range is 80-150 ° C, the pressure is maintained at 0.5-2.0 MPa, and the residence time is 10-200 seconds; 3) Step 2 ) The product obtained from the outlet of the microchannel reaction module enters the cooling module. The invention utilizes the characteristics of the microchannel reactor, and can realize the rapid preparation of peracetic acid by continuous flow. Compared with the traditional process, the invention greatly shortens the reaction time, improves the production efficiency, effectively reduces the safety risk, and is easy to carry out industrialized amplification. and produce.
Description
技术领域technical field
本发明属于精细化工与医药化工领域,尤其是涉及一种连续流快速制备 过氧乙酸的方法。The invention belongs to the fields of fine chemical industry and pharmaceutical chemical industry, and particularly relates to a method for rapidly preparing peracetic acid by continuous flow.
背景技术Background technique
过氧乙酸(Peracetic acid,CH3COOOH)是一种无色透明液体,具有较 强的氧化性,广泛应用于化工行业的材料合成、石油行业柴油脱硫、轻纺行 业的织物漂白以及医疗卫生领域的杀菌消毒。更具体地,在化工合成中,过 氧乙酸可以作为环氧化剂进行烯烃环氧化制备环氧单体,用以合成环氧丙烷、 己内酰胺、甘油、环氧增塑剂、戊内酯和己内酯等;在医疗领域中,过氧乙 酸是一种高效广谱化学消毒剂,具有使用浓度低、杀菌作用强、消毒时间短、 分解物无毒等优点,广泛应用于医疗器械消毒、灭菌以及环境、物表、空气 等疫源地消毒和预防性消毒,在2003年非典疫情期间,作为消毒剂主力军 用于医院和其他公共场所的杀菌消毒。Peracetic acid (CH 3 COOOH) is a colorless and transparent liquid with strong oxidizing properties. It is widely used in material synthesis in the chemical industry, diesel desulfurization in the petroleum industry, fabric bleaching in the light textile industry, and medical and health fields. sterilization and disinfection. More specifically, in chemical synthesis, peracetic acid can be used as an epoxidizing agent to carry out olefin epoxidation to prepare epoxy monomers for the synthesis of propylene oxide, caprolactam, glycerol, epoxy plasticizer, valerolactone and caprolactone. In the medical field, peracetic acid is a kind of high-efficiency broad-spectrum chemical disinfectant, which has the advantages of low concentration, strong bactericidal effect, short disinfection time, non-toxic decomposition products, etc. It is widely used in disinfection, sterilization and During the SARS epidemic in 2003, it was used as the main force of disinfectants for sterilization and disinfection in hospitals and other public places.
过氧乙酸合成工艺主要有两种方法:乙醛空气/氧气氧化法和过氧化氢法。 其中乙醛空气/氧气氧化法虽然成本相对较低,但所需设备复杂、投资大、安 全风险较高,同时生产过程中产生的乙醛单过乙酸酯是温敏性易爆物,爆炸 风险性较高;若采用重金属酸性催化剂抑制乙醛单过乙酸酯的形成,则后期 需要对重金属酸性催化剂进行去除,否则会影响过氧乙酸的稳定性。过氧化 氢法则是由30~90wt%过氧化氢与冰醋酸在强酸性催化剂(硫酸或磺酸型离 子交换树脂)存在下反应4~36h制备过氧乙酸,其反应式如(I)所示。另外, 也可采用醋酸酐代替醋酸作为原料,虽能提高过氧乙酸的浓度,但反应过程 中会生成易爆炸的二酰基过氧化物副产物,因此工业生产中仍多采用醋酸- 过氧化氢反应进行过氧乙酸的生产。There are two main methods for the synthesis of peracetic acid: acetaldehyde air/oxygen oxidation and hydrogen peroxide. Among them, although the cost of acetaldehyde air/oxygen oxidation is relatively low, the required equipment is complex, the investment is large, and the safety risk is high. The risk is high; if heavy metal acid catalyst is used to inhibit the formation of acetaldehyde monoperacetate, the heavy metal acid catalyst needs to be removed later, otherwise the stability of peracetic acid will be affected. The hydrogen peroxide rule is to prepare peracetic acid by reacting 30 to 90 wt% hydrogen peroxide with glacial acetic acid in the presence of a strong acid catalyst (sulfuric acid or sulfonic acid ion exchange resin) for 4 to 36 hours. The reaction formula is shown in (I) . In addition, also can adopt acetic anhydride to replace acetic acid as raw material, although can improve the concentration of peracetic acid, but can generate explosive diacyl peroxide by-product in the reaction process, therefore still use acetic acid-hydrogen peroxide more in industrial production The reaction proceeds to the production of peracetic acid.
醋酸-过氧化氢法在工艺合成方面也存在巨大挑战:首先,反应体系放热 非常明显。反应过程中需要慢速加入物料并不断强烈搅拌移除反应热,防止 反应飞温造成爆炸等生产事故,而慢速加料势必会导致反应时间延长,生产 效率低下;其次,过氧化氢与过氧乙酸不稳定。传统工艺一般在较低温度 (40~60℃)下进行,反应接近平衡时间至少数小时,且需要占用较大的反应 器体积。提高双氧水浓度,虽可加快反应速度,但生产效率依然很低;提高 反应温度虽能加快反应速度提高生产效率,但过氧化氢在35℃以上开始放热 分解。The acetic acid-hydrogen peroxide method also has great challenges in terms of process synthesis: First, the exothermicity of the reaction system is very obvious. During the reaction process, it is necessary to slowly add materials and continuously and vigorously stir to remove the heat of reaction, so as to prevent production accidents such as explosion caused by the overheating of the reaction, and slow feeding will inevitably lead to prolonged reaction time and low production efficiency; secondly, hydrogen peroxide and peroxygen Acetic acid is unstable. The traditional process is generally carried out at a relatively low temperature (40-60 °C), the reaction is close to the equilibrium time for at least several hours, and a large reactor volume is required. Although increasing the hydrogen peroxide concentration can speed up the reaction speed, the production efficiency is still very low; although increasing the reaction temperature can speed up the reaction speed and improve the production efficiency, the hydrogen peroxide begins to decompose exothermically above 35°C.
传统的釜式反应器,传质、传热差(液液传质系数0.05~0.1s-1,总传热 系数为1~10KW/m3·K),无法避免返流现象,且持液量大,易造成局部物料 浓度、温度不均,在合成过氧乙酸过程中存在巨大安全风险;静态混合器或 管式反应器,换热面积较釜式反应器提升很多(液液传质系数0.1~10s-1,总 传热系数为200~800KW/m3·K),且解决了反流问题,但混合仍以分散-湍 流方式完成,需要较长的时间实现混合均匀,对于某些对传质要求高,两相 物料参与的反应仍不能达到理想的传质效果及反应选择性;连续流微通道反 应器是指经过微加工和精密加工技术制造的小型反应系统,包括化工单元反 应所需的混合器、换热器、反应器和控制器等,但其管道尺寸远远小于常规 的管式反应器,一般在微米至毫米级别。连续流微通道反应器内因为相界面 对流体的分隔作用和微通道对于流体的摩擦作用的存在,使得反应器内存在 强烈的内循环和二次流流动,对反应物之间传质的强化有重要作用,加之通 过强化混合,如分离再混合、层流扩散等手段,可促使反应在毫秒至秒级完成(液液传质系数为1~41s-1);同时,微通道反应器的反应通道尺寸小在缩 短分子扩散距离、增加传质效率的同时,反应区持液量很小,与换热区比表 面积非常大,传热能力非常强(总传热系数为1500KW/m3·K以上),温升 效果并不明显,可实现“数增放大”,且无放大效应,安全系数高。因此, 使用微通道反应器往往能在很短的停留时间内快速完成反应,得到的产物选 择性较传统工艺要高,副产物较低,尤其适用于放热剧烈、反应物或产物不 稳定、反应物配比要求严格、危险系数较高、易燃易爆的反应等。The traditional tank reactor has poor mass transfer and heat transfer (liquid-liquid mass transfer coefficient is 0.05~0.1s -1 , and the total heat transfer coefficient is 1~10KW/m 3 ·K), the backflow phenomenon cannot be avoided, and liquid retention The amount is large, which is easy to cause uneven local material concentration and temperature, and there is a huge safety risk in the process of synthesizing peracetic acid; static mixer or tubular reactor, the heat exchange area is much higher than that of the tank reactor (liquid-liquid mass transfer coefficient). 0.1~10s -1 , the total heat transfer coefficient is 200~800KW/m 3 ·K), and the reverse flow problem is solved, but the mixing is still done in a dispersion-turbulent flow method, which takes a long time to achieve uniform mixing. The requirements for mass transfer are high, and the reaction involving two-phase materials still cannot achieve the ideal mass transfer effect and reaction selectivity; continuous flow microchannel reactor refers to a small reaction system manufactured by micromachining and precision machining technology, including chemical unit reactions The required mixers, heat exchangers, reactors and controllers, etc., but the pipe size is much smaller than the conventional tubular reactor, generally in the order of micrometers to millimeters. In the continuous flow microchannel reactor, because of the separation effect of the phase interface on the fluid and the friction effect of the microchannel on the fluid, there is a strong internal circulation and secondary flow in the reactor, which strengthens the mass transfer between the reactants. It plays an important role. In addition, by means of strengthening mixing, such as separation and remixing, laminar diffusion, etc., the reaction can be completed in milliseconds to seconds (the liquid-liquid mass transfer coefficient is 1 to 41s -1 ); The small size of the reaction channel shortens the molecular diffusion distance and increases the mass transfer efficiency, while the liquid holdup in the reaction zone is very small, the specific surface area with the heat exchange zone is very large, and the heat transfer capacity is very strong (the total heat transfer coefficient is 1500KW/m 3 · Above K), the temperature rise effect is not obvious, and the "number increase magnification" can be realized, and there is no magnification effect, and the safety factor is high. Therefore, the use of microchannel reactors can often complete the reaction quickly in a very short residence time, and the obtained product selectivity is higher than that of the traditional process, and the by-products are lower, especially suitable for severe exotherm, unstable reactants or products, The ratio of reactants is strict, the risk factor is high, and the reaction is flammable and explosive.
如何实现连续流快速制备过氧乙酸的目的,成为亟待解决的问题。How to realize the purpose of rapid preparation of peracetic acid by continuous flow has become an urgent problem to be solved.
发明内容SUMMARY OF THE INVENTION
有鉴于此,本发明旨在提出一种连续流快速制备过氧乙酸的方法,以克 服现有技术中反应时间长、生产效率低、工艺相对复杂、设备投资大、制造 成本较高、安全风险较高等问题。In view of this, the present invention aims to propose a method for the rapid preparation of peracetic acid in a continuous flow, to overcome the long reaction time, low production efficiency, relatively complex process, large equipment investment, high manufacturing cost and safety risk in the prior art. higher issues.
为达到上述目的,本发明的技术方案是这样实现的:In order to achieve the above object, the technical scheme of the present invention is achieved in this way:
一种连续流快速制备过氧乙酸的方法,利用连续流微通道反应器进行反 应,包括以下步骤,A method for preparing peracetic acid in a continuous flow, utilizes a continuous flow microchannel reactor to react, comprising the following steps,
1)将醋酸、过氧化氢溶液、催化剂和稳定剂混合后一起通入微通道反应 预热模块;1) acetic acid, hydrogen peroxide solution, catalyst and stabilizer are mixed together and passed into the microchannel reaction preheating module;
2)使步骤1)预热后混合物连续进入微通道反应模块,反应温度范围 80~150℃,压力维持0.5~2.0MPa,停留时间为10~200秒;2) Make the preheated mixture in step 1) continuously enter the microchannel reaction module, the reaction temperature range is 80~150℃, the pressure is maintained at 0.5~2.0MPa, and the residence time is 10~200 seconds;
3)使步骤2)微通道反应模块出口得到的产物进入冷却模块。3) The product obtained from the outlet of the microchannel reaction module in step 2) enters the cooling module.
利用微通道反应器反应通道尺寸小、持液量低、无返混、传质传热快、 停留时间分布窄等特点,大大提高了反应效率和稳定性,同时极大地降低了 因反应温度失控引发的安全风险。Utilizing the characteristics of small reaction channel size, low liquid holdup, no back-mixing, fast mass transfer and heat transfer, and narrow residence time distribution, the reaction efficiency and stability of the microchannel reactor are greatly improved, and the runaway temperature caused by the reaction is greatly reduced. resulting security risks.
优选的,连续流微通道反应器的传质系数为1~41s-1、总传热系数为 1500KW/m3·K以上。Preferably, the mass transfer coefficient of the continuous flow microchannel reactor is 1-41 s -1 , and the total heat transfer coefficient is 1500KW/m 3 ·K or more.
优选的,所述催化剂为浓硫酸、甲磺酸、苯磺酸中的一种或两种以上, 优选浓硫酸;所述的稳定剂为磷酸钠、焦磷酸钠、羟基乙叉二磷酸、乙二胺 四乙酸、8-羟基喹啉、吡啶-2,6-二甲酸中的一种或两种以上,优选为8-羟基 喹啉和乙二胺四乙酸中的一种或两种的混合物。Preferably, the catalyst is one or more of concentrated sulfuric acid, methanesulfonic acid and benzenesulfonic acid, preferably concentrated sulfuric acid; the stabilizer is sodium phosphate, sodium pyrophosphate, hydroxyethylidene diphosphoric acid, ethyl acetate One or more of diaminetetraacetic acid, 8-hydroxyquinoline, and pyridine-2,6-dicarboxylic acid, preferably a mixture of one or two of 8-hydroxyquinoline and ethylenediaminetetraacetic acid .
优选的,步骤1)中,醋酸与过氧化氢的摩尔比为(1~10):1,优选比 例为(1.5~4):1;过氧化氢溶液的浓度为25~75wt%,优选30~70wt%;所 述催化剂添加量为反应总物料的0.5~10wt%,优选1~5wt%;所述稳定剂添 加量为反应总物料的0.01~0.5wt%;优选0.15~0.3wt%。Preferably, in step 1), the molar ratio of acetic acid to hydrogen peroxide is (1-10): 1, and the preferred ratio is (1.5-4): 1; the concentration of the hydrogen peroxide solution is 25-75wt%, preferably 30 ~70wt%; the catalyst addition amount is 0.5-10wt% of the total reaction material, preferably 1-5wt%; the stabilizer addition amount is 0.01-0.5wt% of the total reaction material; preferably 0.15-0.3wt%.
优选的,步骤2)中,微通道反应模块的反应温度为100~130℃,反应 压力为1.2~1.5MPa,停留时间为15~45秒。Preferably, in step 2), the reaction temperature of the microchannel reaction module is 100-130 °C, the reaction pressure is 1.2-1.5 MPa, and the residence time is 15-45 seconds.
优选的,步骤1)中,微通道反应预热模块的预热温度为80~150℃,优 选100~130℃;步骤3)中,所述的冷却模块,其冷却温度为0~30℃,优选 5~20℃。Preferably, in step 1), the preheating temperature of the microchannel reaction preheating module is 80-150°C, preferably 100-130°C; in step 3), the cooling temperature of the cooling module is 0-30°C, Preferably it is 5-20 degreeC.
优选的,所述连续流微通道反应器为增强混合式微通道反应器、薄层连 续切分式微通道反应器、微孔阵列式微通道反应器、翅片式微通道反应器、 毛细管微通道反应器或多股并流式微反应器。Preferably, the continuous flow microchannel reactor is an enhanced hybrid microchannel reactor, a thin-layer continuous split microchannel reactor, a micropore array microchannel reactor, a fin-type microchannel reactor, a capillary microchannel reactor or Multi-strand co-flow microreactors.
优选的,所述微通道反应器的反应模块内的微通道结构为直流型通道结 构或增强混合型通道结构;优选的是,所述直流型通道结构为管状结构,所 述增强混合型通道结构为T型结构、球形结构、球形带挡板结构、水滴状结 构、心形结构、锯齿形或伞形结构,且通道直径为0.5~10mm。Preferably, the microchannel structure in the reaction module of the microchannel reactor is a direct current channel structure or an enhanced mixed channel structure; preferably, the direct current channel structure is a tubular structure, and the enhanced mixed channel structure It is a T-shaped structure, a spherical structure, a spherical structure with baffles, a droplet-shaped structure, a heart-shaped structure, a zigzag-shaped or an umbrella-shaped structure, and the diameter of the channel is 0.5-10 mm.
本发明同时提供如上所述的方法在制备过氧乙酸中的应用。The present invention also provides the application of the above-mentioned method in the preparation of peracetic acid.
本发明提供的方法,所述醋酸和过氧化氢的氧化反应在连续微通道反应 器内进行,可以按照需求将预热模块、反应模块、冷却模块和传热模块进行 连接。微通道反应器连接好后,可以采用导热油进行传热,采用乙醇/乙二醇 进行冷却。In the method provided by the present invention, the oxidation reaction of acetic acid and hydrogen peroxide is carried out in a continuous microchannel reactor, and a preheating module, a reaction module, a cooling module and a heat transfer module can be connected as required. After the microchannel reactor is connected, heat transfer oil can be used for heat transfer, and ethanol/ethylene glycol can be used for cooling.
相对于现有技术,本发明所述的连续流快速制备过氧乙酸的方法,具有 以下优势:With respect to the prior art, the method for rapidly preparing peracetic acid with continuous flow of the present invention has the following advantages:
(1)本发明所述的方法,采用醋酸与过氧化氢在连续流微通道反应器 进行反应。利用微通道反应器的特点,即反应通道尺寸为微米至毫米级,分 子扩散距离短,无返混、传质传热快、停留时间分布窄,在制备过氧乙酸反 应中可将传统工艺的反应温度大幅提升至80~150℃,极大地提高了反应效 率,停留时间降低至10~200s,而极短的停留时间又使得过氧化氢在反应结 束前来不及分解,大大降低了过氧化氢在高温下分解、放热的趋势。持液量 极小的反应模块放出的热量在单位体积比表面积超大、传热速度超快的作用 下被迅速移除,大大降低了因反应温度失控引发的安全风险,实现本质安全 生产。(1) method of the present invention adopts acetic acid and hydrogen peroxide to react in continuous flow microchannel reactor. Taking advantage of the characteristics of the microchannel reactor, that is, the size of the reaction channel is from micrometers to millimeters, the molecular diffusion distance is short, there is no backmixing, mass and heat transfer is fast, and the residence time distribution is narrow. In the preparation of peracetic acid, the traditional process can be used. The reaction temperature is greatly increased to 80-150 °C, which greatly improves the reaction efficiency, and the residence time is reduced to 10-200s, and the extremely short residence time makes the hydrogen peroxide not decompose in time before the end of the reaction, which greatly reduces the hydrogen peroxide. Tendency to decompose and exothermic at high temperature. The heat released by the reaction module with extremely small liquid holding capacity is quickly removed under the action of the large specific surface area per unit volume and the ultra-fast heat transfer rate, which greatly reduces the safety risk caused by the uncontrolled reaction temperature and realizes intrinsically safe production.
(2)本发明所述的方法,利用微通道反应器可同时实现“尺寸放大”和 “数增放大”相结合、无放大效应的特点,易于进行工业化放大和生产,同 时设备占地小、投资小,生产灵活性和安全性很高。(2) The method of the present invention can realize the combination of "size amplification" and "number amplification" at the same time by using the microchannel reactor, and has no amplification effect. Small investment, high production flexibility and safety.
(3)本发明所述的方法,使过氧化氢的转化率达到99%以上,制备的过 氧乙酸浓度高,浓度在20~35%之间。同时,因稳定剂的存在,过氧乙酸在 常温高浓度下稳定保存,降解率较低,克服了现有技术中过氧乙酸易分解、 不耐储存的缺点。该发明制备的过氧乙酸溶液经蒸馏水稀释到规定的浓度后, 即可直接作为医用消毒剂使用。(3) The method of the present invention makes the conversion rate of hydrogen peroxide reach more than 99%, and the prepared peracetic acid concentration is high, and the concentration is between 20~35%. At the same time, because of the existence of stabilizer, peracetic acid is stably preserved at normal temperature and high concentration, and degradation rate is lower, overcoming the shortcoming of peracetic acid being easily decomposed and intolerant of storage in the prior art. The peracetic acid solution prepared by the invention can be directly used as a medical disinfectant after being diluted with distilled water to a prescribed concentration.
附图说明Description of drawings
图1为本发明所用以增强混合式微通道反应器为例连续流微通道反应器 系统装置图。Fig. 1 is an example of a continuous flow microchannel reactor system device diagram of an enhanced mixed microchannel reactor used in the present invention.
具体实施方式Detailed ways
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术 人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明, 均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。Unless otherwise defined, technical terms used in the following examples have the same meanings as commonly understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples are conventional biochemical reagents unless otherwise specified; the experimental methods are conventional methods unless otherwise specified.
下面结合实施例来详细说明本发明。The present invention will be described in detail below with reference to the embodiments.
实施例1Example 1
选用1块增强混合式微通道模块作为预混预热模块、6块增强混合式 微通道模块作为反应模块、1块增强混合式微通道模块作为冷却模块,按照 反应流程组成连续流微通道反应系统。One enhanced hybrid microchannel module was selected as the premix preheating module, six enhanced hybrid microchannel modules were used as the reaction module, and one enhanced hybrid microchannel module was used as the cooling module, and a continuous flow microchannel reaction system was formed according to the reaction process.
各模块的其微通道结构为增强混合型通道心形结构,且通道直径为 0.5~10mm;至于模块的数量设置,主要是保证能够有足够的停留时间即可。The microchannel structure of each module is an enhanced hybrid channel heart-shaped structure, and the diameter of the channel is 0.5-10mm; as for the number of modules, it is mainly to ensure that there is enough residence time.
预热模块和反应模块换热介质采用导热油,冷却模块换热介质采用乙二 醇/乙醇。根据微通道反应器强制传热原理,尽在该反应器进料口和出料口设 置两个测温点。反应前对微通道反应系统及连接管路分别进行除水、除油处 理,采用氮气对系统进行1.0MPa气密性检查。The heat exchange medium of the preheating module and the reaction module adopts heat conduction oil, and the heat exchange medium of the cooling module adopts ethylene glycol/ethanol. According to the principle of forced heat transfer in the microchannel reactor, two temperature measurement points are set at the inlet and outlet of the reactor. Before the reaction, the microchannel reaction system and the connecting pipelines were dewatered and deoiled respectively, and the air tightness of the system was checked by nitrogen gas at 1.0MPa.
步骤(1):按醋酸与过氧化氢摩尔比2:1,将醋酸、50wt%过氧化氢溶 液进行混合,然后分别加入反应液总质量1wt%的质量浓度98%浓硫酸和 0.2wt%的8-羟基喹啉并混合均匀,通过柱塞泵向微通道反应系统连续稳定泵 入反应液混合物,设定预热模块换热器温度为100℃。Step (1): according to the molar ratio of acetic acid and hydrogen peroxide of 2:1, acetic acid and 50wt% hydrogen peroxide solution are mixed, and then the mass concentration of 1wt% of the total mass of the reaction solution is 98% concentrated sulfuric acid and 0.2wt% are added respectively. 8-hydroxyquinoline was mixed uniformly, and the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 100°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为100℃,调节背压阀使反应体系压力维持在 1.0MPa,设定柱塞泵流量使得反应停留时间为15s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 100°C, adjust the back pressure valve to maintain the pressure of the reaction system at 1.0MPa, set the column The plug pump flow was such that the reaction residence time was 15 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为10℃,最后收集反应产物。Step (3): The product obtained from the outlet of the microchannel reaction module in step (2) is allowed to enter the cooling module, the cooling module heat exchange temperature is 10°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到24wt%。The peracetic acid content was determined to be 24 wt % by iodometry.
实施例2Example 2
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比1.1:1,将醋酸、70wt%过氧化氢 进行混合,然后分别加入反应液总质量0.5wt%的质量分数98%浓硫酸和 0.3wt%的乙二胺四乙酸并混合均匀,通过柱塞泵向微通道反应系统连续稳定 泵入反应液混合物,设定预热模块换热器温度为80℃。Step (1): According to the molar ratio of acetic acid and hydrogen peroxide of 1.1:1, acetic acid and 70wt% hydrogen peroxide are mixed, and then the total mass of the reaction solution is 0.5wt% and 98% concentrated sulfuric acid and 0.3wt% are respectively added. Ethylenediaminetetraacetic acid was mixed evenly, and the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 80°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为80℃,调节背压阀使反应体系压力维持在 0.5MPa,设定柱塞泵流量使得反应停留时间为33s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 80°C, adjust the back pressure valve to maintain the pressure of the reaction system at 0.5MPa, set the column The plug pump flow was such that the reaction residence time was 33 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为15℃,最后收集反应产物。Step (3): The product obtained from the outlet of the microchannel reaction module in step (2) is put into a cooling module, and the heat exchange temperature of the cooling module is 15°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到32wt%。The peracetic acid content was determined to be 32 wt% by iodometry.
实施例3Example 3
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比4:1,将醋酸、30wt%过氧化氢进 行混合,然后分别加入反应液总质量5wt%的甲磺酸和0.5wt%的磷酸钠并混 合均匀,通过柱塞泵向微通道反应系统连续稳定泵入反应液混合物,设定预 热模块换热器温度为148℃。Step (1): according to the molar ratio of acetic acid and hydrogen peroxide of 4:1, acetic acid and 30wt% hydrogen peroxide are mixed, and then 5wt% methanesulfonic acid and 0.5wt% sodium phosphate of the total mass of the reaction solution are respectively added and mixed. Evenly, the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 148°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为148℃,调节背压阀使反应体系压力维持在 1.3MPa,设定柱塞泵流量使得反应停留时间为10s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 148°C, adjust the back pressure valve to maintain the pressure of the reaction system at 1.3MPa, set the column The plug pump flow was such that the reaction residence time was 10 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为18℃,最后收集反应产物。Step (3): the product obtained from the outlet of the microchannel reaction module in step (2) is put into a cooling module, and the heat exchange temperature of the cooling module is 18°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到16.5wt%。The peracetic acid content was determined to be 16.5 wt % by iodometry.
实施例4Example 4
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比10:1,将醋酸、30wt%过氧化氢进 行混合,然后分别加入反应液总质量10wt%的苯磺酸和0.01wt%的焦磷酸钠 并混合均匀,通过柱塞泵向微通道反应系统连续稳定泵入反应液混合物,设 定预热模块换热器温度为130℃。Step (1): according to the molar ratio of acetic acid and hydrogen peroxide 10:1, acetic acid and 30wt% hydrogen peroxide are mixed, then 10wt% benzenesulfonic acid and 0.01wt% sodium pyrophosphate of the total mass of the reaction solution are added respectively, Mix evenly, continuously and stably pump the reaction mixture into the microchannel reaction system through a plunger pump, and set the temperature of the preheating module heat exchanger to 130°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为130℃,调节背压阀使反应体系压力维持在 1.9MPa,设定柱塞泵流量使得反应停留时间为162s。Step (2): After preheating in step (1), the reaction mixture continuously enters the microchannel reaction module, the temperature of the heat exchanger in the reaction module is set to 130°C, the back pressure valve is adjusted to maintain the pressure of the reaction system at 1.9MPa, and the column is set The plug pump flow was such that the reaction residence time was 162 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为25℃,最后收集反应产物。Step (3): the product obtained from the outlet of the microchannel reaction module in step (2) is allowed to enter the cooling module, the cooling module heat exchange temperature is 25°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到10wt%。The peracetic acid content was determined to reach 10 wt% by iodometric method.
实施例5Example 5
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比将醋酸、50wt%过氧化氢按摩尔 比1.5:1进行混合,然后分别加入反应液总质量2wt%的98%浓硫酸和 0.15wt%的羟基乙叉二磷酸并混合均匀,通过柱塞泵向微通道反应系统连续 稳定泵入反应液混合物,设定预热模块换热器温度为120℃。Step (1): mix acetic acid and 50wt% hydrogen peroxide in a molar ratio of 1.5:1 according to the molar ratio of acetic acid and hydrogen peroxide, then add 98% concentrated sulfuric acid and 0.15wt% hydroxyl group of 2wt% of the total mass of the reaction solution respectively Ethylene diphosphoric acid was mixed uniformly, and the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 120°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为120℃,调节背压阀使反应体系压力维持在 0.9MPa,设定柱塞泵流量使得反应停留时间为44s。Step (2): After preheating in step (1), the reaction mixture continuously enters the microchannel reaction module, the temperature of the heat exchanger in the reaction module is set to 120°C, the back pressure valve is adjusted to maintain the pressure of the reaction system at 0.9MPa, and the column is set The plug pump flow was such that the reaction residence time was 44 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为5℃,最后收集反应产物。Step (3): the product obtained from the outlet of the microchannel reaction module in step (2) is allowed to enter the cooling module, the cooling module heat exchange temperature is 5°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到25.6wt%。The peracetic acid content was determined to be 25.6 wt % by iodometry.
实施例6Example 6
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比2.5:1,将醋酸、70wt%过氧化氢 进行混合,然后分别加入反应液总质量1.3wt%的98%浓硫酸和0.2wt%的吡 啶-2,6-二甲酸并混合均匀,通过柱塞泵向微通道反应系统连续稳定泵入反应 液混合物,设定预热模块换热器温度为125℃。Step (1): according to the acetic acid and hydrogen peroxide molar ratio of 2.5:1, acetic acid and 70wt% hydrogen peroxide are mixed, and then 98% concentrated sulfuric acid and 0.2wt% pyridine- 2,6-dicarboxylic acid was mixed evenly, the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 125°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为125℃,调节背压阀使反应体系压力维持在 1.5MPa,设定柱塞泵流量使得反应停留时间为20s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 125°C, adjust the back pressure valve to maintain the pressure of the reaction system at 1.5MPa, set the column The plug pump flow was such that the reaction residence time was 20 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为15℃,最后收集反应产物。Step (3): The product obtained from the outlet of the microchannel reaction module in step (2) is put into a cooling module, and the heat exchange temperature of the cooling module is 15°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到30.8wt%。The peracetic acid content was determined to be 30.8 wt % by iodometry.
实施例7Example 7
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比2:1,将醋酸、50wt%过氧化氢进 行混合,然后分别加入反应液总质量1wt%的甲磺酸和0.2wt%的8-羟基喹啉 并混合均匀,通过柱塞泵向微通道反应系统连续稳定泵入反应液混合物,设 定预热模块换热器温度为110℃。Step (1): according to the molar ratio of acetic acid and hydrogen peroxide of 2:1, acetic acid and 50wt% hydrogen peroxide are mixed, and then 1wt% methanesulfonic acid and 0.2wt% 8-hydroxyquinoline of the total mass of the reaction solution are added respectively. The reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 110 °C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为110℃,调节背压阀使反应体系压力维持在 0.8MPa,设定柱塞泵流量使得反应停留时间为18s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 110°C, adjust the back pressure valve to maintain the pressure of the reaction system at 0.8MPa, set the column The plug pump flow was such that the reaction residence time was 18 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为20℃,最后收集反应产物。Step (3): the product obtained from the outlet of the microchannel reaction module in step (2) is allowed to enter the cooling module, the cooling module heat exchange temperature is 20°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到22wt%。The peracetic acid content was determined to be 22 wt% by iodometry.
实施例8Example 8
使用与实施例1同样的微通道反应器,并按照同样的连接方式及控制方 法。本实施例改变反应条件。The same microchannel reactor as in Example 1 was used, and the same connection method and control method were used. This example changes the reaction conditions.
步骤(1):按醋酸与过氧化氢摩尔比2:1,醋酸、70wt%过氧化氢进行 混合,然后分别加入反应液总质量1wt%的苯磺酸和0.08wt%的乙二胺四乙 酸并混合均匀,通过柱塞泵向微通道反应系统连续稳定泵入反应液混合物, 设定预热模块换热器温度为110℃。Step (1): according to the molar ratio of acetic acid and hydrogen peroxide 2:1, acetic acid and 70wt% hydrogen peroxide are mixed, and then 1wt% benzenesulfonic acid and 0.08wt% ethylenediaminetetraacetic acid of the total mass of the reaction solution are added respectively. The mixture was mixed evenly, and the reaction mixture was continuously and stably pumped into the microchannel reaction system through a plunger pump, and the temperature of the preheating module heat exchanger was set to 110°C.
步骤(2):使步骤(1)预热后反应混合物连续进入微通道反应模块, 设定反应模块换热器温度为110℃,调节背压阀使反应体系压力维持在 1.1MPa,设定柱塞泵流量使得反应停留时间为26s。Step (2): Make the reaction mixture continuously enter the microchannel reaction module after preheating in step (1), set the temperature of the heat exchanger of the reaction module to 110°C, adjust the back pressure valve to maintain the pressure of the reaction system at 1.1MPa, set the column The plug pump flow was such that the reaction residence time was 26 s.
步骤(3):使步骤(2)微通道反应模块出口得到的产物进入冷却模块, 冷却模块换热温度为30℃,最后收集反应产物。Step (3): the product obtained from the outlet of the microchannel reaction module in step (2) is allowed to enter the cooling module, the cooling module heat exchange temperature is 30°C, and the reaction product is finally collected.
采用碘量法测定过氧乙酸含量达到28.7wt%。The peracetic acid content was determined to be 28.7 wt % by iodometry.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本 发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在 本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the present invention. within the scope of protection.
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Cited By (4)
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| CN112825856A (en) * | 2021-02-09 | 2021-05-25 | 中国天辰工程有限公司 | A kind of method for rapidly preparing peracetic acid disinfectant with low-concentration hydrogen peroxide |
| CN112958079A (en) * | 2021-02-09 | 2021-06-15 | 中国天辰工程有限公司 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
| CN113105380A (en) * | 2021-04-16 | 2021-07-13 | 河北载和新材料科技有限公司 | Novel process for preparing peroxyacetic acid by using acetic acid as raw material through microreactor |
| CN114100527A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Reactive distillation device and method for producing peroxycarboxylic acid |
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| CN114100527A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Reactive distillation device and method for producing peroxycarboxylic acid |
| CN112825856A (en) * | 2021-02-09 | 2021-05-25 | 中国天辰工程有限公司 | A kind of method for rapidly preparing peracetic acid disinfectant with low-concentration hydrogen peroxide |
| CN112958079A (en) * | 2021-02-09 | 2021-06-15 | 中国天辰工程有限公司 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
| CN113105380A (en) * | 2021-04-16 | 2021-07-13 | 河北载和新材料科技有限公司 | Novel process for preparing peroxyacetic acid by using acetic acid as raw material through microreactor |
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