WO2019144647A1 - 一种高选择性2-甲基烯丙基氯的合成方法及合成反应器 - Google Patents

一种高选择性2-甲基烯丙基氯的合成方法及合成反应器 Download PDF

Info

Publication number
WO2019144647A1
WO2019144647A1 PCT/CN2018/109596 CN2018109596W WO2019144647A1 WO 2019144647 A1 WO2019144647 A1 WO 2019144647A1 CN 2018109596 W CN2018109596 W CN 2018109596W WO 2019144647 A1 WO2019144647 A1 WO 2019144647A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
synthesis
isobutylene
inlet tube
tube
Prior art date
Application number
PCT/CN2018/109596
Other languages
English (en)
French (fr)
Inventor
尹红
陈志荣
王新荣
王伟松
余渊荣
王胜利
王月芬
马振强
赵兴军
钱建芳
Original Assignee
浙江大学
浙江皇马科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江大学, 浙江皇马科技股份有限公司 filed Critical 浙江大学
Priority to US16/759,931 priority Critical patent/US11407698B2/en
Priority to KR1020207010733A priority patent/KR102364277B1/ko
Priority to JP2020560524A priority patent/JP7016472B2/ja
Publication of WO2019144647A1 publication Critical patent/WO2019144647A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2425—Tubular reactors in parallel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/04—Chloro-alkenes
    • C07C21/067—Allyl chloride; Methallyl chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • B01J2219/00792—One or more tube-shaped elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00869—Microreactors placed in parallel, on the same or on different supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00873—Heat exchange

Definitions

  • the invention relates to the chlorination reaction and equipment of organic substances, and belongs to the field of organic synthesis reaction.
  • 2-methyl-3-chloroallyl is an important organic synthesis intermediate widely used in medicine, pesticides, perfume monomers, polymer materials and other fields.
  • 2-Methyl-3-chloroallyl is usually obtained by gas phase chlorination of isobutylene with chlorine.
  • the early chlorination reaction is carried out in a tubular reactor with a cooling jacket.
  • the reaction temperature is below 100 ° C
  • the pressure is normal pressure
  • the reaction residence time is in the range of 0.5 seconds to several seconds.
  • DE 3402446 proposes that a certain amount of oxygen can be added during the reaction, but this method is prone to produce a mixture of excess isobutylene and oxygen, which poses a safety risk.
  • CN1030407 proposes that the method of injecting chlorine gas at multiple locations along the length of the jacket cooling reaction tube can solve the temperature fluctuation problem, but it is required to ensure that the chlorine gas flow rate reaches 150-260 m/s and the reaction selectivity is 86.5%. .
  • tubular reactor Since the tubular reactor has a small heat exchange area per unit volume of the reactor, a significant temperature distribution is generated along the length of the reaction tube, and local high temperature causes an increase in side reactions and a decrease in reaction selectivity.
  • CN1288119 uses a concentric nozzle while removing the heat of reaction by directly circulating the chlorinated reactant cycle with the reaction gas, but no selectivity data is given.
  • CN101182279 employs a plurality of concentric nozzles while removing the heat of reaction by direct chlorination of the reactants in contact with the reaction gas.
  • the highest selectivity given by the examples is 85.9%.
  • the disadvantage of the above chlorination technique is that the reaction site has no cooling surface and the temperature cannot be controlled. Therefore, there are many side reactions, low selectivity, and the nozzle or the nozzle is blocked by excessive chlorination coking.
  • CN202044960 proposes to adopt a flat nozzle in the utility model patent, and at the same time, the reaction heat is removed by direct contact with the reaction gas in the chlorination reactant cycle, but the patent does not give an example to solve the problem.
  • the coking problem has not been exemplified, and the content of the product in the reaction liquid has reached 88%.
  • the present invention proposes a highly selective 2-methylallyl chloride synthesis method which uses special equipment and has a stable reaction process.
  • the control is good; the reaction selectivity is high, the side reaction is small, and no coking phenomenon occurs.
  • the present invention also provides the synthesis reactor.
  • a highly selective 2-methyl-3-chloroallyl synthesis method in which isobutylene and chlorine are used as raw materials to undergo chlorination in a synthesis reactor with a cooling surface to obtain 2-methyl-3-chloro Allyl characterized in that the synthesis reactor is a synthetic reaction tube with an isobutylene inlet tube and a chlorine gas inlet tube, and the isobutylene and chlorine gas form a mixed raw material and enter a synthesis reaction tube for gas phase chlorination reaction, the chlorination
  • the reaction temperature is 0-30 ° C
  • the diameter of the isobutylene inlet tube, the chlorine gas inlet tube and the synthesis reaction tube is 0.2-0.5 mm
  • the cooling surface of the synthesis reactor has an actual reaction volume of 8000-20000 m 2 /m 3 The heat exchange area.
  • the molar ratio of isobutylene to chlorine is preferably from 1.005 to 1.02:1.
  • the chlorination reaction residence time is from 0.1 to 1 second.
  • a highly selective 2-methyl-3-chloroallyl synthesis reactor characterized in that the synthesis reactor is a synthesis reaction with an isobutylene inlet tube and a chlorine gas inlet tube wrapped in a cooling jacket
  • the tube, the isobutylene inlet tube, the chlorine gas inlet tube and the synthetic reaction tube are connected in a three-way form.
  • the isobutylene inlet tube, the chlorine gas inlet tube, and the synthetic reaction tube are connected in a T shape or a Y shape.
  • the isobutylene inlet tube and the chlorine gas inlet tube are connected in a U shape, and the upper end of the synthetic reaction tube is connected to the U-shaped bottom.
  • the isobutylene inlet tube, the chlorine gas inlet tube and the synthesis reaction tube have a diameter of 0.2 to 0.5 mm, and the cooling surface of the synthesis reactor has a heat exchange area of 8000 to 20,000 m 2 /m 3 in terms of an actual reaction volume.
  • a highly selective 2-methyl-3-chloroallyl synthesis reactor combination comprising a plurality of the above-described synthesis reactors, the cooling jackets of the plurality of synthesis reactors being in communication with one another.
  • the plurality of synthesis reactors are juxtaposed in the same cooling jacket.
  • the inventors of the present invention have found that the gas phase chlorination reaction of isobutylene is a strong exothermic reaction. Under the equimolar ratio of isobutylene to chlorine, the adiabatic temperature rise of the complete reaction can reach 440 ° C, and the higher the reaction temperature, the faster the reaction. The more side reactions, the more likely to cause coking problems. Therefore, in order to control the reaction temperature and increase the reaction selectivity, it is necessary to effectively control the reaction temperature.
  • Theoretical calculations and experimental verifications show that when the heat exchange area in the actual reaction volume reaches 8000 m 2 /m 3 or more and the reaction is carried out at 0 to 30 ° C, the reaction can be carried out at a substantially constant temperature, and the hot spot temperature is not Exceeded the set temperature of 3 °C.
  • the specially designed synthesis reactor of the present invention which is also called a microchannel reactor, can meet the requirements.
  • a T-type microchannel reactor is more suitable.
  • a slight excess of isobutylene molar ratio is suitable.
  • the reaction residence time is preferably 0.1 to 1 second.
  • the process of the invention controls the reaction temperature, increases the heat exchange area, and carries out the chlorination reaction in a tiny reaction tube, ensuring a constant reaction temperature, no coking and good selectivity.
  • the reaction process is stable and the controllability is good; the reaction selectivity is high, the side reaction is small, and no coking phenomenon occurs.
  • microchannel reactor of the present invention is carried out in a small reaction tube, a plurality of synthesis reactors can be combined in production to share the same cooling jacket, and the reaction efficiency can be improved.
  • Figure 1 is a schematic view showing the structure of a synthesis reactor of the present invention
  • Figure 2 is a schematic view showing the structure of a synthetic reactor combination of the present invention
  • the present invention is a synthesis reactor with a cooling jacket 1, which is an elongated reaction tube 4, to which a raw material chlorine gas inlet pipe 2 and isobutylene pass are connected at the upper port of the reaction tube 4.
  • the inlet pipe 3 and the lower port are connected with the reaction product outlet pipe 5; the chlorine inlet pipe 2, the isobutylene pipe 3 and the reaction pipe 4 of the present invention only need to ensure that the two raw materials enter the reaction pipe 4 at the same time for mixing reaction.
  • the other end of the reaction tube 4 is a product outlet, and preferably: the chlorine inlet tube 2, the isobutylene inlet tube 3, and the reaction tube 4 are T-shaped or Y-shaped.
  • each reactor is a separate reaction tube 4, with independent chlorine gas inlet pipe 2 and isobutylene inlet pipe 3 and reaction product outlet pipe 5,
  • the reactors share the same cooling jacket 1, and a plurality of synthetic reactors of the present invention are juxtaposed and fixed in the same cooling jacket, which can effectively utilize space and utilize energy, and improve reaction efficiency.
  • the composition of the liquid product was sampled from the outlet of the reactor, and its mass content was: 89.6% for 2-methylallyl chloride, 2.3% for chloro-tert-butane, 1.3% for isobutenyl chloride, and unclear
  • the butane was 5.6% and the dichloroisobutylene was 1.2%; the 2-methylallyl chloride selectivity was calculated to be 91.4%.
  • microchannel reactor channel diameter 0.5 mm, heat exchange area calculated according to the actual reaction volume is 8000 m 2 /m 3 ) as shown in Fig. 1, isobutylene and chlorine gas are respectively introduced, and the flow rates of isobutylene and chlorine gas are controlled by adjustment,
  • the reaction residence time was brought to 0.1 second, the molar ratio of isobutylene to chlorine was 1.02:1, and the reaction temperature was controlled by low temperature water to be 30 °C.
  • 2-methylallyl chloride was 88.7%, chloro-tert-butane 2.1%, isobutylene chloride 1.5%, dichloro-tert Butane 6.0%, dichloroisobutylene 1.5%; thus the 2-methylallyl chloride selectivity was calculated to be 90.5%.
  • the composition of the liquid product was sampled from the outlet of the reactor, and its mass content was: 89.3% of 2-methylallyl chloride, 2.3% of chloro-tert-butane, 1.4% of isobutylene chloride, and unclear
  • the butane was 5.7% and the dichloroisobutylene was 1.3%; the selectivity of 2-methylallyl chloride was calculated to be 91.1%.
  • the composition of the liquid product was sampled from the outlet of the reactor, and its mass content was: 2-methylallyl chloride 89.1%, chloro-tert-butane 2.2%, isobutenyl chloride 1.5%, dichloro-tert Butane was 5.8% and dichloroisobutylene was 1.4%; the 2-methylallyl chloride selectivity was calculated to be 90.9%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及一种高选择性2-甲基烯丙基氯的合成方法及合成反应器，是以异丁烯和氯气为原料，在有冷却面的微通道反应器中进行气相氯化反应得到。异丁烯和氯气在T字型微通道反应器中进行反应，其混合速度极快，同时，巨大的单位反应体积换热面积可保证反应在基本恒定的温度下稳定进行，可控性好；因此可有效抑制因局部温度过高引起的副反应，反应选择性高，不会产生结焦现象。

Description

一种高选择性2-甲基烯丙基氯的合成方法及合成反应器 技术领域
本发明涉及有机物的氯化反应及装备，属于有机合成反应领域。
背景技术
2-甲基-3-氯烯丙基是一种重要的有机合成中间体，广泛应用于医药、农药、香料单体、高分子材料等领域。
2-甲基-3-氯烯丙基通常由异丁烯与氯气进行气相氯化反应得到。
早期氯化反应都在带有冷却夹套的管式反应器中进行，反应温度在100℃以下，压力为常压，反应停留时间在0.5秒至数秒的范围，为了避免深度氯化副反应，通常需要保持异丁烯过量，两种原料以喷射方式加入反应管中。
为避免反应过程的温度产生波动，DE3402446提出可在反应过程中加入一定量的氧气，但该方法易产生过量异丁烯与氧气的混合物，有安全风险。为此，CN1030407提出将氯气在沿夹套冷却反应管长度方向的多个位置注入的方法可以解决温度波动问题，但要求保证氯气的流速达到150-260米/秒，反应选择性最高为86.5％。
管式反应器由于单位体积反应器的换热面积小，因此，在反应管沿长度方向会产生明显的温度分布，局部高温会导致副反应增加，反应选择性下降。
针对管式反应器存在的问题，CN1288119采用同心喷嘴，同时以氯化反应物循环直接与反应气体接触冷却的方式移除反应热，但没有给出选择性数据。
CN101182279采用多个同心喷头，同时以氯化反应物循环直接与反应气体接触冷却的方式移除反应热，实施例给出的最高选择性为85.9％。
上述氯化技术的缺点是反应场所没有冷却面，温度无法控制，因此，副反应多，选择性低，且会因过度氯化结焦堵塞喷嘴或喷头。
针对喷头容易结焦的问题，CN202044960在实用新型专利中提出采用扁型喷嘴，同时以氯化反应物循环直接与反应气体接触冷却的方式移除反应热，但专利中并未给出实施例证明解决了结焦问题，也没有实施例证明反应液中产物含量达到了88％。
发明内容
针对文献报道的2-甲基烯丙基氯合成过程中存在的问题，本发明提出了一种高选择性2- 甲基烯丙基氯合成方法，该反应采用特制设备，反应过程稳定，可控性好；反应选择性高，副反应少，不会产生结焦现象。
本发明同时提供该合成反应器。
一种高选择性2-甲基-3-氯烯丙基的合成方法，以异丁烯和氯气为原料，在带有冷却面的合成反应器中发生氯化反应得到2-甲基-3-氯烯丙基，其特征是：所述合成反应器为带有异丁烯通入管和氯气通入管的合成反应管，所述异丁烯、氯气形成混合原料进入合成反应管进行气相氯化反应，所述氯化反应温度为0-30℃,所述异丁烯通入管、氯气通入管和合成反应管的直径为0.2-0.5毫米,所述合成反应器的冷却面具有以实际反应体积计8000-20000m 2/m 3的换热面积。
所述氯化反应中异丁烯稍微过量。
所述异丁烯与氯气的摩尔比优选为1.005-1.02:1。
所述氯化反应停留时间为0.1-1秒。
一种高选择性2-甲基-3-氯烯丙基的合成反应器，其特征在于：所述合成反应器为包裹在冷却夹套内的带有异丁烯通入管和氯气通入管的合成反应管，所述异丁烯通入管、氯气通入管以及合成反应管呈三通形式连接。
所述异丁烯通入管、氯气通入管以及合成反应管呈T形或Y形连接。
所述异丁烯通入管、氯气通入管连接形U形，所述合成反应管的上端与U形底部连接。
所述异丁烯通入管、氯气通入管和合成反应管的直径为0.2-0.5毫米,所述合成反应器的冷却面具有以实际反应体积计8000-20000m 2/m 3的换热面积。
一种高选择性2-甲基-3-氯烯丙基的合成反应器组合，含有若干个上述合成反应器，所述若干个合成反应器的冷却夹套相互连通。
所述若干个合成反应器并列固定于同一个冷却夹套中。
本发明的发明人研究发现，异丁烯的气相氯化反应是强放热反应，在异丁烯与氯气等摩尔比条件下，完全反应的绝热温升可达到440℃，并且反应温度越高，反应越快，副反应越多，容易导致结焦问题。因此，要想控制反应温度，提高反应选择性，就必须有效控制反应温度。经过理论计算和实验验证表明，当以实际反应体积计的换热面积达到8000m 2/m 3以上，且在0～30℃条件下反应时，反应可以在基本恒定的温度下进行，热点温度不超过设定温度3℃。要达到这么大的单位反应体积换热面积，只有将反应通道直径缩小到0.5毫米以下才有可能，本发明特别设计的合成反应器又称为微通道反应器正好可以满足要求。为促进异丁烯与氯气的混合，T型微通道反应器更加适合。为保证选择性，稍微过量的异丁烯摩尔比是合适的。为保证氯气反应充分，反应停留时间以0.1～1秒为宜。
本发明工艺为控制反应温度，提高换热面积，将氯化反应在微小的反应管内进行，保证了反应温度的恒定，不结焦且选择性好。
为实现本发明工艺设计的微通道反应器进行异丁烯的氯化反应，反应过程稳定，可控性好；反应选择性高，副反应少，不会产生结焦现象。
本发明的微通道反应器因为是在微小的反应管内进行的，因此在生产中可以将多个合成反应器组合在一起，共用同一冷却夹套，可以提高的反应效率。
附图说明
图1是本发明合成反应器的结构示意图，
图2是本发明合成反应器组合的结构示意图，
1－冷却夹套，2－氯气通入管，3－异丁烯通入管，4－反应管，5－反应产物导出管。
具体实施方式
下面结合附图和实施例，对本发明的技术方案做进一步说明。
如图1所示，本发明是带有冷却夹套1的合成反应器，该反应器为一根细长的反应管4，在反应管4的上端口连接有原料氯气通入管2和异丁烯通入管3，下端口连接有反应产物导出管5；本发明氯入通入管2、异丁烯通入管3与反应管4的连接方式只需要保证两原料是同时进入反应管4的一端进行混合反应即可，如呈三通形式连接；反应管4的另一端则是产物出口，优选：氯入通入管2、异丁烯通入管3和反应管4呈T形或Y形。
如图2所示，多个本发明合成反应器组合的连接方式，每个反应器是独立的反应管4，带有独立的氯气通入管2和异丁烯通入管3和反应产物导出管5，多个反应器共有同一个冷却夹套1，相当地将多个本发明的合成反应器并列固定在同一个冷却夹套中，可以有效利用空间和利用能源，提高的反应效率。
实施例1
在如图1所示的微通道反应器(通道直径为0.2毫米，按实际反应体积计算的换热面积为20000m 2/m 3)中分别通入异丁烯和氯气，通过调节控制异丁烯和氯气流量，使反应停留时间达到1秒，异丁烯与氯气的摩尔比为1.005:1，通过冷冻盐水控制反应温度为0℃。稳定运行30分钟以后，从反应器出口取样分析液体产物组成，其质量含量为：2-甲基烯丙基氯为89.6％，氯代叔丁烷2.3％，异丁烯基氯1.3％，二氯叔丁烷5.6％，二氯异丁烯1.2％；以此计算2-甲基烯丙基氯选择性为91.4％。
实施例2
在如图1所示的微通道反应器(通道直径为0.5毫米，按实际反应体积计算的换热面积 为8000m 2/m 3)中分别通入异丁烯和氯气，通过调节控制异丁烯和氯气流量，使反应停留时间达到0.1秒，异丁烯与氯气的摩尔比为1.02:1，通过低温水控制反应温度为30℃。稳定运行30分钟以后，从反应器出口取样分析液体产物组成，其质量含量为：2-甲基烯丙基氯为88.7％，氯代叔丁烷2.1％，异丁烯基氯1.5％，二氯叔丁烷6.0％，二氯异丁烯1.5％；以此计算2-甲基烯丙基氯选择性为90.5％。
实施例3
在如图1所示的微通道反应器(通道直径为0.4毫米，按实际反应体积计算的换热面积为10000m 2/m 3)中分别通入异丁烯和氯气，通过调节控制异丁烯和氯气流量，使反应停留时间达到0.5秒，异丁烯与氯气的摩尔比为1.01:1，通过冷冻盐水控制反应温度为10℃。稳定运行30分钟以后，从反应器出口取样分析液体产物组成，其质量含量为：2-甲基烯丙基氯为89.3％，氯代叔丁烷2.3％，异丁烯基氯1.4％，二氯叔丁烷5.7％，二氯异丁烯1.3％；以此计算2-甲基烯丙基氯选择性为91.1％。
实施例4
在如图2所示的微通道反应器(通道直径为0.3毫米，按实际反应体积计算的换热面积为13330m 2/m 3)中分别通入异丁烯和氯气，通过调节控制异丁烯和氯气流量，使反应停留时间达到0.3秒，异丁烯与氯气的摩尔比为1.01:1，通过低温水控制反应温度为20℃。稳定运行30分钟以后，从反应器出口取样分析液体产物组成，其质量含量为：2-甲基烯丙基氯为89.1％，氯代叔丁烷2.2％，异丁烯基氯1.5％，二氯叔丁烷5.8％，二氯异丁烯1.4％；以此计算2-甲基烯丙基氯选择性为90.9％。

Claims (10)

  1. 一种高选择性2-甲基-3-氯烯丙基的合成方法，以异丁烯和氯气为原料，在带有冷却面的合成反应器中发生氯化反应得到2-甲基-3-氯烯丙基，其特征是：所述合成反应器为带有异丁烯通入管和氯气通入管的合成反应管，所述异丁烯、氯气形成混合原料进入合成反应管进行气相氯化反应，所述异丁烯通入管、氯气通入管和合成反应管的直径为0.2-0.5毫米,所述合成反应器的冷却面具有以实际反应体积计8000-20000m 2/m 3的换热面积。
  2. 根据权利要求1所述的合成方法，所述氯化反应中异丁烯稍微过量。
  3. 根据权利要求2所述的合成方法，所述异丁烯与氯气的摩尔比优选为1.005-1.02:1。
  4. 根据权利要求1所述的合成方法，所述氯化反应温度为0-30℃,氯化反应停留时间为0.1-1秒。
  5. 一种高选择性2-甲基-3-氯烯丙基的合成反应器，其特征在于：所述合成反应器为包裹在冷却夹套内的带有异丁烯通入管和氯气通入管的合成反应管，所述异丁烯通入管、氯气通入管以及合成反应管呈三通形式连接。
  6. 根据权利要求5所述的合成反应器，所述异丁烯通入管、氯气通入管以及合成反应管呈T形或Y形连接。
  7. 根据权利要求5所述的合成反应器，所述异丁烯通入管、氯气通入管连接形U形，所述合成反应管的上端与U形外底部连接。
  8. 根据权利要求5所述的合成反应器，所述异丁烯通入管、氯气通入管和合成反应管的直径为0.2-0.5毫米,所述合成反应器的冷却面具有以实际反应体积计8000-20000m2/m3的换热面积。
  9. 一种高选择性2-甲基-3-氯烯丙基的合成反应器组合，含有若干个权利要求5－8任一所述的合成反应器，所述若干个合成反应器的冷却夹套相互连通。
  10. 根据权利要求9所述的合成反应器组合，所述若干个合成反应器并列固定于同一个冷却夹套内。
PCT/CN2018/109596 2018-01-29 2018-10-10 一种高选择性2-甲基烯丙基氯的合成方法及合成反应器 WO2019144647A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/759,931 US11407698B2 (en) 2018-01-29 2018-10-10 Synthesis method for highly selective 2-methylallyl chloride and synthesis reactor thereof
KR1020207010733A KR102364277B1 (ko) 2018-01-29 2018-10-10 고선택성 2-메틸알릴 클로라이드의 합성 방법 및 합성 반응기
JP2020560524A JP7016472B2 (ja) 2018-01-29 2018-10-10 高選択率で２－メチルアリルクロリドを合成する方法及び合成反応器

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201810085845.3 2018-01-29
CN201810085845 2018-01-29
CN201810109001.8 2018-02-05
CN201810109001.8A CN108164389B (zh) 2018-01-29 2018-02-05 一种高选择性2-甲基烯丙基氯的合成方法及合成反应器

Publications (1)

Publication Number Publication Date
WO2019144647A1 true WO2019144647A1 (zh) 2019-08-01

Family

ID=62512621

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/109596 WO2019144647A1 (zh) 2018-01-29 2018-10-10 一种高选择性2-甲基烯丙基氯的合成方法及合成反应器

Country Status (5)

Country Link
US (1) US11407698B2 (zh)
JP (1) JP7016472B2 (zh)
KR (1) KR102364277B1 (zh)
CN (1) CN108164389B (zh)
WO (1) WO2019144647A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108164388B (zh) * 2018-02-09 2020-07-10 浙江大学 一种高含量2-甲基烯丙基氯的制备方法
CN110642668A (zh) * 2019-10-19 2020-01-03 湘潭大学 一种低碳烯烃氯化的制备方法
CN110642667A (zh) * 2019-10-19 2020-01-03 湘潭大学 一种由异丁烯氯化联产甲基氯丙烯和氯代叔丁烷的方法
CN112174775B (zh) * 2020-09-29 2023-03-17 浙江皇马科技股份有限公司 一种高氯含量有机混合物的脱色方法
CN114920621B (zh) * 2022-06-01 2023-09-22 浙江皇马科技股份有限公司 一种高选择性3-氯-2-氯甲基丙烯的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2604439A (en) * 1952-07-22 Distillation of
GB684577A (en) * 1949-11-26 1952-12-17 Bataafsche Petroleum Process for separating alkenyl halide mixtures by distillation
CN1456544A (zh) * 2003-05-14 2003-11-19 刘德全 甲代烯丙基氯的合成工艺及设备
CN108164388A (zh) * 2018-02-09 2018-06-15 浙江大学 一种高含量2-甲基烯丙基氯的制备方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53124202A (en) * 1977-04-05 1978-10-30 Toagosei Chem Ind Co Ltd Continuous preparation of methallyl chloride
DE3402446A1 (de) * 1984-01-25 1985-07-25 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von methallylchlorid
DE3721472A1 (de) 1987-06-30 1989-02-02 Huels Chemische Werke Ag Verfahren zur herstellung von methallylchlorid
CN1288119A (zh) 1999-09-09 2001-03-21 吴大乐 Wb型双支点摆线减速机
DE10001317A1 (de) * 2000-01-14 2001-07-19 Merck Patent Gmbh Reaktion von Carbonylverbindungen mit metallorganischen Reagenzien
DE10106952C2 (de) * 2001-02-15 2003-01-16 Cognis Deutschland Gmbh Chip-Reaktor
EP1827678B1 (en) * 2004-08-31 2012-07-18 Total Synthesis Ltd. Method and apparatus for performing micro-scale chemical reactions
EP1915214A4 (en) * 2005-08-11 2017-11-08 GlaxoSmithKline LLC Flow reactor method and apparatus
CN101182279B (zh) 2007-01-22 2010-09-29 丁凌 3-氯-2-甲基-1-丙烯的制备方法
CN200995994Y (zh) * 2007-01-22 2007-12-26 丁凌 由氯和异丁烯制备3－氯－2－甲基－1－丙烯的氯化反应装置
JP5092443B2 (ja) * 2007-02-20 2012-12-05 富士ゼロックス株式会社 マイクロ流体デバイス、反応装置、及び、反応方法
CN202044960U (zh) * 2011-04-12 2011-11-23 宁波锦莱化工有限公司 一种扁形氯化反应装置
CN102872786A (zh) * 2012-09-11 2013-01-16 宁波锦莱化工有限公司 一种扁形氯化反应装置
EP3218098B1 (en) * 2014-11-11 2022-05-11 H. C. Starck Inc Microreactor systems and methods
CN106608811B (zh) * 2015-10-27 2019-09-17 江西天宇化工有限公司 一种采用微通道反应器制备氯丙烷的方法
EP3395436B1 (en) * 2015-12-25 2023-08-09 Ushio Chemix Corporation Microreactor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2604439A (en) * 1952-07-22 Distillation of
GB684577A (en) * 1949-11-26 1952-12-17 Bataafsche Petroleum Process for separating alkenyl halide mixtures by distillation
CN1456544A (zh) * 2003-05-14 2003-11-19 刘德全 甲代烯丙基氯的合成工艺及设备
CN108164388A (zh) * 2018-02-09 2018-06-15 浙江大学 一种高含量2-甲基烯丙基氯的制备方法

Also Published As

Publication number Publication date
JP2021511373A (ja) 2021-05-06
US11407698B2 (en) 2022-08-09
US20210179520A1 (en) 2021-06-17
JP7016472B2 (ja) 2022-02-07
CN108164389A (zh) 2018-06-15
KR20200049862A (ko) 2020-05-08
KR102364277B1 (ko) 2022-02-17
CN108164389B (zh) 2020-07-10

Similar Documents

Publication Publication Date Title
WO2019144647A1 (zh) 一种高选择性2-甲基烯丙基氯的合成方法及合成反应器
EP3490961B1 (en) Oxidative dehydrogenation (odh) of ethane
CN102405202A (zh) 制备2-氯-3,3,3-三氟丙烯的方法
CN105536654B (zh) 一种大型轴向多段混合换热式丁烯氧化脱氢反应器
CA3031565A1 (en) Oxidative dehydrogenation (odh) of ethane
CN106831306A (zh) 甲烷氧化偶联制乙烯反应工艺
CN106732201A (zh) 甲烷氧化偶联制乙烯反应器
KR20070057883A (ko) 수평 반응 용기
CN108654549B (zh) 一种油酸酰胺连续化合成装置及其使用方法
CN103813852A (zh) 用于由甲醇制备二甲醚的冷却反应器
JPS60225632A (ja) 反応器
CN211078991U (zh) 一种合成4-氰基吡啶的装置
CN105585465B (zh) 一种3,3‑二甲基丁醛制备工艺和制备装置
JP2019522013A5 (zh)
JP2019522012A (ja) ペンタクロロプロパンの製造及び転化方法
CN207525169U (zh) 一种连续化生产硝基甲烷的反应器
CN107857703A (zh) 一种连续化生产硝基甲烷的反应器及方法
CN110327846A (zh) 等温反应器及利用其进行甲烷化反应的装置和方法
CN114920621B (zh) 一种高选择性3-氯-2-氯甲基丙烯的制备方法
JPS6029369B2 (ja) 酸化エチレン高付加物の製法
CN202447060U (zh) 多管氧化反应器
RU2452559C2 (ru) Реактор паровой и пароуглекислотной конверсии легких углеводородов для получения газа, содержащего водород и окись углерода
CN106588603A (zh) 一种邻氟甲苯连续氧化制备邻氟苯甲醛的方法
CA3031565C (en) Oxidative dehydrogenation (odh) of ethane
CN114605222A (zh) 一种高效合成氯甲烷的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18902858

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20207010733

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2020560524

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18902858

Country of ref document: EP

Kind code of ref document: A1