Continuous production system and method of fenpropimorph

Abstract

The present invention provides a continuous production system and continuous production method of fenpropimorph. The system includes a continuous aldehyde amine condensation hydrogenation reaction device, a first continuous gas-liquid separation device, a continuous mixing device, a continuous hydrogenation dehalogenation reaction device, a second continuous gas-liquid separation device and a continuous rectification device. The continuous aldehyde amine condensation hydrogenation reaction device is used to make 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine carry out continuous aldehyde amine condensation hydrogenation reaction in the presence of a first catalyst, a first hydrogen and a solvent, and obtain a first product system containing a condensation hydrogenation reaction product; the continuous hydrogenation dehalogenation reaction device is used to make the first liquid phase product and the second hydrogen carry out continuous hydrogenation dehalogenation reaction in the presence of a second catalyst and an acid binding agent, and then obtain fenpropimorph with higher purity after purification by a continuous rectification device. Production using the above system can improve product selectivity and the yield of fenpropimorph, and achieve efficient, continuous and stable production.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a continuous production system and a continuous production method of fenpropimorph. Background Art

[0002] Fenpropimorph, also known as Fenpropimorph, is a broad-spectrum, systemic morphine fungicide and ergosterol biosynthesis inhibitor with preventive and therapeutic effects. It is mainly used to control powdery mildew, leaf rust, stripe rust of barley and wheat, smut of cereals, and damping-off of cotton. It is particularly effective in controlling powdery mildew of cereals, and also has a good preventive effect on rust. In view of the wide application of fenpropimorph in the field of crop protection, its efficient and economical synthesis process has attracted widespread attention in the industry.

[0003] The existing synthesis method of fenpropimorph is to use 2-methyl-3-(p-tert-butyl)phenylacrolein as a raw material to obtain 2-methyl-3-(p-tert-butyl)phenylpropanal through a selective hydrogenation reaction, and then react with 2,6-dimethylmorpholine to obtain fenpropimorph. However, it is difficult to control the protection of the aldehyde group during the hydrogenation reaction, and it is easy to over-hydrogenate and produce more impurity alcohols, thereby reducing the selectivity of the product and resulting in a low yield of fenpropimorph.

[0004] At present, the existing synthesis method of fenpropimorph mainly adopts intermittent production. The intermittent process has the problems of complex process, low production efficiency, high energy consumption and high cost. In addition, the process of preparing fenpropimorph involves high-risk processes such as hydrogenation. The intermittent autoclave reaction has the problems of large reaction heat release, low heat transfer efficiency, and easy heat accumulation, which leads to the risk of explosion. In addition, the intermittent autoclave reaction uses a large amount of catalyst and is complicated to recover, which increases the cost and difficulty of safety control. As the reaction system expands, it becomes difficult to accurately control the reaction parameters, which easily leads to reaction out of control, resulting in batch differences in product yield and purity, and the overall yield can only reach 60-70%.

[0005] In summary, researching and developing a continuous production system and method for fenpropimorph is of great significance for improving the product selectivity and yield of fenpropimorph, as well as for improving its production efficiency and production safety and reducing production costs. Summary of the invention

[0006] The main purpose of the present invention is to provide a continuous production system and a continuous production method of fenpropimorph, so as to solve the problems of poor selectivity and low yield in the fenpropimorph synthesis route in the prior art, and the problems of complex operation, poor safety, low production efficiency, unstable product yield and purity, and high cost in the fenpropimorph production process.

[0007] In order to achieve the above-mentioned purpose, the present invention provides a continuous production system of butylfenmorph, which includes a continuous aldehyde amine condensation hydrogenation reaction device, a first continuous gas-liquid separation device, a continuous mixing device, a continuous hydrogenation dehalogenation reaction device, a second continuous gas-liquid separation device and a continuous distillation device. The continuous aldehyde amine condensation hydrogenation reaction device is used to carry out a continuous aldehyde amine condensation hydrogenation reaction of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine in the presence of a first catalyst, a first hydrogen and a solvent to obtain a first product system containing a condensation hydrogenation reaction product; the continuous aldehyde amine condensation hydrogenation reaction device is provided with a raw material inlet, a first hydrogen inlet and a first product system outlet; the raw material inlet is used to introduce a first mixed liquid containing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and a solvent; The aldehyde-amine condensation hydrogenation reaction device is provided with a first catalyst bed layer inside, and the first catalyst is loaded in the first catalyst bed layer; the first continuous gas-liquid separation device is used to separate the first product system to obtain a first liquid phase product and a first recovered hydrogen; the first continuous gas-liquid separation device is provided with a first product system inlet, a first liquid phase product outlet and a first recovered hydrogen outlet; the first recovered hydrogen outlet is connected to the first hydrogen inlet; the continuous mixing device is used to mix the first liquid phase product with an acid binding agent to obtain a second mixed liquid; the continuous mixing device is provided with the first liquid phase product The continuous hydrodehalogenation reaction device is used to carry out a continuous hydrodehalogenation reaction of the first liquid phase product with the second hydrogen under the catalysis of the second catalyst and the presence of the acid binding agent to obtain a second product system containing fenpropimorph; the continuous hydrodehalogenation reaction device is provided with a mixed liquid inlet, a second hydrogen inlet and a second product system outlet; the mixed liquid inlet is connected with the mixed liquid outlet; a second catalyst bed is arranged inside the continuous hydrodehalogenation reaction device, and the second catalyst is loaded in the second catalyst bed; a second continuous gas-liquid separation device is used to separate the second product system to obtain a second liquid phase product and a second recovered hydrogen; the second continuous gas-liquid separation device is provided with a second product system inlet, a second liquid phase product outlet and a second recovered hydrogen outlet; the second product system inlet is connected with the second product system outlet, and the second recovered hydrogen outlet is connected with the first hydrogen inlet and / or the second hydrogen inlet; the continuous distillation device is provided with a second liquid phase product inlet and a fenpropimorph outlet, and the second liquid phase product inlet is connected with the second liquid phase product outlet.

[0008] Furthermore, the continuous distillation device is also provided with an outlet for recovering 2,6-dimethylmorpholine, an outlet for recovering an acid binding agent and an outlet for recovering a solvent; the outlet for recovering 2,6-dimethylmorpholine is connected to the raw material inlet; the outlet for recovering an acid binding agent is connected to the acid binding agent inlet; and the outlet for recovering a solvent is connected to the raw material inlet.

[0009] Furthermore, the continuous distillation device is a plate tower or a packed tower.

[0010] Furthermore, the continuous aldehyde-amine condensation hydrogenation reaction unit and the continuous hydrogenation dehalogenation reaction unit are each independently a continuous fixed bed reactor; preferably, the continuous production system comprises at least two continuous aldehyde-amine condensation hydrogenation reaction units arranged in series; preferably, the continuous production system comprises at least two continuous hydrogenation dehalogenation reaction units arranged in series.

[0011] Furthermore, the outside of the continuous aldehyde-amine condensation hydrogenation reaction device and the outside of the continuous hydrogenation dehalogenation reaction device are each independently provided with a first heating component, and the first heating component is filled with a heat exchange medium; preferably, the inside of the continuous aldehyde-amine condensation hydrogenation reaction device and the continuous hydrogenation dehalogenation reaction device are each independently provided with a second heating component.

[0012] Furthermore, the continuous mixing device is a continuous microchannel mixer.

[0013] Furthermore, the loading amount of the first catalyst is 10 to 90 vol % based on the volume percentage of the continuous aldehyde-amine condensation hydrogenation reaction device.

[0014] Furthermore, the loading amount of the second catalyst is 10 to 90 vol % based on the volume percentage of the continuous hydrodehalogenation reaction device.

[0015] Furthermore, the first continuous gas-liquid separation device and the second continuous gas-liquid separation device are each independently selected from a gravity sedimentation separator, a baffle separator or a packing separator.

[0016] In order to achieve the above-mentioned purpose, another aspect of the present invention further provides a continuous production method of fenpropimorph, which continuously produces fenpropimorph using the continuous production system of fenpropimorph provided by the present application. The continuous production method comprises: step S1, in the presence of a first catalyst and a first hydrogen and a solvent, 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine are subjected to a continuous aldehyde amine condensation hydrogenation reaction in a continuous aldehyde amine condensation hydrogenation reaction device to obtain a first product system containing a condensation hydrogenation reaction product; step S2, using a first continuous gas-liquid separation device to perform a first continuous gas-liquid separation on the first product system to obtain a first liquid phase product and a first recovered hydrogen, and at least a portion of the first The recovered hydrogen is returned to step S1; step S3, the first liquid phase product and the acid binding agent are continuously mixed by a continuous mixing device to obtain a second mixed liquid; step S4, under the catalysis of a second catalyst and in the presence of an acid binding agent, the first liquid phase product and the second hydrogen are subjected to a continuous hydrodehalogenation reaction in a continuous hydrodehalogenation reaction device to obtain a second product system containing fenpropimorph; step S5, the second product system is subjected to a second continuous gas-liquid separation by a second continuous gas-liquid separation device to obtain a second liquid phase product and a second recovered hydrogen, and at least part of the second recovered hydrogen is returned to step S1 and / or step S4; step S6, the second liquid phase product is continuously distilled by a continuous rectification device to obtain fenpropimorph.

[0017] Furthermore, the reaction temperature of the continuous aldehyde amine condensation hydrogenation reaction is 80-120° C., and the reaction pressure is 0.5-6 MPa.

[0018] Further, the feed rate ratio of the first hydrogen gas to 4-tert-butyl-β-chloro-α-methylcinnamaldehyde is (236-950) mL / min:1.0 g / min.

[0019] Furthermore, in the continuous aldehyde amine condensation hydrogenation reaction device, the liquid hourly space velocity of the first mixed liquid is 0.034 to 0.21 h -1 .

[0020] Furthermore, the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:(0.49-0.98); preferably, the weight ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to the volume ratio of the solvent is 1 g:(5-10) mL.

[0021] Furthermore, the reaction temperature of the continuous hydrodehalogenation reaction is 85-125° C., and the reaction pressure is 0.5-1.5 MPa.

[0022] Furthermore, the feed rate ratio of the second hydrogen to the first liquid phase product is (101-603) mL / min:1.0 g / min.

[0023] Furthermore, in the continuous mixing device, the feed rate ratio of the first liquid phase product to the acid binding agent is 1:(0.3-0.5); the residence time of the first liquid phase product and the acid binding agent is independently 1-10 minutes.

[0024] Furthermore, in the continuous hydrodehalogenation reaction device, the liquid hourly space velocity of the second mixed liquid is 0.3 to 0.9 h -1 .

[0025] Further, the solvent is selected from one or more of the group consisting of methanol, ethanol, n-butanol, isobutanol, tert-butanol, isopropanol, ethylene glycol, ethyl acetate and isopropyl acetate.

[0026] Furthermore, the first catalyst is a supported catalyst; preferably, the active ingredient in the first catalyst is selected from one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium; more preferably, the first catalyst is selected from one or more of the group consisting of nickel / alumina catalyst, palladium-carbon catalyst and platinum / TS-1 catalyst.

[0027] Further, the first liquid phase product is selected from one or more of (2R,6S)-4-((Z)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine, (2R,6S)-4-(3-(4-(tert-butyl)phenyl)-3-chloro-2-methylpropyl)-2,6-dimethylmorpholine and (2R,6S)-4-((E)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine.

[0028] Further, the acid binding agent is a base; the base is selected from an organic base and / or an inorganic base; preferably, the organic base is selected from one or more of the group consisting of trimethylamine, triethylamine, diethylamine and ethylenediamine; preferably, the inorganic base is selected from one or more of the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate.

[0029] Furthermore, the second catalyst is a supported catalyst; preferably, the active ingredient in the second catalyst is selected from one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium; more preferably, the second catalyst is selected from one or more of the group consisting of palladium / alumina catalyst, platinum / silicon dioxide catalyst, ruthenium / ZSM-5 catalyst and rhodium / TS-1 catalyst.

[0030] Furthermore, in step S6, recovered 2,6-dimethylmorpholine, recovered acid-binding agent and recovered solvent are obtained; at least part of the recovered 2,6-dimethylmorpholine and at least part of the recovered solvent are returned to step S1, and at least part of the recovered acid-binding agent is returned to step S3.

[0031] Applying the technical scheme of the present invention, the present application provides a continuous production system of fenpropimorph, which includes a continuous aldehyde amine condensation hydrogenation reaction device, a first continuous gas-liquid separation device, a continuous mixing device, a continuous hydrogenation dehalogenation reaction device, a second continuous gas-liquid separation device and a continuous distillation device. The setting of the continuous aldehyde amine condensation hydrogenation reaction device in the present application can cause 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine to undergo a continuous aldehyde amine condensation hydrogenation reaction in a solvent under the action of a first catalyst and hydrogen, and obtain a first product system containing a condensation hydrogenation reaction product, thereby playing a role in protecting the aldehyde group, wherein the enamine intermediate generated by the continuous aldehyde amine condensation reaction undergoes a continuous catalytic hydrogenation reduction reaction with hydrogen, and a first product system containing a condensation hydrogenation reaction product can be obtained. The setting of the first continuous gas-liquid separation device is used to separate the liquid phase and the gas phase in the first product system, and obtain a first liquid phase product and a first recovered hydrogen. The first recovered hydrogen can be returned to the continuous aldehyde amine condensation hydrogenation reaction device for recycling, thereby improving the recovery rate of hydrogen. The setting of the continuous mixing device is used to mix the first liquid phase product with the acid binding agent to obtain the second mixed solution, which can realize the instant mixing of the first liquid phase product and the acid binding agent on the one hand, suppress the deterioration of the raw material, and on the other hand, the mixing efficiency can be improved by using the continuous mixing method, thereby improving production efficiency. The setting of the continuous hydrodehalogenation reaction device is used to make the first liquid phase product obtained and hydrogen react with each other under the action of the second catalyst and the acid binding agent to obtain the second product system containing fenpropimorph. The setting of the second continuous gas-liquid separation device is used to separate the liquid phase and the gas phase in the second product system, obtain the second liquid phase product and the second recovered hydrogen, and the second recovered hydrogen can be returned to the continuous aldehyde amine condensation hydrogenation reaction device and / or the continuous hydrodehalogenation reaction device for recycling, thereby improving the recovery rate of hydrogen. The setting of the continuous rectification device is used to continuously rectify the second liquid phase product to obtain fenpropimorph with higher purity.

[0032] Compared with the intermittent production system, the continuous production system of fenpropimorph described in the present application can more accurately control the reaction conditions. On the one hand, it can inhibit the occurrence of side reactions (such as over-reduction) and improve the selectivity of the product, thereby increasing the yield of fenpropimorph. On the other hand, it can reduce safety accidents caused by runaway reactions and improve production safety. In addition, the use of a continuous production system can reduce the number of repeated heating and cooling of materials in intermittent production, while improving the heat transfer efficiency of the reaction and inhibiting heat accumulation, thereby reducing energy consumption and production costs, improving production efficiency and production safety, and achieving more efficient, continuous and stable production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0034] Figure 1 A schematic structural diagram of a continuous production system of fenpropimorph in one embodiment of the present application is shown;

[0035] Figure 2 A schematic structural diagram of a continuous production system of fenpropimorph in another embodiment of the present application is shown.

[0036] The above drawings include the following reference numerals:

[0037] 100. Continuous aldehyde amine condensation hydrogenation reaction device; 101. Raw material inlet; 102. First hydrogen inlet;

[0038] 200, a first continuous gas-liquid separation device; 201, a first hydrogen recovery outlet;

[0039] 300, continuous mixing device; 301, acid binding agent inlet;

[0040] 400, continuous hydrogenation dehalogenation reaction device; 401, second hydrogen inlet;

[0041] 500, a second continuous gas-liquid separation device; 501, a second hydrogen recovery outlet;

[0042] 600, continuous distillation device; 601, fenpropimorph outlet; 602, 2,6-dimethylmorpholine recovery outlet; 603, acid-binding agent recovery outlet; 604, solvent recovery outlet;

[0043] 700. Mixing device. DETAILED DESCRIPTION

[0044] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0045] As described in the background technology, the existing fenpropimorph production process has the problems of poor selectivity of the synthetic route, low yield, complex production process operation, poor safety, low production efficiency, unstable product yield and purity, and high cost. In order to solve the above technical problems, the first aspect of the present application provides a continuous production system of fenpropimorph, such as Figure 1As shown, the system includes a continuous aldehyde amine condensation hydrogenation reaction device 100, a first continuous gas-liquid separation device 200, a continuous mixing device 300, a continuous hydrogenation dehalogenation reaction device 400, a second continuous gas-liquid separation device 500 and a continuous distillation device 600. The continuous aldehyde amine condensation hydrogenation reaction device 100 is used to carry out a continuous aldehyde amine condensation hydrogenation reaction of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine in the presence of a first catalyst, a first hydrogen and a solvent to obtain a first product system containing a condensation hydrogenation reaction product; the continuous aldehyde amine condensation hydrogenation reaction device 100 is provided with a raw material inlet 101, a first hydrogen inlet 102 and a first product system outlet; the raw material inlet 101 is used to introduce a first mixed solution containing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and a solvent; the continuous aldehyde amine condensation hydrogenation reaction device 100 is used to carry out a continuous aldehyde amine condensation hydrogenation reaction of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine in the presence of a first catalyst, a first hydrogen and a solvent to obtain a first product system containing a condensation hydrogenation reaction product; the continuous aldehyde amine condensation hydrogenation reaction device 100 is provided with a raw material inlet 101, a first hydrogen inlet 102 and a first product system outlet; the raw material inlet 101 is used to introduce a first mixed solution containing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and a solvent; The hydrogenation reaction device 100 is provided with a first catalyst bed layer inside, and the first catalyst is loaded in the first catalyst bed layer; the first continuous gas-liquid separation device 200 is used to separate the first product system to obtain a first liquid phase product and a first recovered hydrogen; the first continuous gas-liquid separation device 200 is provided with a first product system inlet, a first liquid phase product outlet and a first recovered hydrogen outlet 201; the first recovered hydrogen outlet 201 is connected to the first hydrogen inlet 102; the continuous mixing device 300 is used to mix the first liquid phase product with an acid binding agent to obtain a second mixed liquid; the continuous mixing device 300 is provided with a first liquid phase product The first liquid phase product inlet is connected to the first liquid phase product outlet; the continuous hydrodehalogenation reaction device 400 is used to carry out a continuous hydrodehalogenation reaction of the first liquid phase product with the second hydrogen in the presence of a second catalyst and an acid binding agent to obtain a second product system containing fenpropimorph; the continuous hydrodehalogenation reaction device 400 is provided with a mixed liquid inlet, a second hydrogen inlet 401 and a second product system outlet; the mixed liquid inlet is connected to the mixed liquid outlet; a second catalyst bed is provided inside the continuous hydrodehalogenation reaction device 400, and the second catalyst is loaded in the second In the catalyst bed; the second continuous gas-liquid separation device 500 is used to separate the second product system to obtain a second liquid phase product and a second recovered hydrogen; the second continuous gas-liquid separation device 500 is provided with a second product system inlet, a second liquid phase product outlet and a second recovered hydrogen outlet 501; the second product system inlet is connected to the second product system outlet, and the second recovered hydrogen outlet 501 is connected to the first hydrogen inlet 102 and / or the second hydrogen inlet 401; the continuous distillation device 600 is provided with a second liquid phase product inlet and a fenpropimorph outlet 601, and the second liquid phase product inlet is connected to the second liquid phase product outlet.

[0046] The present application provides a continuous production system of fenpropimorph, which includes a continuous aldehyde amine condensation hydrogenation reaction device 100, a first continuous gas-liquid separation device 200, a continuous mixing device 300, a continuous hydrogenation dehalogenation reaction device 400, a second continuous gas-liquid separation device 500 and a continuous distillation device 600. The setting of the continuous aldehyde amine condensation hydrogenation reaction device 100 in the present application can cause 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine to undergo a continuous aldehyde amine condensation hydrogenation reaction in a solvent under the action of a first catalyst and hydrogen to obtain a first product system containing a condensation hydrogenation reaction product, thereby playing a role in protecting the aldehyde group, wherein the enamine intermediate generated by the continuous aldehyde amine condensation reaction undergoes a continuous catalytic hydrogenation reduction reaction with hydrogen to obtain a first product system containing a condensation hydrogenation reaction product. The first continuous gas-liquid separation device 200 is provided for separating the liquid phase and the gas phase in the first product system, and the first liquid phase product and the first recovered hydrogen are obtained, and the first recovered hydrogen can be returned to the continuous aldehyde amine condensation hydrogenation reaction device 100 for recycling, so as to improve the recovery rate of hydrogen. The continuous mixing device 300 is provided for mixing the first liquid phase product with an acid binding agent to obtain a second mixed solution, which can realize the instant mixing of the first liquid phase product with an acid binding agent on the one hand, suppress the deterioration of the raw material, and on the other hand, the mixing efficiency can be improved by using a continuous mixing method, so as to improve production efficiency. The continuous hydrogenation dehalogenation reaction device 400 is provided for causing the first liquid phase product obtained to undergo a continuous hydrogenation dehalogenation reaction with hydrogen under the action of a second catalyst and an acid binding agent, and obtains a second product system containing fenpropimorph. The second continuous gas-liquid separation device 500 is used to separate the liquid phase and the gas phase in the second product system to obtain a second liquid phase product and a second recovered hydrogen, which can be returned to the continuous aldehyde amine condensation hydrogenation reaction device 100 and / or the continuous hydrogenation dehalogenation reaction device 400 for recycling, thereby improving the recovery rate of hydrogen. The continuous distillation device 600 is used to continuously distill the second liquid phase product to obtain fenpropimorph with higher purity.

[0047] Compared with the intermittent production system, the continuous production system of fenpropimorph described in the present application can more accurately control the reaction conditions. On the one hand, it can inhibit the occurrence of side reactions (such as over-reduction) and improve the selectivity of the product, thereby increasing the yield of fenpropimorph. On the other hand, it can reduce safety accidents caused by runaway reactions and improve production safety. In addition, the use of a continuous production system can reduce the number of repeated heating and cooling of materials in intermittent production, while improving the heat transfer efficiency of the reaction and inhibiting heat accumulation, thereby reducing energy consumption and production costs, improving production efficiency and production safety, and achieving more efficient, continuous and stable production.

[0048] In a preferred embodiment, the continuous mixing device 300 is a continuous microchannel mixer. Compared with other types, the continuous mixing device 300 of the above type is conducive to the instant mixing of the first liquid phase product and the acid binding agent, which is conducive to inhibiting the deterioration of the raw materials. On the other hand, the continuous mixing method is conducive to improving the mixing efficiency, thereby helping to improve the production efficiency and the yield of fenpropimorph.

[0049] In a preferred embodiment, Figure 2 As shown, the continuous distillation device 600 is also provided with an outlet 602 for recovering 2,6-dimethylmorpholine, an outlet 603 for recovering an acid-binding agent, and an outlet 604 for recovering a solvent; the outlet 602 for recovering 2,6-dimethylmorpholine is connected to the raw material inlet 101; the outlet 603 for recovering an acid-binding agent is connected to the acid-binding agent inlet 301; and the outlet 604 for recovering a solvent is connected to the raw material inlet 101. The continuous distillation device 600 is used to purify fenpropimorph and separate unreacted cis-2,6-dimethylmorpholine, the acid-binding agent, and the solvent, thereby facilitating the improvement of the recovery rate of the raw materials and further facilitating the reduction of production costs.

[0050] In order to further improve the separation efficiency of cis-2,6-dimethylmorpholine, acid binder and solvent and fenpropimorph, thereby further improving the recovery rate of raw materials, further improving the yield of fenpropimorph, and further reducing production costs, preferably, the continuous distillation device 600 includes but is not limited to a plate tower or a packed tower.

[0051] In a preferred embodiment, Figure 2 As shown, the continuous production system of fenpropimorph also includes a mixing device 700, which is used to mix 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and a solvent to obtain a first mixed solution; the outlet of the mixing device 700 is connected to the raw material inlet 101 of the continuous aldehyde amine condensation hydrogenation reaction device 100 through a first mixed solution delivery pipeline; the inlet of the mixing device 700 is connected to the outlet 602 for recovering 2,6-dimethylmorpholine and / or the outlet 604 for recovering solvent. The setting of the mixing device 700 is conducive to pre-preparing the first mixed solution containing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and a solvent, which is conducive to improving the dispersibility of the above-mentioned raw materials, thereby facilitating the improvement of the reaction efficiency of the subsequent continuous aldehyde amine condensation hydrogenation reaction, and then facilitating the improvement of the conversion rate of the raw materials, and also facilitating the improvement of production efficiency. The inlet of the mixing device 700 is connected to the recovery 2,6-dimethylmorpholine outlet 602 and / or the recovery solvent outlet 604, which facilitates the introduction of the recovered 2,6-dimethylmorpholine and the recovered solvent obtained by continuous distillation into the continuous aldehyde amine condensation hydrogenation reaction device 100, thereby facilitating the improvement of the recovery rate of the raw materials and further facilitating the reduction of production costs.

[0052] In order to more accurately control the feed amount and feed rate of the first mixed liquid, thereby further improving the reaction efficiency and the conversion rate of the subsequent continuous aldehyde amine condensation hydrogenation reaction, and at the same time to further improve the production efficiency, preferably, a first continuous feed pump is provided on the first mixed liquid delivery pipeline.

[0053] In order to facilitate more accurate control of the feed amount and feed rate of the second mixed liquid, thereby further improving the reaction efficiency of the continuous hydrogenation dehalogenation reaction, thereby further improving the yield of butyl fenpropimorph, in a preferred embodiment, the mixed liquid outlet of the continuous mixing device 300 is connected to the mixed liquid inlet of the continuous hydrogenation dehalogenation reaction device 400 through a second mixed liquid delivery pipeline, and a second continuous feed pump is provided on the second mixed liquid delivery pipeline.

[0054] Continuous fixed-bed reactor refers to filling granular solid catalyst or solid reactant inside the reactor, forming a certain height of stacked bed, gas or liquid material flows through the static fixed bed through the particle gap, realizing the process of heterogeneous reaction, due to the effective contact between fluid and catalyst, continuous fixed-bed reactor can achieve higher conversion rate and selectivity, and its parameters are controllable, easy and stable to operate, suitable for continuous large-scale industrial production. In a preferred embodiment, continuous aldehyde amine condensation hydrogenation reaction device 100 and continuous hydrogenation dehalogenation reaction device 400 are each independently a continuous fixed-bed reactor. Compared to other types of reactors, using a continuous fixed-bed reactor is conducive to improving the use efficiency of the catalyst, and is conducive to improving the stability and safety of continuous aldehyde amine condensation hydrogenation and continuous hydrogenation dehalogenation, so as to be conducive to improving the conversion rate of raw materials and the selectivity of fenpropimorph, and then to be conducive to improving the yield of fenpropimorph, and also to improve production efficiency.

[0055] In order to further improve the reaction efficiency of the continuous aldehyde-amine condensation hydrogenation reaction, further improve the conversion rate of the raw materials and the selectivity of the condensation hydrogenation reaction products, thereby further improving the reaction efficiency of the subsequent continuous hydrogenation dehalogenation reaction, preferably, the continuous production system includes at least two continuous aldehyde-amine condensation hydrogenation reaction devices 100 arranged in series.

[0056] In order to further improve the reaction efficiency of the continuous hydrogenation dehalogenation reaction, further improve the conversion rate of the condensation hydrogenation reaction product, and further improve the selectivity and yield of fenpropimorph, preferably, the continuous production system includes at least two continuous hydrogenation dehalogenation reaction devices 400 arranged in series.

[0057] In a preferred embodiment, a first heating component is independently provided on the outside of the continuous aldehyde-amine condensation hydrogenation reaction device 100 and the outside of the continuous hydrogenation dehalogenation reaction device 400. The first heating component is used to preheat the continuous aldehyde-amine condensation hydrogenation reaction device 100 and the continuous hydrogenation dehalogenation reaction device 400. The provision of the first heating component is conducive to improving the preheating efficiency, thereby facilitating the improvement of the reaction efficiency of the continuous aldehyde-amine condensation reaction and the continuous hydrogenation dehalogenation reaction, and also conducive to improving the production efficiency.

[0058] In order to improve the efficiency of heat exchange, thereby more accurately controlling the preheating temperature and further improving the stability and safety of the reaction, preferably, the first heating component is filled with a heat exchange medium.

[0059] In order to more accurately control the reaction temperature during the continuous aldehyde-amine condensation hydrogenation reaction and the continuous hydrogenation dehalogenation reaction, thereby further improving the efficiency and selectivity of the reaction and further improving the yield of butyl fenpropimorph, in a preferred embodiment, a second heating component is independently provided inside the continuous aldehyde-amine condensation hydrogenation reaction device 100 and the continuous hydrogenation dehalogenation reaction device 400.

[0060] In a preferred embodiment, the loading amount of the first catalyst is 10-90 vol% based on the volume percentage of the continuous aldehyde-amine condensation hydrogenation reaction device 100. The loading amount of the first catalyst includes but is not limited to the above range. Limiting it within the above range is conducive to improving the use efficiency of the first catalyst, and is conducive to improving the catalytic efficiency of the first catalyst for the continuous aldehyde-amine condensation hydrogenation reaction, thereby helping to improve the reaction efficiency of the continuous aldehyde-amine condensation hydrogenation reaction, and is also conducive to extending the service life of the first catalyst, thereby helping to improve its utilization rate, and further helping to reduce production costs.

[0061] In a preferred embodiment, the loading amount of the second catalyst is 10-90 vol% in terms of volume percentage of the continuous hydrodehalogenation reaction device 400. The loading amount of the second catalyst includes but is not limited to the above range. Limiting it within the above range is conducive to improving the use efficiency of the second catalyst, and is conducive to improving the catalytic efficiency of the second catalyst for the continuous hydrodehalogenation reaction, thereby helping to improve the reaction efficiency of the continuous hydrodehalogenation reaction, and further helping to improve the yield of fenpropimorph, and at the same time, it is also conducive to extending the service life of the second catalyst, thereby helping to improve its utilization rate, and further helping to reduce production costs.

[0062] In a preferred embodiment, the first continuous gas-liquid separation device 200 and the second continuous gas-liquid separation device 500 each independently include but are not limited to a gravity settling separator, a baffle separator or a packing separator. Compared with other types, the use of the above-mentioned type of gas-liquid separation device is conducive to improving the separation efficiency of the first continuous gas-liquid separation and the second continuous gas-liquid separation, and is conducive to improving the recovery and utilization rate of hydrogen, thereby helping to reduce production costs.

[0063] The second aspect of the present application also provides a continuous production method of fenpropimorph, which continuously produces fenpropimorph using the above-mentioned continuous production system provided by the present application. The continuous production method comprises: step S1, in the presence of a first catalyst and a first hydrogen and a solvent, 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine are subjected to a continuous aldehyde amine condensation hydrogenation reaction in a continuous aldehyde amine condensation hydrogenation reaction device 100 to obtain a first product system containing a condensation hydrogenation reaction product; step S2, using a first continuous gas-liquid separation device 200 to perform a first continuous gas-liquid separation on the first product system to obtain a first liquid phase product and a first recovered hydrogen, and returning at least a portion of the first recovered hydrogen to step S1 step S3, continuously mixing the first liquid phase product and the acid binding agent by a continuous mixing device 300 to obtain a second mixed liquid; step S4, in the presence of a second catalyst and an acid binding agent, subjecting the first liquid phase product and the second hydrogen to a continuous hydrogenation dehalogenation reaction device 400 for a continuous hydrogenation dehalogenation reaction to obtain a second product system containing fenpropimorph; step S5, performing a second continuous gas-liquid separation on the second product system by a second continuous gas-liquid separation device 500 to obtain a second liquid phase product and a second recovered hydrogen, and returning at least a portion of the second recovered hydrogen to step S1 and / or step S4; step S6, continuously rectifying the second liquid phase product by a continuous rectification device 600 to obtain fenpropimorph.

[0064] In the present application, through step S1, 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine undergo a continuous aldehyde amine condensation hydrogenation reaction under the above conditions to obtain a first product system containing a condensation hydrogenation reaction product. After a first continuous gas-liquid separation, step S4 is then performed to allow the obtained first liquid phase product to undergo a continuous hydrogenation dehalogenation reaction with hydrogen under the above conditions to obtain a second product system containing fenpropimorph. After a second continuous gas-liquid separation and continuous distillation, fenpropimorph with a higher purity is obtained.

[0065] Compared with the prior art, 2-methyl-3-(p-tert-butyl)phenylpropanal is usually first reacted with selective hydrogenation to obtain 2-methyl-3-(p-tert-butyl)phenylpropanal, and then fenpropimorph is prepared. The present application sequentially performs continuous aldehyde amine condensation hydrogenation reaction and continuous hydrogenation dehalogenation reaction, which can protect the aldehyde group on the one hand, suppress the occurrence of side reactions (such as the reaction of aldehyde transition reduction to impurity alcohol), and on the other hand, can improve the selectivity of the product, thereby improving the yield of fenpropimorph. Step S2 performs a first continuous gas-liquid separation on the first product system containing the condensation hydrogenation product, and the first recovered hydrogen obtained can be returned to step S1 to achieve recycling. Step S3 can achieve instant mixing of the first liquid phase product and the acid binding agent, suppress the deterioration of the raw material, and the continuous mixing method can also improve the mixing efficiency, thereby improving production efficiency. Step S5 performs a second gas-liquid separation on the second product system containing fenpropimorph, and the second recovered hydrogen obtained can be returned to step S1 and / or step S4 to achieve recycling, thereby improving the recovery rate of hydrogen. By continuously distilling the first liquid phase product in step S6, fenpropimorph with higher purity can be obtained.

[0066] Compared with the intermittent production method, the continuous production method of butyl fenpropimorph provided in the present application can more accurately control the reaction conditions. On the one hand, it can inhibit the occurrence of side reactions (such as over-reduction) and improve the selectivity of the product, thereby increasing the yield of butyl fenpropimorph. On the other hand, it can reduce safety accidents caused by runaway reactions and improve production safety. In addition, the continuous production method can reduce the number of repeated heating and cooling of materials in intermittent production, improve the heat transfer efficiency of the reaction, and inhibit heat accumulation, thereby reducing energy consumption and production costs, improving production efficiency and production safety, and thus achieving more efficient, continuous and stable production.

[0067] The synthetic route of fenpropimorph in this application is as follows:

[0068] .

[0069] In a preferred embodiment, the reaction temperature of the continuous aldehyde amine condensation hydrogenation reaction is 80-120° C., and the reaction pressure is 0.5-6 MPa. The reaction temperature and reaction pressure of the continuous aldehyde amine condensation hydrogenation reaction include but are not limited to the above ranges, and limiting them within the above ranges is conducive to improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, thereby helping to improve the conversion rate of the raw materials and the selectivity of the condensation hydrogenation reaction product.

[0070] In order to improve the utilization efficiency of hydrogen, further improve the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, and improve the conversion rate of the raw materials and the selectivity of the condensation hydrogenation reaction products, in a preferred embodiment, the feed rate ratio of the first hydrogen to 4-tert-butyl-β-chloro-α-methylcinnamaldehyde is (236-950) mL / min:1.0 g / min.

[0071] In a preferred embodiment, in the continuous aldehyde amine condensation hydrogenation reaction device 100, the liquid hourly space velocity of the first mixed liquid is 0.034 to 0.21 h -1 The liquid hourly space velocity of the first mixed liquid includes but is not limited to the above range. Limiting it within the above range is beneficial to improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, and is beneficial to improving the conversion rate of raw materials and the selectivity of products.

[0072] In a preferred embodiment, before step S1, the continuous production method further comprises: mixing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and the solvent using a mixing device 700 to obtain a first mixed solution. Before step S1, mixing the above raw materials in advance to obtain the first mixed solution is beneficial to improving the dispersibility of the above raw materials, thereby facilitating the improvement of the reaction efficiency of the subsequent continuous aldehyde amine condensation hydrogenation reaction, improving the raw material conversion rate and the selectivity of the condensation hydrogenation reaction product, and also facilitating the improvement of production efficiency.

[0073] In order to further improve the dispersibility of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine, thereby further improving the raw material conversion rate and product selectivity of the continuous aldehyde amine condensation hydrogenation reaction, and at the same time to improve the raw material utilization rate, preferably, the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:(0.49~0.98).

[0074] In order to further improve the dispersibility of the raw materials in the first mixed liquid, thereby further improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, and at the same time to improve the utilization rate of the solvent, preferably, the weight ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to the volume ratio of the solvent is 1g: (5-10)mL.

[0075] In a preferred embodiment, the reaction temperature of the continuous hydrodehalogenation reaction is 85-125° C., and the reaction pressure is 0.5-1.5 MPa. The reaction temperature and reaction pressure of the continuous hydrodehalogenation reaction include but are not limited to the above ranges, and limiting them within the above ranges is conducive to improving the reaction efficiency of the continuous hydrodehalogenation reaction, thereby helping to improve the conversion rate of the condensation hydrogenation reaction product and the selectivity of fenpropimorph, and then helping to improve the yield of fenpropimorph.

[0076] In order to improve the utilization efficiency of hydrogen, further improve the reaction efficiency of the continuous hydrogenation dehalogenation reaction, and improve the conversion rate of the condensation hydrogenation reaction product and the selectivity of butylfenmorph, in a preferred embodiment, the feed rate ratio of the second hydrogen to the first liquid phase product is (101~603) mL / min:1.0 g / min.

[0077] In order to further improve the dispersibility of the first liquid phase product and the acid binding agent, and at the same time to introduce a more suitable amount of the acid binding agent into the reaction system of the continuous hydrodehalogenation reaction to neutralize the acidic substances such as hydrogen chloride generated during the reaction, thereby further improving the reaction efficiency of the continuous hydrodehalogenation reaction and the yield of fenpropimorph, preferably, the feed rate ratio of the first liquid phase product to the acid binding agent is 1:(0.3-0.5).

[0078] In order to further inhibit the deterioration of the first liquid phase product and further improve the dispersibility of the first liquid phase product and the acid binding agent, thereby further improving the reaction efficiency of the continuous hydrodehalogenation reaction and the yield of fenpropimorph, preferably, the residence time of the first liquid phase product and the acid binding agent is independently 1 to 10 minutes.

[0079] In a preferred embodiment, the liquid hourly space velocity of the second mixed liquid is 0.3 to 0.9 h -1 The liquid hourly space velocity of the second mixed liquid includes but is not limited to the above range. Limiting it within the above range is beneficial to improving the reaction efficiency of the continuous hydrodehalogenation reaction, and is beneficial to improving the conversion rate of the first liquid phase product and the selectivity of fenpropimorph, thereby helping to improve the yield of fenpropimorph.

[0080] In order to improve the dispersibility of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and the acid-binding agent in the solvent, thereby improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction and the continuous hydrogenation dehalogenation reaction, in a preferred embodiment, the solvent includes but is not limited to one or more of the group consisting of methanol, ethanol, n-butanol, isobutanol, tert-butanol, isopropanol, ethylene glycol, ethyl acetate and isopropyl acetate.

[0081] In a preferred embodiment, the first catalyst is a supported catalyst; the active components in the first catalyst include, but are not limited to, one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium. Compared with other types, the use of the first catalyst of the above type is conducive to improving its catalytic efficiency for the continuous aldehyde amine condensation hydrogenation reaction, thereby facilitating the improvement of the conversion rate of the raw material and the selectivity of the first liquid phase product.

[0082] In order to further improve the catalytic efficiency of the first catalyst for the continuous aldehyde-amine condensation hydrogenation reaction, thereby further improving the conversion rate of the raw material and the selectivity of the first liquid phase product, preferably, the first catalyst includes but is not limited to nickel / alumina (Ni / Al2 O 3 ) catalyst, palladium carbon (Pd / C) catalyst and platinum / TS-1 (Pt / TS-1) catalyst.

[0083] In a preferred embodiment, the first liquid phase product includes, but is not limited to, one or more of (2R,6S)-4-((Z)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine (hereinafter referred to as the first intermediate), (2R,6S)-4-(3-(4-(tert-butyl)phenyl)-3-chloro-2-methylpropyl)-2,6-dimethylmorpholine (hereinafter referred to as the second intermediate), and (2R,6S)-4-((E)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine (hereinafter referred to as the third intermediate). 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine undergo continuous aldehyde amine condensation reaction and continuous catalytic hydrogenation reduction reaction under the action of the first catalyst and hydrogen to obtain the above three intermediates. The above three intermediates can all be used to synthesize fenpropimorph through subsequent continuous hydrogenation and dehalogenation reactions, which is beneficial to improving the selectivity of fenpropimorph and further beneficial to improving the yield of fenpropimorph.

[0084] In order to neutralize the acidic substances such as hydrogen chloride generated during the continuous hydrodehalogenation reaction, inhibit the side reaction of aldehyde groups being reduced in a protic hydrogen environment to produce hydroxyl impurities, thereby improving the reaction efficiency of the continuous hydrodehalogenation reaction, improving the conversion rate of the first liquid phase product and the selectivity of fenpropimorph, and then improving the yield of fenpropimorph, in a preferred embodiment, the acid binding agent is a base.

[0085] In order to further neutralize the acidic substances such as hydrogen chloride generated during the continuous hydrodehalogenation reaction, further inhibit the side reaction of aldehyde groups being reduced in a protic hydrogen environment to produce hydroxyl impurities, thereby further improving the reaction efficiency of the continuous hydrodehalogenation reaction, preferably, the base includes but is not limited to an organic base and / or an inorganic base.

[0086] In order to further neutralize the acidic substances such as hydrogen chloride generated during the continuous hydrodehalogenation reaction, further inhibit the side reaction of aldehyde groups being reduced in a protic hydrogen environment to produce hydroxyl impurities, thereby further improving the reaction efficiency of the continuous hydrodehalogenation reaction, more preferably, the organic base includes but is not limited to one or more of the group consisting of trimethylamine, triethylamine, diethylamine and ethylenediamine; the inorganic base includes but is not limited to one or more of the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate.

[0087] In a preferred embodiment, the second catalyst is a supported catalyst; the active ingredients in the second catalyst include, but are not limited to, one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium. Compared with other types, the use of the second catalyst of the above type is conducive to improving the catalytic efficiency of the second catalyst for the continuous hydrodehalogenation reaction, thereby facilitating the improvement of the conversion rate of the first liquid phase product and the selectivity of fenpropimorph, and further facilitating the improvement of the yield of fenpropimorph.

[0088] In order to further improve the catalytic efficiency of the second catalyst for the continuous hydrodehalogenation reaction, thereby further improving the conversion rate of the first liquid phase product and the selectivity of fenpropimorph, and further improving the yield of fenpropimorph, preferably, the second catalyst includes but is not limited to palladium / aluminum oxide (Pd / Al 2 O 3 ) catalyst, platinum / silicon dioxide (Pt / SiO 2 ) catalyst, one or more of the group consisting of a ruthenium / ZSM-5 (Ru / ZSM-5) catalyst and a rhodium / TS-1 (Rh / TS-1) catalyst.

[0089] In a preferred embodiment, step S6 also recovers 2,6-dimethylmorpholine, an acid-binding agent, and a solvent; at least part of the recovered 2,6-dimethylmorpholine and at least part of the recovered solvent are returned to step S1, and at least part of the recovered acid-binding agent is returned to step S3. The above method is conducive to separating and recovering unreacted cis-2,6-dimethylmorpholine, an acid-binding agent, and a solvent, thereby improving the recycling rate of the above raw materials and reducing production costs.

[0090] In a preferred embodiment, before step S1, the continuous production method further comprises: sequentially performing a system airtightness test and a preheating treatment on the continuous aldehyde amine condensation hydrogenation reaction device 100 and / or the continuous hydrogenation dehalogenation reaction device 400. Performing a system airtightness test is beneficial to improving the stability and safety of the continuous aldehyde amine condensation hydrogenation reaction and the continuous hydrogenation dehalogenation reaction, and performing a preheating treatment is beneficial to shortening the heating time, improving the reaction efficiency, and thus improving the production efficiency.

[0091] In order to further improve the reaction efficiency of the continuous aldehyde-amine condensation hydrogenation reaction and the continuous hydrogenation dehalogenation reaction, and further improve the production efficiency and safety of continuous production, preferably, before step S1, the continuous aldehyde-amine condensation hydrogenation reaction device 100 is preheated to 50-70°C, and the continuous hydrogenation dehalogenation reaction device 400 is preheated to 20-70°C.

[0092] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0093] Example 1

[0094] A continuous production method of fenpropimorph, using Figure 2 The continuous production system of fenpropimorph shown in the figure continuously produces fenpropimorph, and specifically comprises the following steps:

[0095] (1) System tightness test: A Pt / TS-1 catalyst bed is set inside the continuous aldehyde amine condensation hydrogenation fixed bed reactor, and a Pd / Al catalyst bed is set inside the continuous hydrogenation dehalogenation fixed bed reactor. 2 O 3 Catalyst bed; the above-mentioned continuous aldehyde amine condensation hydrogenation fixed bed reactor and the continuous hydrogenation dehalogenation fixed bed reactor were pressure tested; wherein, the loading amount of Pt / TS-1 catalyst was 80vol%, based on the volume percentage of the continuous aldehyde amine condensation hydrogenation fixed bed reactor, and the loading amount of Pd / Al 2 O 3 The loading amount of catalyst is 80 vol%;

[0096] (2) placing 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, cis-2,6-dimethylmorpholine and methanol in a mixing kettle and mixing them to obtain a first mixed solution; wherein the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:0.73, and the weight ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to the volume of methanol is 1 g:10 mL;

[0097] (3) nitrogen is introduced into the continuous aldehyde amine condensation fixed bed reactor to replace the air in the reactor, and the operation is repeated three times. Then, hydrogen is introduced into the reactor to replace the nitrogen in the reactor. After repeating the operation three times, hydrogen is introduced into the reactor, and the back pressure valve is adjusted to make the pressure in the reactor constant at 1.0 MPa, and then the hydrogen inlet valve is adjusted to set the feed rate ratio of hydrogen to 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to 437 mL / min:1 g / min; the first mixed solution obtained in step (2) is preheated to 40° C., and then pumped into the continuous aldehyde amine condensation hydrogenation fixed bed reactor at a rate of 3 g / min through a feed pump to carry out a continuous aldehyde amine condensation hydrogenation reaction to obtain a first product system; wherein the liquid hourly space velocity of the first mixed solution is 0.21 h -1 , the temperature in the continuous aldehyde amine condensation hydrogenation fixed bed reactor is 100°C, and the residence time of the first mixed liquid is 20min;

[0098] (4) introducing the first product system into a baffle separator for continuous gas-liquid separation to obtain a first liquid phase product and recovered hydrogen, and introducing all the recovered hydrogen into a continuous aldehyde amine condensation hydrogenation fixed bed reactor for reuse; wherein the introduction rate of the first product system is 3 g / min, the residence time is 20 min, and the first liquid phase product includes 5.51 wt% of the first intermediate, 2.56 wt% of the second intermediate and 0.67 wt% of the third intermediate in terms of weight percentage of the first liquid phase product;

[0099] (5) introducing the first liquid phase product and triethylamine into a continuous microchannel mixer (using the continuous microchannel mixer in Chinese patent application CN202320266137.6) for mixing to obtain a second mixed liquid; wherein the feed rate ratio of the first liquid phase product to triethylamine is 1:0.4, and the residence time is 2 min;

[0100] (6) nitrogen is introduced into the continuous hydrodehalogenation fixed-bed reactor to replace the air in the reactor, and the operation is repeated three times. Then, hydrogen is introduced into the reactor to replace the nitrogen in the reactor. After repeating the operation three times, hydrogen is introduced into the reactor, and the back pressure valve is adjusted to make the pressure in the reactor constant at 1.0 MPa, and then the hydrogen inlet valve is adjusted to set the feed rate ratio of hydrogen to the first liquid phase product to 335 mL / min:1 g / min; the second mixed solution obtained in step (5) is preheated to 50° C., and then pumped into the continuous hydrodehalogenation fixed-bed reactor at a rate of 1.5 g / min through a feed pump for continuous hydrodehalogenation reaction to obtain a second product system; wherein the liquid hourly space velocity of the second mixed solution is 0.41 h -1 , the temperature in the continuous hydrodehalogenation fixed bed reactor is 95°C, and the residence time of the second mixed liquid is 6.5 min;

[0101] (7) introducing the second product system into a baffle separator for continuous gas-liquid separation to obtain a second liquid phase product and recovered hydrogen, and introducing the recovered hydrogen into a continuous aldehyde amine condensation hydrogenation fixed bed reactor and a continuous hydrogenation dehalogenation fixed bed reactor for reuse; wherein the introduction rate of the second product system is 1.2 g / min, and the residence time is 20 min;

[0102] (8) The second liquid phase product is introduced into a continuous distillation tower for continuous distillation to separate butylfenmorph, unreacted cis-2,6-dimethylmorpholine, triethylamine and methanol solvent, and the separated cis-2,6-dimethylmorpholine and methanol are all returned to the mixing kettle for recycling, and the separated triethylamine is all introduced into a continuous microchannel mixer for recycling; wherein, the introduction rate of the second liquid phase product is 1.2 g / min, the residence time is 20.4 min, the number of plates of the continuous distillation tower is 10, the tower top temperature is 55°C, the tower bottom temperature is 165°C, the operating pressure is 0.025 mmHg (millimeters of mercury), and the reflux ratio is 5:1.

[0103] Example 2

[0104] The difference from Example 1 is that in this example, the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:0.49; the remaining steps are the same as in Example 1.

[0105] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 6.5 wt % of the first intermediate, 1.48 wt % of the second intermediate and 0.23 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0106] Example 3

[0107] The difference from Example 1 is that in this example, the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:0.98; the remaining steps are the same as in Example 1.

[0108] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 7.28 wt % of the first intermediate, 1.43 wt % of the second intermediate and 0.23 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0109] Example 4

[0110] The difference from Example 1 is that in this example, the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine is 1:0.39; the remaining steps are the same as in Example 1.

[0111] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 5.27 wt % of the first intermediate, 1.40 wt % of the second intermediate and 0.54 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0112] Example 5

[0113] The difference from Example 1 is that the temperature in the continuous aldehyde amine condensation hydrogenation fixed bed reactor is 80° C. and the pressure is 6 MPa; the remaining steps are the same as in Example 1.

[0114] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 1.21 wt % of the first intermediate, 1.43 wt % of the second intermediate and 6.16 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0115] Example 6

[0116] The difference from Example 1 is that the temperature in the continuous aldehyde amine condensation hydrogenation fixed bed reactor is 120° C. and the pressure is 0.5 MPa; the remaining steps are the same as in Example 1.

[0117] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 5.17 wt % of the first intermediate, 2.18 wt % of the second intermediate and 0.69 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0118] Example 7

[0119] The difference from Example 1 is that the temperature in the continuous aldehyde amine condensation hydrogenation fixed bed reactor is 130° C. and the pressure is 0.4 MPa; the remaining steps are the same as in Example 1.

[0120] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 4.48 wt % of the first intermediate, 2.09 wt % of the second intermediate and 0.20 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0121] Example 8

[0122] The difference from Example 1 is that the temperature in the continuous hydrodehalogenation fixed bed reactor is 85° C. and the pressure is 1.5 MPa; the remaining steps are the same as in Example 1.

[0123] Example 9

[0124] The difference from Example 1 is that the temperature in the continuous hydrodehalogenation fixed bed reactor is 125° C. and the pressure is 0.5 MPa; the remaining steps are the same as in Example 1.

[0125] Example 10

[0126] The difference from Example 1 is that the temperature in the continuous hydrodehalogenation fixed bed reactor is 75° C. and the pressure is 0.3 MPa; the remaining steps are the same as in Example 1.

[0127] Embodiment 11

[0128] The difference from Example 1 is that in step (5), the feed rate ratio of the first liquid phase product to triethylamine is 1:0.3; the remaining steps are the same as Example 1.

[0129] Example 12

[0130] The difference from Example 1 is that in step (5), the feed rate ratio of the first liquid phase product to triethylamine is 1:0.5; the remaining steps are the same as Example 1.

[0131] Example 13

[0132] The difference from Example 1 is that in step (5), the feed rate ratio of the first liquid phase product to triethylamine is 1:0.25; the remaining steps are the same as Example 1.

[0133] Embodiment 14

[0134] The difference from Example 1 is that in the continuous aldehyde-amine condensation hydrogenation reaction of this example, the liquid hourly space velocity of the first mixed liquid is 0.034h -1 ; The remaining steps are the same as in Example 1.

[0135] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 1.01 wt % of the first intermediate, 2.32 wt % of the second intermediate and 4.62 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0136] Embodiment 15

[0137] The difference from Example 1 is that in the continuous aldehyde-amine condensation hydrogenation reaction of this example, the liquid hourly space velocity of the first mixed liquid is 0.21h -1 ; The remaining steps are the same as in Example 1.

[0138] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 5.64 wt % of the first intermediate, 2.62 wt % of the second intermediate and 0.69 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0139] Example 16

[0140] The difference from Example 1 is that in the continuous aldehyde-amine condensation hydrogenation reaction of this embodiment, the liquid hourly space velocity of the first mixed liquid is 0.02h -1 ; The remaining steps are the same as in Example 1.

[0141] In the continuous aldehyde amine condensation hydrogenation reaction of this embodiment, the first liquid phase product includes 2.40 wt % of the first intermediate, 2.04 wt % of the second intermediate and 2.54 wt % of the third intermediate in terms of weight percentage of the first liquid phase product.

[0142] Embodiment 17

[0143] The difference from Example 1 is that in the continuous hydrodehalogenation reaction of this embodiment, the liquid hourly space velocity of the second mixed liquid is 0.3h -1 ; The remaining steps are the same as in Example 1.

[0144] Embodiment 18

[0145] The difference from Example 1 is that in the continuous hydrodehalogenation reaction of this embodiment, the liquid hourly space velocity of the second mixed liquid is 0.9h -1 ; The remaining steps are the same as in Example 1.

[0146] Embodiment 19

[0147] The difference from Example 1 is that in the continuous hydrodehalogenation reaction of this embodiment, the liquid hourly space velocity of the second mixed liquid is 1.3h -1 ; The remaining steps are the same as in Example 1.

[0148] Comparative Example 1

[0149] A batch production method of fenpropimorph comprises the following steps:

[0150] (1) Using 10.0231 g of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde as a starting material, a catalytic hydrogenation dehalogenation reaction was carried out with hydrogen in ethanol in a hydrogenation reactor under the catalysis of 502.1 mg of Pd / C catalyst to obtain 5.1219 g of lily of the valley aldehyde; wherein the temperature of the catalytic hydrogenation reduction reaction was 100° C. and the pressure was 1.2 MPa;

[0151] (2) In a hydrogenation reactor, 5.1219 g of lily of the valley aldehyde and 3.1759 g of 2,6-dimethylmorpholine are reacted in ethanol in the presence of 256.1 mg of Raney nickel catalyst and hydrogen to produce 5.3256 g of butylfenmorpholine; wherein the temperature of the aldehyde amine condensation hydrogenation reaction is 100° C. and the pressure is 1.0 MPa.

[0152] The conversion rate of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, the combined selectivity and combined conversion rate of the three intermediates, and the yield of butylfenmorph in the production of butylfenmorph in the above-mentioned Examples 1 to 19 of the present application are shown in Table 1; the conversion rate of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, the selectivity and conversion rate of the intermediate lily of the valley aldehyde, and the yield of butylfenmorph in the production of butylfenmorph in Comparative Example 1 are shown in Table 2. Among them, the conversion rate refers to the proportion of the reacted material to the weight of the initial material.

[0153] Table 1

[0154]

[0155] Table 2

[0156]

[0157] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0158] By comparing Example 1 and Comparative Example 1, it can be seen that the present application sequentially performs continuous aldehyde amine condensation hydrogenation reaction and continuous hydrogenation dehalogenation reaction, which can protect the aldehyde group and inhibit the occurrence of side reactions (such as the transition reduction of aldehydes to impurity alcohols), and can improve the selectivity of the product, thereby improving the yield of butylfenmorph; at the same time, compared with the intermittent production method, the above-mentioned continuous production method of butylfenmorph in the present application can more accurately control the reaction conditions, which can inhibit the occurrence of side reactions (such as excessive reduction) and improve the selectivity of the product, thereby improving the yield of butylfenmorph, and can reduce the safety accidents caused by runaway reactions and improve production safety; and the continuous production method can reduce the number of repeated heating and cooling of materials in intermittent production, improve the heat transfer efficiency of the reaction, and inhibit heat accumulation, thereby reducing energy consumption and production costs, improving production efficiency and production safety, and thus achieving more efficient, continuous and stable production.

[0159] Comparing Examples 1 to 4, it can be seen that, compared with other ranges, limiting the feed rate ratio of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to cis-2,6-dimethylmorpholine within the above-mentioned range of the present application is beneficial to improving the dispersibility of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine, and is beneficial to inhibiting the hydrogenation-reduction side reaction of 4-tert-butyl-β-chloro-α-methylcinnamaldehyde with hydrogen, thereby helping to improve the product selectivity of the continuous aldehyde amine condensation hydrogenation reaction, and further helping to improve the yield of butylfenmorph.

[0160] By comparing Examples 1, 5 to 7, it can be seen that the reaction temperature and reaction pressure of the continuous aldehyde amine condensation hydrogenation reaction include but are not limited to the above ranges. Limiting them within the above ranges is beneficial to improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, and is beneficial to suppressing the occurrence of side reactions, thereby helping to improve the selectivity of the condensation hydrogenation reaction product, and further helping to improve the yield of butyl fenpropimorph.

[0161] Comparing Examples 1, 8 to 10, it can be seen that the reaction temperature and reaction pressure of the continuous hydrodehalogenation reaction include but are not limited to the above ranges. Limiting them within the above ranges is beneficial to improving the reaction efficiency of the continuous hydrodehalogenation reaction, and is beneficial to suppressing the occurrence of side reactions, thereby helping to improve the conversion rate of the condensation hydrogenation reaction product and the selectivity of fenpropimorph, and further helping to improve the yield of fenpropimorph.

[0162] Comparing Examples 1, 11 to 13, it can be seen that, compared with other ranges, limiting the feed rate ratio of the first liquid phase product to the acid binding agent within the above range of the present application is beneficial to improving the dispersibility of the first liquid phase product and the acid binding agent, and is beneficial to introducing a more suitable amount of acid binding agent into the reaction system of the continuous hydrodehalogenation reaction to neutralize the acidic substances such as hydrogen chloride generated during the reaction, thereby promoting the forward progress of the continuous hydrodehalogenation reaction, and further helping to improve the yield of fenpropimorph.

[0163] By comparing Examples 1 and 14 to 16, it can be seen that, compared with other ranges, limiting the liquid hourly space velocity of the first mixed liquid within the above-mentioned range of the present application is beneficial to improving the reaction efficiency of the continuous aldehyde amine condensation hydrogenation reaction, is beneficial to suppressing the occurrence of side reactions, is beneficial to improving the selectivity of the condensation hydrogenation reaction products, and thus is beneficial to improving the yield of butyl fenpropimorph.

[0164] By comparing Examples 1 and 17 to 19, it can be seen that, compared with other ranges, limiting the liquid hourly space velocity of the second mixed liquid within the above-mentioned range of the present application is beneficial to improving the reaction efficiency of the continuous hydrodehalogenation reaction, suppressing the occurrence of side reactions, and improving the selectivity of the continuous hydrodehalogenation reaction, thereby helping to increase the yield of butyl fenpropimorph.

[0165] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0166] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A continuous production system of fenpropimorph, characterized in that, The continuous production system of fenpropimorph comprises: A continuous aldehyde amine condensation hydrogenation reaction device (100) is used for carrying out a continuous aldehyde amine condensation hydrogenation reaction on 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine in the presence of a first catalyst, a first hydrogen gas and a solvent to obtain a first product system containing a condensation hydrogenation reaction product; the continuous aldehyde amine condensation hydrogenation reaction device (100) is provided with a raw material inlet (101), a first hydrogen gas inlet (102) and a first product system outlet; the raw material inlet (101) is used for introducing a first mixed liquid containing the 4-tert-butyl-β-chloro-α-methylcinnamaldehyde, the cis-2,6-dimethylmorpholine and the solvent; a first catalyst bed is provided inside the continuous aldehyde amine condensation hydrogenation reaction device (100), and the first catalyst is loaded in the first catalyst bed; a first continuous gas-liquid separation device (200), used for separating the first product system to obtain a first liquid phase product and a first recovered hydrogen; the first continuous gas-liquid separation device (200) is provided with a first product system inlet, a first liquid phase product outlet and a first recovered hydrogen outlet (201); the first recovered hydrogen outlet (201) is in communication with the first hydrogen inlet (102); A continuous mixing device (300) is used to mix the first liquid phase product with an acid binding agent to obtain a second mixed liquid; the continuous mixing device (300) is provided with a first liquid phase product inlet, an acid binding agent inlet (301) and a mixed liquid outlet; the first liquid phase product inlet is connected to the first liquid phase product outlet; A continuous hydrodehalogenation reaction device (400) is used for performing a continuous hydrodehalogenation reaction between the first liquid phase product and the second hydrogen in the presence of a second catalyst and an acid binding agent to obtain a second product system containing fenpropimorph; the continuous hydrodehalogenation reaction device (400) is provided with a mixed liquid inlet, a second hydrogen inlet (401) and a second product system outlet; the mixed liquid inlet is connected to the mixed liquid outlet; a second catalyst bed is provided inside the continuous hydrodehalogenation reaction device (400), and the second catalyst is loaded in the second catalyst bed; A second continuous gas-liquid separation device (500) is used to separate the second product system to obtain a second liquid phase product and a second recovered hydrogen; the second continuous gas-liquid separation device (500) is provided with a second product system inlet, a second liquid phase product outlet and a second recovered hydrogen outlet (501); the second product system inlet is connected to the second product system outlet, and the second recovered hydrogen outlet (501) is connected to the first hydrogen inlet (102) and / or the second hydrogen inlet (401); A continuous distillation device (600) is provided with a second liquid phase product inlet and a fenpropimorph outlet (601), wherein the second liquid phase product inlet is connected to the second liquid phase product outlet.

2. The continuous production system of fenpropimorph according to claim 1, characterized in that, The continuous mixing device (300) is a continuous microchannel mixer.

3. The continuous production system of fenpropimorph according to claim 1, characterized in that, The continuous distillation device (600) is further provided with an outlet (602) for recovering 2,6-dimethylmorpholine, an outlet (603) for recovering an acid binding agent, and an outlet (604) for recovering a solvent; the outlet (602) for recovering 2,6-dimethylmorpholine is connected to the raw material inlet (101); the outlet (603) for recovering an acid binding agent is connected to the acid binding agent inlet (301); and the outlet (604) for recovering a solvent is connected to the raw material inlet (101).

4. The continuous production system of fenpropimorph according to claim 3, characterized in that, The continuous distillation device (600) is a plate tower or a packed tower.

5. The continuous production system of fenpropimorph according to claim 1, characterized in that, The continuous aldehyde-amine condensation hydrogenation reaction device (100) and the continuous hydrogenation dehalogenation reaction device (400) are each independently a continuous fixed bed reactor.

6. The continuous production system of fenpropimorph according to any one of claims 1 to 5, characterized in that, The continuous production system comprises at least two continuous aldehyde amine condensation hydrogenation reaction devices (100) arranged in series.

7. The continuous production system of fenpropimorph according to any one of claims 1 to 5, characterized in that, The continuous production system comprises at least two continuous hydrodehalogenation reaction devices (400) arranged in series.

8. The continuous production system of fenpropimorph according to claim 1, characterized in that, The outside of the continuous aldehyde-amine condensation hydrogenation reaction device (100) and the outside of the continuous hydrogenation dehalogenation reaction device (400) are each independently provided with a first heating component, and the first heating component is filled with a heat exchange medium.

9. The continuous production system of fenpropimorph according to claim 1, characterized in that, The continuous aldehyde-amine condensation hydrogenation reaction device (100) and the continuous hydrogenation dehalogenation reaction device (400) are each independently provided with a second heating component inside.

10. The continuous production system of fenpropimorph according to claim 1, characterized in that, Calculated by volume percentage of the continuous aldehyde-amine condensation hydrogenation reaction device (100), the loading amount of the first catalyst is 10-90 vol%.

11. The continuous production system of fenpropimorph according to claim 1, characterized in that, Calculated by volume percentage of the continuous hydrodehalogenation reaction device (400), the loading amount of the second catalyst is 10-90 vol%.

12. The continuous production system of fenpropimorph according to claim 1, characterized in that, The first continuous gas-liquid separation device (200) and the second continuous gas-liquid separation device (500) are each independently selected from a gravity sedimentation separator, a baffle separator or a packing separator.

13. A continuous production method of fenpropimorph, characterized in that: The continuous production system of fenpropimorph according to claim 1 is used to continuously produce fenpropimorph, and the continuous production method comprises: Step S1, in the presence of a first catalyst, a first hydrogen gas and a solvent, 4-tert-butyl-β-chloro-α-methylcinnamaldehyde and cis-2,6-dimethylmorpholine are subjected to a continuous aldehyde-amine condensation hydrogenation reaction in a continuous aldehyde-amine condensation hydrogenation reaction device (100) to obtain a first product system containing a condensation hydrogenation reaction product; Step S2, using a first continuous gas-liquid separation device (200) to perform a first continuous gas-liquid separation on the first product system to obtain a first liquid phase product and a first recovered hydrogen, and returning at least a portion of the first recovered hydrogen to the step S1; Step S3, using a continuous mixing device (300) to continuously mix the first liquid phase product and the acid binding agent to obtain a second mixed liquid; Step S4, in the presence of the second catalyst and the acid-binding agent, the first liquid phase product and the second hydrogen are subjected to a continuous hydrogenation dehalogenation reaction in a continuous hydrogenation dehalogenation reaction device (400) to obtain a second product system containing fenpropimorph; Step S5, using a second continuous gas-liquid separation device (500) to perform a second continuous gas-liquid separation on the second product system to obtain a second liquid phase product and a second recovered hydrogen, and returning at least a portion of the second recovered hydrogen to the step S1 and / or the step S4; Step S6, using a continuous distillation device (600) to continuously distill the second liquid phase product to obtain the fenpropimorph.

14. The continuous production method of fenpropimorph according to claim 13, characterized in that: The reaction temperature of the continuous aldehyde amine condensation hydrogenation reaction is 80-120° C., and the reaction pressure is 0.5-6 MPa.

15. The continuous production method of fenpropimorph according to claim 14, characterized in that, The feed rate ratio of the 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to the cis-2,6-dimethylmorpholine is 1:(0.49-0.98); and / or, the feed rate ratio of the first hydrogen to the 4-tert-butyl-β-chloro-α-methylcinnamaldehyde is (236-950) mL / min:1.0 g / min; and / or, in the continuous aldehyde amine condensation hydrogenation reaction device (100), the liquid hourly space velocity of the first mixed liquid is 0.034-0.21 h -1 ; and / or, the weight ratio of the 4-tert-butyl-β-chloro-α-methylcinnamaldehyde to the volume ratio of the solvent is 1 g: (5 to 10) mL.

16. The continuous production method of fenpropimorph according to claim 13, characterized in that: The reaction temperature of the continuous hydrodehalogenation reaction is 85-125° C., and the reaction pressure is 0.5-1.5 MPa.

17. The continuous production method of fenpropimorph according to claim 13, characterized in that: In the continuous mixing device (300), the feed rate ratio of the first liquid product to the acid binding agent is 1:(0.3-0.5); the residence time of the first liquid product and the acid binding agent is independently 1-10 min; and / or, the feed rate ratio of the second hydrogen to the first liquid product is (101-603) mL / min:1.0 g / min; and / or, in the continuous hydrogenation dehalogenation reaction device (400), the liquid hourly space velocity of the second mixed liquid is 0.3-0.9 h -1 .

18. The continuous production method of fenpropimorph according to claim 13, characterized in that: The solvent is selected from one or more of the group consisting of methanol, ethanol, n-butanol, isobutanol, tert-butanol, isopropanol, ethylene glycol, ethyl acetate and isopropyl acetate.

19. The continuous production method of fenpropimorph according to claim 13, characterized in that: The first catalyst is a supported catalyst, and the active component in the first catalyst is selected from one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium.

20. The continuous production method of fenpropimorph according to claim 19, characterized in that: The first catalyst is selected from one or more of the group consisting of a nickel / alumina catalyst, a palladium / carbon catalyst and a platinum / TS-1 catalyst.

21. The continuous production method of fenpropimorph according to claim 13, characterized in that: The first liquid phase product is selected from one or more of (2R, 6S)-4-((Z)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine, (2R, 6S)-4-(3-(4-(tert-butyl)phenyl)-3-chloro-2-methylpropyl)-2,6-dimethylmorpholine and (2R, 6S)-4-((E)-3-(4-(tert-butyl)phenyl)-3-chloro-2-methylallyl)-2,6-dimethylmorpholine.

22. The continuous production method of fenpropimorph according to claim 13, characterized in that: The acid binding agent is a base, and the base is selected from an organic base and / or an inorganic base.

23. The continuous production method of fenpropimorph according to claim 22, characterized in that: The organic base is selected from one or more of the group consisting of trimethylamine, triethylamine, diethylamine and ethylenediamine; the inorganic base is selected from one or more of the group consisting of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate.

24. The continuous production method of fenpropimorph according to claim 13, characterized in that: The second catalyst is a supported catalyst, and the active component in the second catalyst is selected from one or more of the group consisting of nickel, palladium, rhodium, platinum, zinc and ruthenium.

25. The continuous production method of fenpropimorph according to claim 24, characterized in that: The second catalyst is selected from one or more of the group consisting of palladium / alumina catalyst, platinum / silicon dioxide catalyst, ruthenium / ZSM-5 catalyst and rhodium / TS-1 catalyst.

26. The continuous production method of fenpropimorph according to claim 13, characterized in that: In step S6, recovered 2,6-dimethylmorpholine, recovered acid-binding agent and recovered solvent are obtained; at least part of the recovered 2,6-dimethylmorpholine and at least part of the recovered solvent are returned to step S1, and at least part of the recovered acid-binding agent is returned to step S3.

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