CN112221444B - System and method for continuously synthesizing clethodim - Google Patents
System and method for continuously synthesizing clethodim Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- C—CHEMISTRY; METALLURGY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00867—Microreactors placed in series, on the same or on different supports
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- B01J2219/00781—Aspects relating to microreactors
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Abstract
The invention belongs to the technical field of chemical product synthesis, and relates to a micro-reaction system and a micro-reaction method for synthesizing herbicide clethodim. The system is formed by sequentially connecting a micro-channel reactor I, a micro-channel reactor II and a collector in series. The synthesis method comprises the steps of taking an ethanol solution of 5- [2- (ethylmercapto) propyl ] -2-propionyl-1, 3-cyclohexanedione (abbreviated as "seminal trione") and chloroallyloxyamine (abbreviated as "chloramine") as raw materials, respectively and continuously conveying the raw materials into a microchannel reactor I through a metering pump to realize intensive mixing and reaction, continuously mixing and reacting the reacted materials in a microchannel reactor II, controlling the temperature of a system through a heat exchanger, feeding the reaction product into a collector, and performing acid washing and separation to obtain the clethodim product. The system and the method can realize the low-energy consumption, safe and continuous production of clethodim, and under the condition that the molar ratio of chloramine to trione is 1.20, the conversion rate of the trione is higher than 99 percent, and the yield of the product clethodim is higher than 95 percent.
Description
Technical Field
The invention belongs to the technical field of chemical product synthesis, and particularly relates to a micro-reactor system and a method for synthesizing herbicide clethodim.
Background
Clethodim is a cyclohexanone herbicide developed by Chevron chemical company in 1982, and the product has the advantages of good herbicidal activity, high selectivity, easiness in degradation and the like, and has a wide market prospect.
At present, clethodim is industrially prepared by adopting an intermittent kettle type reaction, the 5- [2- (ethylmercapto) propyl ] -2-propionyl-1, 3-cyclohexanedione (protamine) and petroleum ether are mixed, the temperature is increased to 30-35 ℃, chloroallyloxyamine (chloroamine) is dripped, the dripping is finished within 2-3 hours, the temperature is kept at 30-35 ℃ for reaction for 5-6 hours, and the reaction is finished when the content of the protamine is detected to be less than 1%; and then washing with acid water, and performing desolventizing under reduced pressure at 40-50 ℃ to obtain clethodim. The conventional batch reactor has many problems: firstly, the reaction kettle has large volume and poor mechanical stirring effect, so that the concentration distribution of reaction materials is easily uneven, local hot spots are generated, and safety accidents are caused; and secondly, the intermittent kettle type reaction time is long, the energy consumption is high, and clethodim decomposition is more obvious due to poor stability and overlong reaction time of the clethodim. In the current industrial production process, the yield of clethodim is between 85 and 88 percent. Some process improvements have been reported, but are still in the laboratory stage.
A master paper of Nanjing university of science and technology, namely synthesis and process optimization of clethodim (2013), researches that n-hexane and water are used as solvents, and the reaction is carried out for 24 hours under stirring at 60 ℃; the yield is only about 50%, and the yield is more difficult to guarantee in scale-up.
The synthetic route of clethodim is as follows:
with the development of modern chemical technology, the reaction process is miniaturized to be an important trend. Compared with the conventional reaction device, the micro chemical technology can realize rapid mixing, strengthen the mass transfer and heat transfer performance and improve the safety of the process. Therefore, an effective way is provided for solving the problems in the prior art by adopting the micro-reaction device to synthesize clethodim, and the green, safe and efficient production of clethodim is favorably realized.
Disclosure of Invention
The method aims to solve the problems of long reaction time, low yield, low clethodim content and the like in the existing clethodim synthesis technology. The invention provides a micro-reaction system and a method for synthesizing clethodim, which have the advantages of high reaction speed, high yield of prepared clethodim, safe process, simple post-treatment, recyclable solvent, small environmental pollution and suitability for continuous large-scale production.
The technical scheme of the invention is as follows:
on one hand, the invention provides a micro-reaction system for continuously synthesizing clethodim, which comprises a micro-channel reactor I, a micro-channel reactor II and a product collector which are sequentially connected in series; the microchannel reactor I comprises a microstructure mixing chip set and a reaction chip set which are communicated with each other; the microstructure mixing chip set is a channel structure with diamond-shaped grooves and cylindrical turbulent flow grooves which are alternately arranged; the reaction chip group is of a Z-shaped or zigzag single-channel structure; the microstructure mixed chip set and the reaction chip set are closely arranged together; the microchannel reactor II comprises a reaction chip set; the reaction chip set has a Z-shaped or zigzag single-channel structure.
The reaction chip group is formed by stacking one or more reaction chips which are distributed in parallel; the microstructure hybrid chip set is formed by stacking one or more parallel hybrid chips; the system also comprises two continuous conveying devices which are respectively communicated with the two material inlets of the microchannel reactor I.
The microchannel reactor I and the microchannel reactor II are both provided with heat exchange channels; heating or cooling chips are arranged between the microstructure mixing chip set of the microchannel reactor I and each chip of the reaction chip set; heating or cooling chips are arranged among the chips of the reaction chip group of the microchannel reactor II; and the microchannel reactor I and the microchannel reactor II are respectively provided with a heat exchanger for providing a cold source or a heat source for heating or cooling the chip. The heating or cooling chips have good heat transfer performance, and can control the reaction temperature to be 30-75 ℃ in a non-hot spot area.
The channel angle between the rhombus and the rhombus groove, the Z-shaped channel or the sawtooth-shaped channel with the cylindrical turbulent flow is 90-150 degrees; the hydraulic diameter of the reaction channel is 0.1-3 mm, and the length is 0.2-100 cm; and when the reactants flow in the channel with the angle of 90-150 degrees, the flow direction is continuously changed or turbulent flow is generated, so that mixing and reaction are realized.
The microchannel reactor I further comprises a plurality of micro-structure mixing chips which are distributed in parallel and have a certain volume, so that the material residence time in the microchannel reactor I reaches 1-50 seconds, and the raw material is converted to the maximum extent. The series microchannel reactor II further comprises a plurality of microstructure reaction chips, and a larger internal effective volume is constructed, so that the residence time required by the reaction can be regulated and controlled.
In another aspect, the present invention provides a method for synthesizing clethodim by using the above micro-reaction system, and particularly, the method for preparing clethodim is improved in terms of solvent effect, i.e., polar solvent can facilitate protonation of the protamine, so that condensation reaction with the chloramine can be more easily carried out.
The method comprises the following steps:
(1) dissolving 5- [2- (ethylmercapto) propyl ] -2-propionyl 1, 3-cyclohexanedione (trione) in a polar solvent to obtain a solution I, wherein the concentration of the trione in the solution I is 50-80 wt%;
(2) the solution I and chloroallyloxyamine are passed through a continuous conveying equipment, so that two raw materials are intensively mixed and reacted in a rhombic channel of a microchannel reactor I, and the mixing and reaction temperature is controlled by a heat exchange channel of a microreactor I;
(3) the mixed materials are further mixed and reacted in a zigzag channel of a micro-channel reactor II connected in series behind the micro-channel reactor I, and the reaction temperature of the section is controlled through a heat exchange channel of the micro-reactor II; after the reaction is finished, obtaining a reaction product;
(4) and (3) putting the obtained clethodim into a collection kettle, adding a proper amount of dilute hydrochloric acid, stirring, separating an organic phase, washing with water, drying, and evaporating to remove the solvent to obtain the clethodim.
The specific reaction parameters include:
the content of the trione in the solution is 50-80 wt% by mass, and the content of the chloramine is more than 99%; the polar solvent is ethanol; the feeding ratio of the chloramine to the refined trione is 1.0-1.3 in terms of mole; the reaction temperature of the microchannel reactor I and the microchannel reactor II is 30-85 ℃.
Preferably, the molar ratio of the chloramine to the refined trione is (1.05-1.25) to 1; the reaction temperature of the reaction materials in the microchannel reactor I and the microchannel reactor II is 55-75 ℃.
Preferably, the molar ratio of the chloramine to the refined trione is (1.1-1.2) to 1.
The residence time of the two strands of raw materials in the microchannel reactor I is 1-50 seconds; the residence time in the series microchannel reactor II after the microchannel is not less than 25 seconds, preferably not more than 60 seconds, and the feedstock is converted to at least 98%.
Preferably, the total residence time of the reaction materials in the microchannel reactor I and the microchannel reactor II is 25-60 s.
Slowly adding dilute hydrochloric acid into the collection kettle, wherein the concentration of the dilute hydrochloric acid is 20-80 wt%, the using amount is 0-100 ml, and the adding speed is 20 ml/min; separating the aqueous phase at a temperature not exceeding 40 deg.C, preferably not exceeding 25 deg.C during the addition of acid, washing with water, separating the organic phase, and distilling off the solvent at low pressure and temperature to obtain clethodim.
Advantageous effects
1. The invention takes the microchannel reactor as the core technology, and because of the high-efficiency mass transfer rate, the reaction time required by more than 99 percent of conversion of the raw material, namely the refined trione, is 1 order of magnitude less than that of the traditional process; the special channel structures of the microchannel reactor I and the microchannel reactor II further enhance the mixing, mass transfer and heat transfer among reaction materials, the microchannel reactor II with larger serial connection volume can effectively regulate and control the residence time required by the reaction, and the microchannel reactor I and the microchannel reactor II provide an optimal reaction platform for raw material mixing, reaction and side reaction inhibition.
2. The invention uses ethanol to replace petroleum ether in the traditional method as a solvent, and combines the used microchannel reactor, thereby greatly improving the reaction speed and the selectivity of a target product and realizing efficient, safe and continuous preparation.
3. The system and the method provided by the invention have certain significance on the aspects of continuous safe production and engineering, realize continuous production, rapid and efficient conversion and high selectivity of clethodim, achieve the total yield of about 98 percent and the content of clethodim of about 95 percent, and have higher economic, environmental and social benefits.
Drawings
FIG. 1 is a flow diagram of a system for the continuous synthesis of clethodim according to the present invention.
FIG. 2 is a front view of a micro-structured hybrid chip of microchannel reactor I of the present invention.
FIG. 3 is a front view of a reaction chip of microchannel reactor I and microchannel reactor II according to the present invention.
In the figure, 1-metering pump; 2-microchannel reactor I; 3-microchannel reactor II; 4-product collector.
Detailed Description
The invention will be further illustrated and described with reference to practice of the invention.
The raw materials of the invention, namely the trione, the chloramine and the reagent are all purchased from the market, and the invention is not detailed.
As shown in fig. 1, a flow diagram of a system for the continuous synthesis of clethodim for use in examples 1-9 of the present invention; the system comprises a micro-channel reactor I, a micro-channel reactor II and a product collector which are sequentially connected in series; the microchannel reactor I and the microchannel reactor II are both provided with heat exchange devices; the product collector is a collection kettle; the system also comprises two metering pumps 1; and the two metering pumps are communicated with the inlet of the micro-channel reactor I.
The I channel structure of the microchannel reactor is formed by alternately arranging rhombic grooves and rhombic grooves with cylindrical turbulence, and the inner diameter of the microchannel is 0.1-3 mm.
The channel structure of the microchannel reactor II is arranged in a Z shape or a zigzag shape, and the inner diameter of the microchannel is 0.2-5 mm.
The microchannel of the microchannel reactor I and the microchannel reactor II is made of 316 stainless steel; the volume of the microchannel reactor II is larger than that of the microchannel reactor I.
Example 1
The chloramine (purity: 93.8%) and the trihydroxy ketone (purity: 94.0%) are used as raw materials, and the ethanol is used as a solvent. Dissolving the trione in ethanol to prepare the ethanol solution of the trione with the content of the trione of 50wt percent. The chloramine and the ethanol solution of the refined trione are respectively pumped and fed at the flow rates of 4ml/min and 20ml/min for 5min, and the feeding amounts are respectively: 21.9g (0.19mol) of chloramine and 91.8g (0.16mol) of ethanol solution of the refined trione, and the feeding molar ratio of the chloramine to the refined trione is 1.19. The two raw materials are intensively mixed and reacted in a parallel microchannel reactor I with a channel hydraulic diameter of 0.5mm and a liquid holding volume of 7.2 ml; the reaction mass was further mixed and reacted in microchannel reactor II with a total residence time of 43 seconds for the reaction mass in both reactors. And meanwhile, controlling the reaction temperature of the microchannel reactor I and the microchannel reactor II to be 75 ℃, enabling the product to enter a collector, cooling to 20-25 ℃, adding dilute hydrochloric acid, separating a water phase, washing an organic phase to be neutral, and performing decompression and desolventization to obtain 56.9g of the product. Detecting with Agilent 1260 liquid chromatograph with C-18 chromatographic column and GB22614-2008 to determine product content. After analysis: the concentration of the protamine is 0.7 percent, and the concentration of the clethodim is 96.5 percent. Conversion rate (raw material refined trione mass-product total mass x product refined trione concentration)/(raw material refined trione mass) x 100%
Yield ═ yield (total mass of product × clethodim concentration)/(mass of raw material refined trione × 359.91/270.39) × 100% refined trione conversion ═ (91.8 × 50% × 94% -56.9 × 0.7%)/(91.8 × 50% × 94%)/(91.8 × 50% × 100% > × 99.1% clethodim yield ═ 56.9 × 96.5%)/(91.8 × 50% × 94% × 359.91/270.39) × 95.6%
Examples 2 to 4
Using the same continuous clethodim synthesis system as in example 1, the protamine was dissolved in ethanol to give an ethanol solution containing 50 wt% of protamine. The difference from the embodiment 1 is that: the molar ratio of the chloramine to the refined trione is 1.15, the flow rate of the refined trione is 40ml/min, the flow rate of the chloramine is 8ml/min, and the total reaction residence time of materials in the microchannel reactors I and II is 22 seconds. In the reaction process, the reaction temperatures of the microchannel reactors I and II are the same, and the reaction temperatures are controlled to be 55 ℃, 65 ℃ and 70 ℃ respectively in examples 2-4, and the results of the products are shown in Table 1 respectively.
TABLE 1 influence of different temperatures on the reaction
As can be seen from the data in the table above, the reaction temperature is increased, the mixing and mass transfer rates among materials are accelerated, the reaction rate is increased, the conversion rate of the trione and the yield of the clethodim are both increased, and therefore, the reaction process is facilitated by increasing the reaction temperature.
Examples 5 to 7
The same continuous clethodim synthesis system as in example 1 was used. The differences from example 1 are as follows: in the reaction process, the reaction temperature of the reaction materials in the microchannel reactors I and II is 75 ℃, the flow rate of the refined trione is 40ml/min, the flow rate of the chloramine is 6.5-8 ml/min, the retention time is 22 seconds, and the molar ratio of the chloramine to the refined trione in the feed is controlled to be 1.10, 1.15 and 1.20 respectively. The product results are shown in Table 2.
TABLE 2 influence of the molar ratio of chloramine and Triton on the reaction
As can be seen from the data in the table above, the molar ratio of the chloramine to the protamine is increased, namely, the amount of the chloramine is increased, the conversion rate of the protamine and the yield of the clethodim are correspondingly increased, and the increase of the amount of the chloramine is beneficial to the reaction.
Examples 8 to 9
The same continuous clethodim synthesis system as in example 1 was used. The differences from example 1 are as follows: in the reaction process, the reaction temperature of the reaction materials in the microchannel reactors I and II is 75 ℃, the molar ratio of the chloramine to the fine trione is 1.20, the flow rate of the fine trione is 20ml/min, the flow rate of the chloramine is 4ml/min, and the retention time is 44 s; the flow rate of the refined trione is 40ml/min, and the flow rate of the chloramine is 8 ml/min. The product results are shown in Table 3
TABLE 3 influence of residence time on the reaction
From the data in the table above, it can be seen that the residence time of the material in the reactor is controlled by adjusting the feed flow rate, and the longer the residence time, the longer the reaction time of the material is, the mass and heat transfer of the reaction is facilitated, the conversion rate of the triketone and the yield of the clethodim are facilitated, and the reaction is not facilitated.
Comparative example 1
At present, the process adopted by production enterprises is an intermittent reaction kettle, and the reaction solvent is petroleum ether.
Taking a 250ml three-mouth bottle, adding 50ml petroleum ether and 27g (0.1mol) of refined trione, uniformly stirring, dropwise adding 13g (0.12mol) of chloramine at 35 ℃, raising the temperature of the system to 36 ℃ in the dropwise adding process, continuing to raise the temperature to 75 ℃ for reaction after the dropwise adding is finished within 5 minutes, and sampling in the reaction process to analyze the reaction progress.
TABLE 4 reaction results of different reaction times in the reaction vessel
As can be seen from the above table, under the reaction process conditions adopted in industry, the conversion rate of the raw material, namely the refined trione, and the yield of the clethodim are both low after the reaction is carried out for 30 min. Because of the deficiency of the kettle type reaction in the aspects of mass transfer and heat transfer, the conversion rate of the raw material of the refined trione is slower, the reaction time is longer, and the possibility of side reaction and energy consumption are increased.
Comparative examples 2 to 4
The same continuous clethodim synthesis system as in example 1 was used, and the same petroleum ether solvent was used to dissolve the protriene in petroleum ether to obtain a 50 wt% protriene in petroleum ether, the molar ratio of the chloramine to the protriene feed was 1.15, the protriene flow rate was 40ml/min, the chloramine flow rate was 8ml/min, and the total reaction residence time of the materials in the microchannel reactors I and II was 22 seconds. In the reaction process, the reaction temperature of the reaction materials in the microchannel reactors I and II is the same, the reaction temperature is respectively controlled to be 55 ℃, 65 ℃ and 70 ℃ in comparative examples 2-4, and the results of the products are respectively shown in Table 1.
TABLE 5 influence of petroleum ether as solvent on the reaction
Comparative examples 5 to 7
Clethodim was synthesized using a microchannel reactor, different from that of example 1, which is the microreactor disclosed in this research group patent CN 101613285A. Dissolving the trione in ethanol to obtain an ethanol solution, wherein the content of the trione in the ethanol solution is 50 wt%. The difference from the embodiment 1 is that: the mol ratio of the chloramine to the refined trione is 1.16: 1, the flow rate of the refined trione is 20ml/min, the flow rate of the chloramine is 4ml/min, and the retention time of the materials in the microchannel reactor is 18 seconds. In comparative examples 5 to 7, the reaction temperatures were controlled to 55 ℃ and 65 ℃ and 70 ℃ respectively, and the results of the products are shown in Table 1, respectively.
TABLE 6 influence of different temperatures on the reaction
Claims (8)
1. A method for rapidly synthesizing clethodim by using a micro-reaction system is characterized in that,
the system comprises a micro-channel reactor I, a micro-channel reactor II and a product collector which are sequentially connected in series;
the microchannel reactor I comprises a microstructure mixing chip set and a reaction chip set which are communicated with each other; the microstructure mixing chip set is provided with a channel structure in which rhombic grooves and cylindrical turbulent flow rhombic grooves are alternately arranged; the reaction chip group is of a Z-shaped or zigzag single-channel structure;
the microchannel reactor II comprises a reaction chip set; the reaction chip group is provided with a Z-shaped or zigzag single-channel structure;
the method comprises the following steps:
(1) dissolving the trihydroxy ketone in a polar solvent to obtain a solution I;
(2) the solution I and the chloramine are respectively conveyed into a microchannel reactor I by two continuous conveying devices for mixing and reaction, and the mixing and reaction temperature is controlled by a heat exchange channel of the microchannel reactor I;
(3) the material reacted by the microchannel reactor I enters a microchannel reactor II for further mixing and reaction, the reaction temperature is controlled by a heat exchange channel of the microchannel reactor II, and a reaction product is obtained after the reaction is finished;
(4) feeding the obtained reaction product into a product collector, adding dilute hydrochloric acid for washing, stirring, and separating an organic phase to obtain the clethodim;
the reaction temperature of the reaction materials in the microchannel reactor I and the microchannel reactor II is 55-75 ℃;
the residence time of the reaction materials in the microchannel reactor I is 1-50 seconds; the residence time in the microchannel reactor II is 25-60 seconds.
2. The method of claim 1, wherein the reactive chip set is formed from one or more reactive chip stacks distributed in parallel; the microstructure hybrid chip set is formed by stacking one or more parallel hybrid chips; the system also comprises two continuous conveying devices which are respectively communicated with the two material inlets of the microchannel reactor I.
3. The method of claim 1, wherein the microchannel reactor I and the microchannel reactor II are both provided with heat exchange channels; heating or cooling chips are arranged between the microstructure mixing chip set of the microchannel reactor I and each chip of the reaction chip set; heating or cooling chips are arranged among the chips of the reaction chip group of the microchannel reactor II; and the microchannel reactor I and the microchannel reactor II are respectively provided with a heat exchanger for providing a cold source or a heat source for heating or cooling the chip.
4. The method according to any one of claims 1 to 3, wherein the channel angle of the rhombic or rhombic channel, the Z-shaped channel or the zigzag channel with the cylindrical turbulent flow is 90-150 degrees; the hydraulic diameter of the reaction channels of the micro-channel reactor I and the micro-channel reactor II is 0.1-3 mm, and the length of the reaction channels is 0.2-100 cm.
5. The method of claim 1,
the content of the trione in the solution I is 50-80 wt%, and the polar solvent is ethanol; the molar ratio of the chloramine to the refined trione is (1.00-1.30) to 1.
6. The method according to claim 5, wherein the molar ratio of the chloramine to the protamine is (1.05-1.25) to 1.
7. The method according to claim 6, wherein the molar ratio of the chloramine to the protamine is (1.1-1.2) to 1.
8. The process of claim 1, wherein the total residence time of the reactant material in microchannel reactor i and microchannel reactor ii is from 25 to 60 seconds.
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