CN109627225B - Continuous production method of multi-kettle series triazine herbicide - Google Patents
Continuous production method of multi-kettle series triazine herbicide Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
Abstract
The invention relates to a multi-kettle series connection continuous production method of triazine herbicides, metered cyanuric chloride solution is precooled, mixed with alkylamino R1 in a mixer and then enters a first-section reaction kettle, continuously discharged, neutralized with alkali in the mixer after passing through a heat exchanger and enters a first-section neutralization kettle, mixed with alkylamino R2 in the mixer after passing through a continuous water separator and the heat exchanger after completing the first-section reaction and then enters a second-section reaction kettle, mixed with alkali in the mixer after passing through the heat exchanger and then enters the second-section neutralization kettle, and after neutralization, a continuous layering device separates out a water phase and removes the solvent to obtain the triazine products. The production method has the characteristics of high productivity, good production stability, high efficiency, high product quality and the like, is particularly suitable for technical transformation of the existing production enterprises, has lower transformation cost, basically does not add new reaction equipment, and is easy to master the technology for the existing enterprises.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a multi-kettle series connection continuous production method of triazine herbicides.
Background
Triazine herbicides are among the traditional herbicides launched in the 50 s of the 20 th century and their herbicidal activity was discovered in 1952 by Geigy, switzerland. It acts by inhibiting photosynthesis of plants through photosynthesis system II (PS II) with D1 protein as the target. Through years of experiments, a series of triazine herbicides are developed. The herbicide is prepared by replacing two chlorine atoms in trichloro chloride with two alkylamino groups, wherein the two alkylamino groups include ethylamino, isopropylamino, cyclopropylamino, tert-butylamino, etc. Typical examples of the jin-type herbicides include atrazine (atrazine), simazine, terbuthylazine, and prometryn. The herbicide is a systemic conductive pre-emergence herbicide and post-emergence herbicide, can prevent and kill annual gramineous weeds and broadleaf weeds, and has a certain inhibiting effect on certain perennial weeds. The herbicide is suitable for weeding corn, sorghum, sugarcane, orchards, forest lands and the like, and can also be used as a non-selective herbicide on non-farmland lands and fallow lands.
In the current industrial production of triazine herbicides, cyanuric chloride, various organic amines and liquid alkali are used as main raw materials, firstly, a solution of cyanuric chloride in toluene is prepared, then, the organic amine is dripped at the temperature of a jacket of a synthesis kettle, and then, the liquid alkali is dripped at a controlled temperature to complete one-step substitution, and the two-step substitution is also completed as above. The two-step substitution is carried out in the same reaction kettle, the middle part is separated into a water phase, and the temperature is controlled by a reaction kettle jacket. The inventor finds that: the problems of the prior art are as follows: firstly, the reaction temperature is not easy to control, and because the heat exchange area of the jacket is relatively small and the reaction heat is large, the reaction dripping speed cannot be fast, otherwise the side reaction is aggravated; secondly, the productivity is low, and due to the limitation of the dropping speed, the whole process is completed by the sequencing batch reaction for about 18 to 24 hours; thirdly, side reactions are more, and the side reactions are more and the product purity is poorer due to factors such as inaccurate temperature control, operation factors, local over-concentration and the like; fourthly, the intermittent production equipment is more, the operation is complex, the labor efficiency is lower, and the quality fluctuation caused by manual operation errors is inevitable.
The process for synthesizing triazine herbicide by using microreactors reported in China has the disadvantages of high investment and low cost performance for the ten-thousand-ton product due to low load of a single set of microreactors.
In CN201710663765.7, a mixer and a tubular reactor are adopted to synthesize the triazine herbicide atrazine, although continuous production can be realized, no back mixing process exists in the reaction process, and the acid binding in the substitution reaction and neutralization stages possibly cannot achieve the best effect due to shorter retention time; in addition, the water phase of the first-stage reaction is not separated between the first-stage reaction and the second-stage reaction in the whole process, and impurities and unreacted materials in the water phase are easily brought into the next stage to cause impurity increase.
Disclosure of Invention
The invention provides a continuous production method suitable for large-scale industrialized multi-kettle tandem triazine herbicides, which has the characteristics of high productivity, good production stability, high efficiency, high product quality and the like, is particularly suitable for technical transformation of the existing production enterprises, has lower transformation cost, basically does not add new reaction equipment, and has the technology which is easy to master by the existing enterprises.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a multi-kettle series triazine herbicide continuous production method comprises the following steps:
(1) after dissolving cyanuric chloride in a solvent, mixing the cyanuric chloride with alkylamino R1 in a mixer 3 through a precooler 2, and then entering a first-stage reaction kettle 4;
(2) the reaction material is discharged from the first reaction kettle 4, passes through the heat exchanger 5, part of the reaction material returns to the first-stage reaction kettle 4, part of the reaction material is mixed with alkali in the mixer 6, and the mixture enters the first-stage neutralization kettle 7 to complete first-stage reaction;
(3) the reaction material is discharged from the first-stage neutralization kettle 7, passes through a heat exchanger 8, partially returns to the first-stage neutralization kettle 7, partially passes through a continuous water separator 9 and a heat exchanger 10, is mixed with alkylamino R2 in a mixer 11, and then enters a second-stage reaction kettle 12;
(4) the reaction material is discharged from the second-stage reaction kettle 12, then passes through the heat exchanger 13, part of the reaction material returns to the second-stage reaction kettle 12, part of the reaction material is mixed with alkali in the mixer 14, and enters the second-stage neutralization kettle 15, the material after the second-stage reaction is discharged from the second-stage neutralization kettle 15, then passes through the heat exchanger 16, part of the reaction material returns to the second-stage neutralization kettle 15, and part of the reaction material enters the continuous layering device 17, and after a water phase is separated out, a solvent is removed, and the triazine product is obtained after.
According to the method, continuous layering is performed after the first-stage neutralization kettle and the second-stage neutralization kettle, so that the water phase of the reaction liquid is not brought into the next procedure, the reaction activity is greatly improved, and side reactions are inhibited.
Wherein the structure of the triazine herbicide is shown as a general formula A,
the reaction equation is as follows:
in some embodiments, the R1 is: -NHC2H5(one ethylamino), -NHCH (CH)3)2(isopropylamino), -N (C)2H5)2(diethylamino), -NHC (CN) (CH)3)2(isobutyronitrile amino), -NHC (CH)3)3(tert-butylamino), -NHC3H5(cyclopropylamino), -NHCH2COOH (acetamido), -NHCH (CH)3)(C2H5) (isobutylamino), -NHCH3(a methylamino group), -N (CH)3)2One kind of (dimethylamino) group;
in some embodiments, the compound to which R2 corresponds is: -NHC2H5(one ethylamino), -NHCH (CH)3)2(isopropylamino), -N (C)2H5)2(diethylamino), -NHC (CN) (CH)3)2(isobutyronitrile amino), -NHC (CH)3)3(tert-butylamino), -NHC3H5(cyclopropylamino), -NHCH2COOH (acetamido), -NHCH (CH)3)(C2H5) (isobutylamino), -NHCH3(a methylamino group), -N (CH)3)2One kind of (dimethylamino) group;
in some embodiments, the solvent in the cyanuric chloride solution is chlorobenzene, toluene, xylene, chloroform, carbon tetrachloride, benzene, ethanol or nitrobenzene.
In some embodiments, the operation safety can be significantly improved by stopping the nitrogen feed when the nitrogen is first fed into the compounding tank 1 before compounding and the oxygen content is below the explosive range of the solvent. In order to ensure the continuity of the reaction, two material mixing kettles are selected, one is opened and the other is prepared.
The temperature of each reaction kettle and the mixer in the application is controlled according to different target products, and a temperature range can be adopted.
In some embodiments, the compounding temperature of the compounding kettle 1 is 20 ℃ to 45 ℃.
In some embodiments, the temperature of precooler 2 is between-10 ℃ and 10 ℃.
In some embodiments, the ratio of the feed amount of cyanuric chloride to the amount of feed amount of substance of R1 or R2 is from 1:1.0 to 1.05.
In this application, all the transferred materials of cyanuric chloride solution, R1 and later R2, alkali, etc. are precisely metered by means of flow meters or metering pumps.
In some embodiments, the concentration of R1, R2 is between 50-100%, preferably 50-70% aqueous organic amine solution.
In the present application, all concentrations are mass concentrations.
In some embodiments, the amount of extracorporeal circulation is typically 3 to 20 times the volume of the reaction vessel. The reaction liquid of the first-stage reaction kettle, the first-stage neutralization kettle, the second-stage reaction kettle and the second-stage neutralization kettle is subjected to in-vitro large-flow circulation, an in-vitro circulation heat exchanger can bring accurate temperature control of the reaction, and the reaction can be more fully performed through proper back mixing of the in-vitro circulation.
In some embodiments, the ratio of the amount of base added to the amount of cyanuric chloride species in the mixers 6, 14 is from 1.05 to 1.0: 1.
The base added to the mixer 6 includes, but is not limited to, NaOH, KOH, etc., and the concentration of the base ranges from 10 to 50%.
In some embodiments, the temperature of the heat exchanger 5 is between 0 ℃ and 25 ℃;
in some embodiments, the temperature of the heat exchanger 8 is between 15 ℃ and 30 ℃;
in some embodiments, the temperature of the heat exchanger 10 is between 10 ℃ and 30 ℃;
in some embodiments, the temperature of the heat exchanger 13 is 20 ℃ to 45 ℃;
in some embodiments, the temperature of the heat exchanger 16 is from 35 ℃ to 50 ℃.
In some embodiments, the upper oil phase of the continuous stratifier 17 is desolventized by steam distillation by metering into a subsequent plurality of desolventizing kettles 18; the lower aqueous phase is sent to wastewater treatment.
The invention also provides a triazine herbicide synthesized by any one of the methods, wherein the triazine herbicide is one of atrazine, clonazine, cyanazine, cycloprozine, liquirizine, metribuzine, propazine, cyazone, terbuthylazine, promazine, terbuthylazine and simazine.
The invention has the beneficial effects that:
the method takes cyanuric chloride solution as a raw material, takes alkali as an acid-binding agent, and reacts with R1 and R2 organic amine in sequence to obtain a triazine herbicide target product, and the water phase is separated in the middle and the reaction temperature is strictly controlled through extracorporeal circulation. Compared with the prior art, the production process has the advantages of strong continuity, high productivity, good production stability, easy mastering, few control points in the production process, high product quality, simple equipment, low investment, high process automation degree and good social and economic benefits.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a process flow diagram of the continuous process for the production of triazine herbicides in multi-tank series as in example 1. Wherein, 1 batching kettle, 2 precooler, 3, 6, 11, 14 mixer, 4 first-stage reaction kettle, 5, 8, 10, 13, 16 heat exchanger, 7 first-stage neutralization kettle, 9, 17 continuous layering device, 12 second-stage reaction kettle, 15 second-stage neutralization kettle, 18 desolventizing kettle.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the method aims at solving the problems of difficult control of reaction temperature, low productivity and more side reactions in the prior art. Therefore, the invention provides a multi-kettle series connection triazine herbicide continuous production method, which comprises the following steps:
(1) filling a certain amount of nitrogen into the batching kettle 1 for replacement, and mixing cyanuric chloride and a solvent according to a mass ratio of 1: 5-15, and fully dissolving to obtain the cyanuric chloride solution.
(2) The prepared cyanuric chloride solution is fully mixed with precisely measured R1 in a mixer 3 through a precooler 2 by precise measurement and then enters a first-stage reaction kettle 4.
(3) The reaction liquid in the first-stage reaction kettle 4 enters a heat exchanger 5 through a pump to be subjected to extracorporeal circulation, and is discharged to enter a mixer 6, and is fully mixed with the alkali which is accurately metered in the mixer 6 to enter a first-stage neutralization kettle 7.
(4) The reaction liquid in the first-stage neutralization kettle 7 enters a heat exchanger 8 through a pump for extracorporeal circulation and is discharged to enter a continuous layering device 9.
(5) The oil phase separated out from the upper part of the continuous delayer 9 is precisely metered by a pump and then enters a heat exchanger 10, and then is fully mixed with precisely metered R2 through a mixer 11 and enters a two-stage reaction kettle 12. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
(6) The reaction liquid in the second-stage reaction kettle 12 enters a heat exchanger 13 through a pump to be subjected to extracorporeal circulation, and is discharged to enter a mixer 14, and is fully mixed with the alkali which is accurately metered in the mixer 14 to enter a second-stage neutralization kettle 15.
(7) The reaction liquid in the second-stage neutralization kettle 15 enters a heat exchanger 16 through a pump for extracorporeal circulation and is discharged to enter a continuous layering device 17.
(8) The oil phase separated from the upper part of the continuous delayer 17 is precisely metered by a pump and then enters a desolventizing kettle 18, and the desolventizing kettle is subjected to steam distillation to remove the solvent for subsequent separation and drying, so that the product can be obtained. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
The compound group corresponding to R1 is: -NHC2H5(one ethylamino), -NHCH (CH)3)2(isopropylamino), -N (C)2H5)2(diethylamino), -NHC (CN) (CH)3)2(isobutyronitrile amino), -NHC (CH)3)3(tert-butylamino), -NHC3H5(cyclopropylamino), -NHCH2COOH (acetamido), -NHCH (CH)3)(C2H5) (isobutylamino), -NHCH3(a methylamino group), -N (CH)3)2(dimethylamino group).
The compound corresponding to R2 is: -NHC2H5(one ethylamino), -NHCH (CH)3)2(isopropylamino), -N (C)2H5)2(diethylamino), -NHC (CN) (CH)3)2(isobutyronitrile amino), -NHC (CH)3)3(tert-butylamino), -NHC3H5(cyclopropylamino), -NHCH2COOH (acetamido), -NHCH (CH)3)(C2H5) (isobutylamino), -NHCH3(a methylamino group), -N (CH)3)2(dimethylamino group).
The triazine herbicides corresponding to the target compounds represented by the general formula a include, but are not limited to: atrazine, clonazine, cyanazine, cycloprozine, liquirizine, metribuzin, propazine, hydralazine, metribuzin, terbuthylazine, promazine, terbuthylazine, simazine, etc.
The target compounds also include other compounds formed by free combination of substituents R1, R2.
In the step (1), nitrogen is firstly filled into the batching kettle 1 before batching, and the nitrogen filling can be stopped when the indication of the oxygen content analyzer is lower than the explosion range of the solvent, so that the operation safety can be obviously improved. In order to ensure the continuity of the reaction, two material mixing kettles are selected, one is opened and the other is prepared.
The solvent in the step (1) comprises: chlorobenzene, toluene, xylene, chloroform, carbon tetrachloride, benzene, ethanol, nitrobenzene, and the like, with toluene being preferred as the solvent.
In the step (1), the batching temperature of the batching kettle 1 is controlled between 20 ℃ and 45 ℃.
The temperature of the precooler 2 in the step (2) is controlled between-10 ℃ and 10 ℃.
The mixers 3, 6, 11, 14 in the step (2) include a static mixer, a tubular reactor homogenizing pump, etc., and preferably a static mixer.
In the step (2), all transferred materials such as cyanuric chloride solution, R1, R2 and alkali in the following process are precisely metered, and metering devices comprise various flow meters, metering pumps, weighing devices, liquid level metering devices and the like, preferably mass flow meters and metering pumps.
The ratio of the feeding amount of the cyanuric chloride to the feeding amount of the R1 in the step (2) is 1:1.0-1.05
The temperature of the heat exchanger 5 in the step (3) is controlled between 0 and 25 ℃.
In the step (3), the volume ratio of the extracorporeal circulation quantity of the first-stage reaction kettle to the first-stage reaction kettle is 3-20: 1.
The discharge amount of the first-stage reaction kettle in the step (3) is equal to the feed amount (the sum of the cyanuric chloride solution and the alkali).
The ratio of the amount of the alkali added to the mixer 6 to the amount of the cyanuric chloride substance in step (3) is 1.05-1.0:1
The alkali added in the mixer 6 in the step (3) includes but is not limited to NaOH, KOH, etc., and the concentration of the alkali is in the range of 10-50%.
The temperature of the heat exchanger 8 in the step (4) is controlled between 15 ℃ and 30 ℃.
In the step (4), the volume ratio of the extracorporeal circulation quantity of the first-stage neutralization kettle 7 to the first-stage neutralization kettle is 3-20: 1.
In the step (4), the discharge amount of the first-stage neutralization kettle 7 is equal to the feed amount (the sum of the discharge amount of the first-stage reaction kettle and alkali).
The continuous laminators 9, 17 in step (4) comprise static continuous laminators or centrifugal extractors. A static continuous delayer is preferred.
The temperature of the heat exchanger 10 in the step (5) is controlled between 10 ℃ and 30 ℃.
The ratio of the feeding amount of R2 to the feeding amount of cyanuric chloride in step (5) is 1.0-1.05: 1.
the temperature of the heat exchanger 13 in the step (6) is controlled between 20 and 45 ℃.
In the step (6), the volume ratio of the extracorporeal circulation quantity of the second-stage reaction kettle to the second-stage reaction kettle is 3-20: 1.
The discharge amount of the second-stage reaction kettle in the step (6) is equal to the feed amount (the sum of the oil phase from the continuous demixer and R2).
The ratio of the amount of alkali added to the mixer 14 in step (6) to the amount of cyanuric chloride species is 1.05-1.0: 1.
The alkali added to the mixer 6 in the step (6) includes, but is not limited to, NaOH, KOH, etc., and the concentration of the alkali is in the range of 10 to 50%.
The temperature of the heat exchanger 16 in the step (7) is controlled between 35 and 50 ℃.
In the step (7), the volume ratio of the extracorporeal circulation quantity of the second-stage neutralization kettle to the second-stage neutralization kettle is 3-20: 1.
In the step (7), the discharge amount of the second-stage neutralization kettle is equal to the feed amount (the sum of the discharge amount of the second-stage reaction kettle and the alkali).
And (4) in the step (8), the upper oil phase of the continuous layering device 17 enters a plurality of desolventizing kettles for steam distillation desolventizing through metering. The lower aqueous phase is sent to wastewater treatment.
The reaction liquid of the first-stage reaction kettle, the first-stage neutralization kettle, the second-stage reaction kettle and the second-stage neutralization kettle is subjected to in-vitro large-flow circulation, an in-vitro circulation heat exchanger can bring accurate temperature control of the reaction, and the reaction can be more fully performed through proper back mixing of the in-vitro circulation.
And continuous layering is carried out after the first-stage neutralization kettle and the second-stage neutralization kettle, so that the water phase of the reaction solution is not brought into the next procedure, the reaction activity is greatly improved, and side reactions are inhibited.
The reaction kettle volume of the first-stage reaction kettle 4, the first-stage neutralization kettle 7, the second-stage reaction kettle 12 and the second-stage neutralization kettle 15 in the steps is generally 2-20m3Preferably 5m3And (5) a reaction kettle.
In the above step, the amount of the extracorporeal circulation is generally 3 to 20 times, preferably 5 times, the volume of the reaction vessel.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1: multi-kettle series continuous production method of atrazine
(1) Filling a certain amount of nitrogen into the batching kettle 1 for replacement, and mixing cyanuric chloride and toluene according to a mass ratio of 1: 5, adding the mixture into a batching kettle, and fully dissolving to obtain a toluene solution of cyanuric chloride;
(2) the prepared cyanuric chloride solution passes through a precooler 2 according to the flow rate of 6000 kg/h (wherein the cyanuric chloride flow rate is 1000 kg/h), the material outlet temperature of the precooler 2 is controlled to be 5-7 ℃, the mixed solution is fully mixed with 70 percent of isopropylamine aqueous solution which is accurately metered in a mixer 3 and enters a first-stage reaction kettle 4, and the flow rate of the isopropylamine aqueous solution is controlled to be 460 kg/h.
(3) First stage reaction kettle 4 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 5 through a pump (the temperature of a material outlet is controlled to be 13-15 ℃) to carry out extracorporeal circulation (the circulation flow is 25m3Hour) and simultaneously discharged (the discharge flow is 6460 kg/hour), the mixture enters a mixer 6 and is fully mixed with NaOH accurately metered in the mixer 6, and the mixture enters a first-stage neutralization kettle 7, wherein the concentration of the NaOH is 30 percent, and the flow is 723 kg/hour.
(4) One-stage neutralization kettle 7 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 8 through a pump (the temperature of a material outlet is controlled at 20-23 ℃) to carry out extracorporeal circulation (the circulation flow is 25m3Hour) and simultaneously (discharge rate 7183 kg/hour) into the continuous laminator 9.
(5) The oil phase separated from the upper part of the continuous delayer 9 is accurately metered by a pump (the flow rate is to maintain the liquid level of the delayer to be constant), enters a heat exchanger 10 (the temperature of a material outlet is controlled at 20 ℃), is fully mixed with accurately metered monoethylamine by a mixer 11, and enters a two-stage reaction kettle 12, wherein the monoethylamine is 70% aqueous solution, and the flow rate is controlled at 345.7 kg/h. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
(6) Two-stage reaction kettle 12 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 13 through a pump (the temperature of a material outlet is controlled to be 25-30 ℃) to carry out extracorporeal circulation (the circulation flow is 25m3Hour) and the mixture is discharged (the flow rate is to maintain the liquid level of the second-stage reaction kettle 12 unchanged), and the mixture is fully mixed with the NaOH which is accurately metered in the mixer 4 and enters the second-stage neutralization kettle 15, the concentration of the NaOH is 30 percent, and the flow rate is 723 kg/hour.
(7) Two-stage neutralization kettle 15 (reaction kettle volume 5 m)3) Enters a heat exchanger 16 through a pump (the temperature of a material outlet is controlled to be 40-45 ℃) for extracorporeal circulation and simultaneously discharges the materials into a continuous delayer 17.
(8) The oil phase discharged from the upper part of the continuous delayer 17 is accurately metered by a pump (the flow rate is to maintain the liquid level of the delayer constant), and then enters a desolventizing kettle 18, and the product can be obtained by carrying out steam distillation in the desolventizing kettle to remove the solvent and carrying out subsequent separation and drying. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
The atrazine product can be obtained by the process with the content of 1.159 ton/hour, 98.9 percent and the yield of 99 percent.
Example 2: multi-kettle series continuous production method of simazine
(1) Filling a certain amount of nitrogen into the batching kettle 1 for replacement, and mixing cyanuric chloride and toluene according to a mass ratio of 1: 5, adding the mixture into a batching kettle, and fully dissolving to obtain a toluene solution of cyanuric chloride;
(2) the prepared cyanuric chloride solution passes through a precooler 2 according to the flow rate of 6000 kg/h (wherein the cyanuric chloride is 1000 kg/h), the material outlet temperature of the precooler 2 is controlled to be 5-7 ℃, the prepared cyanuric chloride solution and 70 percent of accurately metered isopropylamine aqueous solution are fully mixed in a mixer 3 and enter a first-stage reaction kettle 4, and the flow rate of monoethylamine aqueous solution is controlled to be 350 kg/h.
(3) First stage reaction kettle 4 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 5 through a pump (the temperature of a material outlet is controlled at 8-10 ℃) to carry out extracorporeal circulation (the circulation flow is 25 m)3Hour) and simultaneously discharged (the discharge flow rate is 6350 kg/hour), the mixture enters a mixer 6 and is fully mixed with accurately metered NaOH in the mixer 6, and the mixture enters a first-stage neutralization kettle 7, wherein the concentration of the NaOH is 30 percent, and the flow rate is 723 kg/hour.
(4) One-stage neutralization kettle 7 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 8 through a pump (the temperature of a material outlet is controlled at 18-20 ℃) to carry out extracorporeal circulation (the circulation flow is 25 m)3Hour) and simultaneously discharged (discharge rate 7073 kg/hour) into the continuous delayer 9.
(5) The oil phase separated from the upper part of the continuous delayer 9 is accurately metered by a pump (the flow is to maintain the liquid level of the delayer to be constant), enters a heat exchanger 10 (the temperature of a material outlet is controlled to be 25-28 ℃), is fully mixed with accurately metered monoethylamine by a mixer 11, and enters a second-stage reaction kettle 12, wherein the monoethylamine is 70% aqueous solution, and the flow is controlled to be 345.7 kg/h. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
(6) Two-stage reaction kettle 12 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 13 through a pump (the temperature of a material outlet is controlled at 30-35 ℃) to carry out extracorporeal circulation (the circulation flow is 25 m)3Hour) and the mixture is discharged (the flow rate is to maintain the liquid level of the second-stage reaction kettle 12 unchanged), and the mixture is fully mixed with the NaOH which is accurately metered in the mixer 4 and enters the second-stage neutralization kettle 15, the concentration of the NaOH is 30 percent, and the flow rate is 723 kg/hour.
(7) Two-stage neutralization kettle 15 (reaction kettle volume 5 m)3) Enters a heat exchanger 16 through a pump (the temperature of a material outlet is controlled to be 35-40 ℃) for extracorporeal circulation and simultaneously discharges the materials into a continuous delayer 17.
(8) The oil phase discharged from the upper part of the continuous delayer 17 is accurately metered by a pump (the flow rate is to maintain the liquid level of the delayer constant), and then enters a desolventizing kettle 18, and the product can be obtained by carrying out steam distillation in the desolventizing kettle to remove the solvent and carrying out subsequent separation and drying. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
The simazine product can be obtained by the processes, wherein the yield is 1.089 tons/hour, the content is 98.8 percent, and the yield is 99.2 percent.
Example 3: multi-kettle series continuous production method of terbuthylazine
(1) Filling a certain amount of nitrogen into the batching kettle 1 for replacement, and mixing cyanuric chloride and toluene according to a mass ratio of 1: 5, adding the mixture into a batching kettle, and fully dissolving to obtain a toluene solution of cyanuric chloride;
(2) the prepared cyanuric chloride solution passes through a precooler 2 according to the flow rate of 6000 kg/h (wherein the cyanuric chloride is 1000 kg/h), the material outlet temperature of the precooler 2 is controlled to be 5-7 ℃, the mixed cyanuric chloride solution and 70 percent aqueous solution of tert-butylamine which is accurately metered are fully mixed in a mixer 3 and enter a first-stage reaction kettle 4, and the flow rate of the aqueous solution of the tert-butylamine is controlled to be 566.5 kg/h.
(3) First stage reaction kettle 4 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 5 through a pump (the temperature of a material outlet is controlled at 10-13 ℃) to carry out extracorporeal circulation (the circulation flow is 25m3Hourly) simultaneous discharge (discharge flow 6566)5 kg/h) into a mixer 6, and is fully mixed with accurately metered NaOH in the mixer 6 into a first-stage neutralization kettle 7, wherein the concentration of the NaOH is 30 percent, and the flow rate is 723 kg/h.
(4) One-stage neutralization kettle 7 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 8 through a pump (the temperature of a material outlet is controlled to be 25-27 ℃) to carry out extracorporeal circulation (the circulation flow is 25m3Hour) and simultaneously discharged (discharge rate 7289.5 kg/hour) into the continuous delayer 9.
(5) The oil phase separated from the upper part of the continuous delayer 9 is accurately metered by a pump (the flow is to maintain the liquid level of the delayer to be constant), enters a heat exchanger 10 (the temperature of a material outlet is controlled to be 20-25 ℃), is fully mixed with accurately metered monoethylamine by a mixer 11, and enters a second-stage reaction kettle 12, wherein the monoethylamine is 70% aqueous solution, and the flow is controlled to be 345.7 kg/h. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
(6) Two-stage reaction kettle 12 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 13 through a pump (the temperature of a material outlet is controlled at 30-35 ℃) to carry out extracorporeal circulation (the circulation flow is 25 m)3Hour) and the mixture is discharged (the flow rate is to maintain the liquid level of the second-stage reaction kettle 12 unchanged), and the mixture is fully mixed with the NaOH which is accurately metered in the mixer 4 and enters the second-stage neutralization kettle 15, the concentration of the NaOH is 30 percent, and the flow rate is 723 kg/hour.
(7) Two-stage neutralization kettle 15 (reaction kettle volume 5 m)3) Enters a heat exchanger 16 through a pump (the temperature of a material outlet is controlled to be 55-60 ℃) to carry out extracorporeal circulation and simultaneously discharge the materials into a continuous delayer 17.
(8) The oil phase discharged from the upper part of the continuous delayer 17 is accurately metered by a pump (the flow rate is to maintain the liquid level of the delayer constant), and then enters a desolventizing kettle 18, and the product can be obtained by carrying out steam distillation in the desolventizing kettle to remove the solvent and carrying out subsequent separation and drying. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
The terbuthylazine product can be obtained by the processes, wherein the terbuthylazine product is 1.231 ton/hour, the content is 99.2 percent, and the yield is 99.1 percent.
Example 4: multi-kettle series continuous production method of propazine
(1) Filling a certain amount of nitrogen into the batching kettle 1 for replacement, and mixing cyanuric chloride and toluene according to a mass ratio of 1: 5, adding the mixture into a batching kettle, and fully dissolving to obtain a toluene solution of cyanuric chloride;
(2) the prepared cyanuric chloride solution passes through a precooler 2 according to the flow rate of 6000 kg/h (wherein the cyanuric chloride flow rate is 1000 kg/h), the material outlet temperature of the precooler 2 is controlled to be 5-7 ℃, the mixed solution is fully mixed with 70 percent of isopropylamine aqueous solution which is accurately metered in a mixer 3 and enters a first-stage reaction kettle 4, and the flow rate of the isopropylamine aqueous solution is controlled to be 915.7 kg/h.
(3) First stage reaction kettle 4 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 5 through a pump (the temperature of a material outlet is controlled to be 15-20 ℃) to carry out extracorporeal circulation (the circulation flow is 30m3Hour) and simultaneously discharged (the discharge flow is 6915.7 kg/hour) to enter a mixer 6, and the mixture is fully mixed with accurately metered NaOH in the mixer 6 to enter a first-stage neutralization kettle 7, wherein the concentration of the NaOH is 30 percent, and the flow is 1450 kg/hour.
(4) One-stage neutralization kettle 7 (reaction kettle volume 5 m)3) The reaction liquid enters a heat exchanger 8 through a pump (the temperature of a material outlet is controlled at 40-50 ℃) to carry out extracorporeal circulation (the circulation flow is 30 m)3Hour) and simultaneously discharged (discharge rate 8365.7 kg/hour) into the continuous delayer 17.
(5) The oil phase discharged from the upper part of the continuous delayer 17 is accurately metered by a pump (the flow rate is to maintain the liquid level of the delayer constant), and then enters a desolventizing kettle 18, and the product can be obtained by carrying out steam distillation in the desolventizing kettle to remove the solvent and carrying out subsequent separation and drying. The water phase separated out from the lower part of the continuous delayer is sent to waste water treatment.
The yield of the product of the promethazine is 98.8 percent with the content of 98.5 percent and 1.237 tons/hour.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A multi-kettle series connection triazine herbicide continuous production method is characterized by comprising the following steps:
(1) pre-cooling the cyanuric chloride solution, mixing the precooled cyanuric chloride solution with alkylamine R1 in a mixer (3), and feeding the mixture into a first-stage reaction kettle (4);
(2) the material is discharged from the first-stage reaction kettle (4), then passes through the heat exchanger (5), part of the material returns to the first-stage reaction kettle (4), part of the material is mixed with alkali in the mixer (6) and enters the first-stage neutralization kettle (7), and the first-stage reaction is completed;
(3) the material is discharged from the first-stage neutralization kettle (7), passes through a heat exchanger (8), returns to the first-stage neutralization kettle (7), passes through a continuous water separator (9) and a heat exchanger (10), is mixed with alkylamine R2 in a mixer (11), and enters a second-stage reaction kettle (12);
(4) after being discharged from the second-stage reaction kettle (12), the material passes through a heat exchanger (13), part of the material returns to the second-stage reaction kettle (12), part of the material is mixed with alkali in a mixer (14) and enters a second-stage neutralization kettle (15), after the material which completes the second-stage reaction is discharged from the second-stage neutralization kettle (15), part of the material returns to the second-stage neutralization kettle (15) through a heat exchanger (16), and part of the material enters a continuous layering device (17) to separate a water phase, remove a solvent and dry the material, so that a triazine product is obtained;
the extracorporeal circulation amount is 3-20 times of the volume of the reaction kettle;
the temperature of the heat exchanger (5) is 0-25 ℃;
the temperature of the heat exchanger (8) is 15-30 ℃;
the temperature of the heat exchanger (10) is 10-30 ℃;
the temperature of the heat exchanger (13) is 20-45 ℃;
the temperature of the heat exchanger (16) is 35-50 ℃.
2. The continuous production method of triazine herbicides with multiple kettles connected in series as claimed in claim 1, wherein R1 is: one of monoethylamine, isopropylamine, diethylamine, isobutyronitrile amine, tert-butylamine, cyclopropylamine, amine acetate, isobutylamine, monomethylamine and dimethylamine.
3. The continuous production method of triazine herbicides with multiple kettles connected in series as claimed in claim 1, wherein the compound corresponding to R2 is: one of monoethylamine, isopropylamine, diethylamine, isobutyronitrile amine, tert-butylamine, cyclopropylamine, amine acetate, isobutylamine, monomethylamine and dimethylamine.
4. The continuous production method of triazine herbicides as set forth in claim 1, wherein the solvent in said cyanuric chloride solution is chlorobenzene, toluene, xylene, chloroform, carbon tetrachloride, benzene, ethanol or nitrobenzene.
5. A method for continuously producing triazine herbicides in series by a plurality of kettles as claimed in claim 1, wherein nitrogen gas is first filled in the compounding kettle (1) before compounding, and when the oxygen content is lower than the explosion range of the solvent, nitrogen gas filling is stopped, and two compounding kettles are selected, one is opened and the other is prepared.
6. The continuous production method of triazine herbicides as claimed in claim 5, wherein the compounding temperature of the compounding kettle (1) is 20-45 ℃; the temperature of the precooler (2) is-10 ℃.
7. The continuous production method of triazine herbicides as set forth in claim 1, wherein the ratio of the amount of cyanuric chloride to the amount of R1 or R2 fed is 1:1.0 to 1.05.
8. The continuous production method of triazine herbicides as claimed in claim 7, wherein the concentration of R1 and R2 is 50-100%.
9. The continuous production method of triazine herbicides as set forth in claim 1, wherein the ratio of the amount of alkali added to the mixer (6) and the mixer (14) to the amount of cyanuric chloride is 1.05-1.0: 1.
10. The continuous production method of triazine herbicides in series connection with multiple kettles as claimed in claim 1, wherein the oil phase at the upper part of the continuous layering device (17) is subjected to steam distillation desolventizing by metering into a plurality of desolventizing kettles (18) in sequence; the lower aqueous phase is sent to wastewater treatment.
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