CN112844281A - Dropwise stirring and acylation reaction method of s-metolachlor - Google Patents
Dropwise stirring and acylation reaction method of s-metolachlor Download PDFInfo
- Publication number
- CN112844281A CN112844281A CN202011580053.7A CN202011580053A CN112844281A CN 112844281 A CN112844281 A CN 112844281A CN 202011580053 A CN202011580053 A CN 202011580053A CN 112844281 A CN112844281 A CN 112844281A
- Authority
- CN
- China
- Prior art keywords
- reaction
- stirring
- reaction kettle
- feeding
- feeding pipeline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000003756 stirring Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005917 acylation reaction Methods 0.000 title claims abstract description 25
- WVQBLGZPHOPPFO-LBPRGKRZSA-N (S)-metolachlor Chemical compound CCC1=CC=CC(C)=C1N([C@@H](C)COC)C(=O)CCl WVQBLGZPHOPPFO-LBPRGKRZSA-N 0.000 title claims abstract description 12
- 239000005617 S-Metolachlor Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 68
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- -1 2-methyl-6-ethylphenyl Chemical group 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 10
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004009 herbicide Substances 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000002363 herbicidal effect Effects 0.000 description 5
- 150000002466 imines Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000005586 Nicosulfuron Substances 0.000 description 3
- 230000010933 acylation Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000012271 agricultural production Methods 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- RXTRRIFWCJEMEL-UHFFFAOYSA-N 2-chloropyridine-3-carbonyl chloride Chemical compound ClC(=O)C1=CC=CN=C1Cl RXTRRIFWCJEMEL-UHFFFAOYSA-N 0.000 description 1
- IBRSSZOHCGUTHI-UHFFFAOYSA-N 2-chloropyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC=CN=C1Cl IBRSSZOHCGUTHI-UHFFFAOYSA-N 0.000 description 1
- 241001504226 Hoodia Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000005578 Mesotrione Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000017277 hoodia Nutrition 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Abstract
The invention discloses a dropwise adding stirring acylation reaction method of s-metolachlor, which comprises the steps of firstly putting a preset amount of sodium carbonate into a reaction kettle, then controlling a first electromagnetic valve to be opened by a control cabinet, and feeding 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine through a first feeding pipeline; opening a second electromagnetic valve, and feeding benzene into a second feeding pipeline; then the motor drives pivot and paddle and begins to rotate, stirs, makes the liquid intensive mixing, and the third solenoid valve is opened afterwards, and the benzene solution of chloracetyl chloride is sent into the cauldron to the third conveying pipeline, instils into in the reaction liquid of below through dropwise add mechanism, slowly stirs until the reaction is accomplished. The mechanical stirring structure and the dripping mechanism adopted by the invention have simple structure and good effect, improve the reaction yield and are beneficial to the popularization of the product in agriculture in China.
Description
Technical Field
The invention relates to the technical field of production and preparation of raw pesticides of agricultural herbicide products, in particular to a dropwise stirring acylation reaction method of s-metolachlor.
Background
With the continuous progress of society, the requirements for agricultural production are more and more important, and in modern agricultural production, the requirements for related pesticides such as herbicides are more and more increased, so that the production scale is enlarged, and high-efficiency and safe production is imperative.
The s-metolachlor is a novel environment-friendly herbicide with high efficiency and high selectivity, can be used for various crops, has the characteristics of safety, high efficiency, low toxicity, low residue, environmental friendliness and the like, is the fourth most herbicide in the world, and is a backbone variety of the herbicide in developed countries and regions such as European Union, America and the like. However, one of the main problems of the product popularized in China at present is that the production cost is too high, the product price is also high, and therefore large-area popularization is difficult at present, and therefore a preparation method which is suitable for large-scale industrial production and has low cost is found, and the preparation method has important significance for popularization of the herbicide in agriculture. The synthesis method of the s-metolachlor produced by the applicant at present adopts an asymmetric catalytic synthesis process, and comprises four steps of synthesis of intermediate methoxy acetone, alkylation dehydration reaction, hydrogenation reduction reaction and acylation reaction, wherein the acylation reaction is to mix amine ether and Na2CO3And adding an organic solvent into the reaction kettle, then adding chloroacetyl chloride, and after the reaction is finished, carrying out post-treatment and refining to obtain the refined metolachlor. The reaction process needs to adopt a reaction kettle, the proportion of each added raw material is accurately controlled, and the preparation is only carried out in a laboratory scale before. In the industrial production, mature preparation processes and process parameters are lacked for reference, so that the research on the aspect has important significance for the application of the product in agriculture in China.
Disclosure of Invention
In order to solve the technical problem, the invention provides a dropwise stirring acylation reaction method of s-metolachlor.
The complete technical scheme of the invention comprises the following steps:
a dropwise adding stirring acylation reaction method of metolachlor, the reaction device includes the reaction kettle, the reaction kettle has mechanical stirring apparatus, the mechanical stirring apparatus includes the overhead agitator motor, the agitator motor connects with the transmission spindle, there are stirring paddle groups on the spindle, the stirring paddle group includes the first stirring paddle located above and the second stirring paddle located below, wherein the second stirring paddle is smaller than the first stirring paddle, and its shape follows the shape of the camber at the bottom of the reaction kettle;
a first feeding pipeline is arranged at one side of the reaction kettle, a first electromagnetic valve and a first flowmeter are arranged on the first feeding pipeline, a second feeding pipeline is arranged at the other side of the reaction kettle, a second electromagnetic valve and a second flowmeter are arranged above the second feeding pipeline,
a third feeding pipeline is arranged above the reaction kettle, a third electromagnetic valve and a third flow meter are arranged above the third feeding pipeline,
a rain dripping mechanism is arranged in the reaction kettle, is positioned above the reaction kettle and is a circular stainless steel plate, uniform holes are formed in the plate, and when reaction is carried out, liquid above enters the kettle through a third feeding pipeline and is dripped into reaction liquid below through the holes in the circular stainless steel plate in a rain mode;
a gas discharge pipeline is arranged above the reaction kettle;
during the acylation reaction, firstly, a preset amount of sodium carbonate is put into a reaction kettle, then the control cabinet controls the first electromagnetic valve to be opened, and 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine is fed into the reaction kettle through a first feeding pipeline; opening a second electromagnetic valve, and feeding benzene into a second feeding pipeline; then the motor drives pivot and paddle and begins to rotate to stir at first rotational speed, makes the liquid intensive mixing, and the third solenoid valve is opened afterwards, and the benzene solution of chloracetyl chloride is sent into the cauldron to the third conveying pipeline, drips into the reaction liquid of below through drenching dropwise add mechanism, and the paddle continues slowly to stir with the second rotational speed this moment, and the reaction is accomplished after 1 h.
Preferably, the dosage ratio of the raw materials is 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine: sodium carbonate: 40.5Kg of benzene: 33.4 Kg: 220L.
Preferably, the first rotational speed is 180 rpm.
Preferably, the second rotation speed is 60 rpm.
The method adopts an industrial-grade automatic control system to automatically control and monitor the feeding and reaction processes in the acylation process of the metolachlor, realizes the accurate control of the feeding amount and the reaction process, and has simple mechanical stirring structure and dripping mechanism structure, good effect and improved reaction yield. The method meets the requirement of industrial production, reduces the cost, is easy to realize and is beneficial to the popularization of the product in agriculture in China.
Drawings
FIG. 1 is a schematic diagram of the dropwise addition stirring acylation reaction structure of s-metolachlor of the present invention.
Fig. 2 is a schematic structural view of the rain dropping mechanism.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only illustrative and are not intended to limit the present application.
The invention is further explained by taking the production process of the original drug of the metolachlor as an example, the synthesis method of the metolachlor adopts an asymmetric catalytic synthesis process, comprises four steps of synthesis of intermediate methoxy acetone, alkylation dehydration reaction, hydrogenation reduction reaction and acylation reaction, and researches in laboratories show that the synthesis by the technical route can shorten the reaction time, improve the conversion rate and ensure reasonable cost. However, for industrial application, it is very important to convert small-dose production in a laboratory into industrial large-scale production, and to realize safe, short-production-cycle, and high-efficiency production. Therefore, the applicant develops verification and research of large-scale production aiming at each link in the synthesis process and designs automation of the whole production process.
The invention relates to a medicinal herb of Hoodia alataThe production process of the amine technical product comprises four steps of synthesis of intermediate methoxy acetone, alkylation dehydration reaction, hydrogenation reduction reaction and acylation reaction, wherein the acylation reaction is to mix amine ether and Na2CO3And adding an organic solvent into the reaction kettle, then adding chloroacetyl chloride, and after the reaction is finished, carrying out post-treatment and refining to obtain the refined metolachlor.
The synthetic method of this process is as shown in fig. 1, the synthesizer includes reation kettle 1, reation kettle has mechanical stirring device, specifically include the agitator motor 2 of top, agitator motor is connected with transmission pivot 3, be equipped with stirring paddle leaf in the pivot, stirring paddle leaf is including the first stirring paddle leaf 4 that is located the top and the second stirring paddle leaf 5 that is located the below, wherein second stirring paddle leaf 5 is less than first stirring paddle leaf, and the camber shape of its shape and reation kettle bottom follows the shape, this is because the used reation kettle is the arc at the bottom, in order to can the intensive mixing, prevent that the liquid reaction of bottom is insufficient, on traditional stirring paddle basis, add a less second stirring paddle, its shape follows the shape at the bottom of with the reation kettle, the liquid of bottom can the intensive mixing.
A first feeding pipeline 6 is arranged at one side of the reaction kettle, a first electromagnetic valve 7 and a first flowmeter 8 are arranged on the first feeding pipeline, a second feeding pipeline 9 is arranged at the other side of the reaction kettle, a second electromagnetic valve 10 and a second flowmeter 11 are arranged above the second feeding pipeline,
a third feeding pipeline 12 is arranged above the reaction kettle, a third electromagnetic valve 13 and a third flow meter 14 are arranged above the third feeding pipeline,
inside rain drop mechanism 15 that is equipped with of reation kettle, this rain drop mechanism is located reation kettle inside top, for circular corrosion resistant plate, even hole 16 has been seted up on the board, when carrying out the reaction, the liquid of top passes through the third conveying pipeline and gets into in the cauldron, and through the hole on the circular corrosion resistant plate with the reaction liquid of rain mode dropwise add to the below, such design is because when carrying out laboratory research, the benzene solution of this process chloracetyl chloride is through dropwise add the reaction liquid, but when carrying out industrial production, can not add with dropwise mode, nevertheless because reaction rate can not be too fast, consequently, the dropwise add mechanism of rain formula has been designed to the reference, make the benzene solution of chloracetyl chloride get into below reaction solution with reasonable speed, reaction efficiency has been improved. A gas discharge pipeline 17 is arranged above the reaction kettle.
During the acylation reaction, firstly, a preset amount of sodium carbonate is put into a reaction kettle, then the control cabinet controls the first electromagnetic valve to be opened, and 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine is fed through the first feeding pipeline 6; the second electromagnetic valve is opened, benzene is fed into the second feeding pipeline 9, and the dosage ratio of the benzene to the benzene fed into the kettle is 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine: sodium carbonate: 40.5Kg of benzene: 33.4 Kg: 220L, then the motor drives the rotating shaft and the paddle to start rotating, and stirring is carried out at the rotating speed of 180rpm, so that the liquid is fully mixed. And then the third electromagnetic valve is opened, the third feeding pipeline 12 feeds the benzene solution of chloracetyl chloride into the kettle, the benzene solution is dripped into the reaction liquid below through the rain dripping mechanism 15, at the moment, the paddle continuously and slowly stirs at the rotating speed of 60rpm, and the reaction is finished after 1 h. And after the reaction is finished, the raw material enters a desolventizing kettle for desolventizing to obtain the original metolachlor.
The acylation reaction device is also suitable for the acylation chlorination reaction of nicosulfuron technical and mesotrione technical, for example, the current synthesis process of the nicosulfuron intermediate of the applicant comprises two steps of synthesis and amination of the intermediate 2-chloronicotinoyl chloride, wherein the acylation chlorination reaction comprises the steps of adding 2-chloronicotinic acid and an organic solvent into a reaction kettle, then adding a solid phosgene solution, and after the reaction is finished, carrying out aftertreatment and refining to obtain the nicosulfuron intermediate. The preparation process has similarities, so that the acylation reaction device can be used in the preparation process of the technical product.
In addition, other steps of the synthetic method of the metolachlor are introduced:
1. and (3) carrying out catalytic dehydrogenation reaction to synthesize intermediate methoxy acetone:
the process adopts a tubular fixed bed reactor, a plurality of reaction tubes are arranged in the reactor, each reaction tube is filled with a Cu/ZnO catalyst, the diameter of the tube is 10cm, the length of the tube is 1.5m, inert magnetic ring fillers with different sizes are filled in sections at the ends, the bottom of the reactor is connected with a feed pipeline, a feed electromagnetic valve and a feed flowmeter are arranged on the feed channel, an air outlet pipeline is arranged at the top of the reactor, a pressure sensor and an air outlet flowmeter are arranged on the air outlet pipeline, and the electromagnetic valve, the pressure sensor and the flowmeters are all connected to a control cabinet.
When the reaction is carried out, the control cabinet controls the feeding electromagnetic valve to be opened, liquid raw material 1-methoxy-2-propanol is added into the reactor from the feeding pipeline through the plunger pump, the feeding flowmeter measures the feeding and transmits the feeding back to the control cabinet, meanwhile, the electric heating device is adopted to heat the reactor, the 1-methoxy-2-propanol generates methoxy acetone under the catalysis effect, the generated hydrogen is discharged from the gas outlet pipeline, the gas outlet flowmeter transmits the hydrogen flow to the control cabinet, the control cabinet calculates the generated hydrogen quality according to the volume flow of the hydrogen and the pressure data transmitted back by the pressure sensor, and monitors the relation between the discharged hydrogen quality in a certain time and the time. The reaction is considered to be normal when the hydrogen amount floats within +/-10% in the time period, when the hydrogen amount continuously decreases and exceeds 10%, a warning is sent out, and after the hydrogen amount continuously decreases and exceeds 20%, the control cabinet control system stops and the catalyst is replaced in time.
The reaction formula of the step is as follows:
meanwhile, in the actual industrial production of the step, the dehydrogenation conversion rate and the speed of the reaction need to be comprehensively considered, although the dehydrogenation conversion rate can be improved by prolonging the reaction time, the production takt can be prolonged, the production efficiency is reduced, and the improper shortening of the reaction time can possibly cause the too low dehydrogenation conversion rate, thereby causing waste, improving the cost and being not beneficial to environmental protection.
The reaction speed mainly depends on the amount of the 1-methoxy-2-propanol added and the reaction conditions, and in the invention, the research shows that in the process, under the condition of a certain amount of raw material added, the bulk density, the amount, the reaction temperature and the like of the used catalyst can cause different reaction speeds and dehydrogenation conversion rates, and the conversion rate of the raw material greatly changes under different combination parameters. Therefore, according to the actual industrial requirements, the reaction speed and yield for industrial production are ensured, and the dehydrogenation conversion rate is maintained at a higher level to improve the yield. In the actual production, the influence of various parameter changes in the reaction process on the reaction is respectively researched, parameters with obvious effects are selected, and the following defined relationship is obtained through analysis fitting and actual production verification:
in the formula: t is reaction temperature, and the control range is 220-280 ℃; a is a conversion coefficient, the conversion coefficient reflects the comprehensive effect of other factors which are not obviously influenced in the actual production, and the value range is 6.2-10.6; rho is the bulk density of the Cu/ZnO catalyst, and the value range is 700-750 Kg/m3(ii) a L is the amount of 1-methoxy-2-propanol fed in unit time, and the range is 10-30 Kg/h; s is the specific surface area of the catalyst and has a value range of 120-150 m2(ii) in terms of/g. In the actual reaction process, under the condition that parameters such as the adding amount of the 1-methoxy-2-propanol, the bulk density of the catalyst and the like are fixed, the proper reaction temperature is selected, and the reaction speed and the dehydrogenation reaction rate are ensured.
2. Alkylation dehydration reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) imine
The reaction formula of the step is as follows:
the alkylation dehydration reaction is to add intermediate methoxy acetone, 2-methyl-6-ethyl aniline and organic solvent into a reaction kettle, react at a certain temperature, and obtain intermediate imine by rectification after the reaction is finished. The feeding in the process is carried out by adopting the automatic control method, and the method adopts an automatic control device which comprises a reaction kettle, a conveying system, a reaction monitoring system and a control system.
The reaction kettle is used as a reaction container and is connected with a conveying system, the conveying system comprises a first conveying pipeline, the first conveying pipeline is connected with a 2-methyl-6-ethylaniline storage tank, and a first conveying pump, a first electromagnetic valve and a first flowmeter are arranged on the first conveying pipeline.
The organic solvent benzene storage tank is connected with the first conveying pipeline, and a first conveying pump, a first electromagnetic valve and a first flowmeter are arranged on the first conveying pipeline.
The reaction device also comprises a third conveying pipeline, wherein the third conveying pipeline is connected with the intermediate 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine reaction fixed bed in the previous working procedure, a buffer tank is arranged between the third conveying pipeline and the fixed bed, and a third conveying pump, a third electromagnetic valve and a third flowmeter are arranged on the third conveying pipeline.
The control system is a PLC, all the electromagnetic valves and the flow meters are connected to the PLC, and real-time flow is transmitted to the PLC.
The reaction monitoring system comprises a temperature sensor and a pressure sensor which are arranged on the reaction kettle, and transmits the real-time reaction pressure and temperature to the PLC.
When the reaction is carried out, the control system respectively controls the electromagnetic valves to be opened according to preset parameters, and the delivery pumps respectively pump 2-methyl-6-ethylaniline, benzene and 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine according to the ratio of 2-methyl-6-ethylaniline: methoxy acetone: benzene 7.5: 15: a flow ratio of 12 was fed into the reactor. Each flowmeter is respectively gathered real-time flow on each pipeline, every 0.5 second is gathered once to give PLC with flow data transmission, PLC calculates the contrast and regulates and control the flow data of gathering, and the concrete mode is: the PLC adds the flow data collected by each conveying pipeline respectively and compares the accumulated values, and the conveying time, the collecting time and the frequency are consistent, so that the volume ratio of each raw material can be reflected by the accumulated values. In particular to the selection of the cumulative flow L of intermediate methoxy acetone3As a reference value, and 2-methyl-6-ethylaniline L1And cumulative flow L of benzene2Dividing by a reference value, and calculating the following two parameters in real time:
when sigma is1Or σ2When the pressure is more than 0.5% or less than-0.5%, the control system controls the electromagnetic valve on the corresponding pipeline to open/close for a short time. E.g. as sigma1If the value is too high, the first electromagnetic valve is closed for a short time, and the feeding amount of the 2-methyl-6-ethylaniline is reduced. Otherwise, the feeding amount of the methoxy acetone and the benzene is closed for a short time. The total flow ratio was made to match the preset 2-methyl-6-ethylaniline: methoxy acetone: benzene 7.5: 15: 12, controlling the reaction temperature to be 75-90 ℃ and the reaction time to be 9-10 hours. After the reaction is finished, benzene is separated out by a decompression method, and the residual reaction liquid is distilled to obtain a liquid product 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) imine.
3. Hydrogenation reduction reaction, synthesis of intermediate 1-methoxy propyl-2- (2-methyl-6-ethyl phenyl) amine:
the reaction formula of the step is as follows:
the synthesis device comprises a high-pressure reaction kettle, wherein a catalyst is placed in the high-pressure reaction kettle, a feeding conveying pipeline for conveying 2-methyl-6-ethyl phenyl-imine is connected to the high-pressure reaction kettle 1, and a feeding electromagnetic valve and a feeding flow meter are arranged on the feeding conveying pipeline.
An air inlet conveying pipeline for conveying hydrogen is connected above the high-pressure reaction kettle, and an air inlet electromagnetic valve, an air inlet flow meter and a pressure sensor are arranged on the air inlet conveying pipeline.
One side of the high-pressure reaction kettle is connected with a buffer tank through an air supply pipeline, and a safety valve is arranged on an exhaust pipeline.
The feeding electromagnetic valve, the feeding flow meter, the air inlet electromagnetic valve, the air inlet flow meter, the pressure sensor and the safety valve are all connected to the control cabinet.
The high-pressure reaction kettle is simultaneously provided with an in-kettle temperature sensor and an in-kettle pressure sensor for monitoring the temperature and the pressure in the kettle, and the temperature and the pressure sensors are also connected to the control cabinet.
When the reaction is carried out, the control cabinet controls the electromagnetic valves to be opened according to preset parameters, 2-methyl-6-ethyl phenyl-imine is pumped into the reaction kettle, the feed flowmeter collects the conveyed flow and sends the collected flow to the control cabinet, and after the preset amount is reached, hydrogen is added to start the reaction, wherein the electromagnetic valves, the pressure sensor, the temperature sensor and the pressure sensor in the autoclave for conveying the hydrogen are interlocked with the control system and the pressure relief safety valve. The reaction temperature is controlled to be 50 +/-5 ℃ in the synthesis process, and the hydrogen pressure is controlled to be 6-8 MPa. In the reaction process, when the pressure value in the reaction kettle exceeds 1.2 times of the preset value, the control system controls the feeding electromagnetic valve to be closed and opens the pressure relief safety valve, so that gas in the kettle enters the buffer tank, the pressure in the kettle is reduced, and the preset value of the pressure in the kettle is 6-8 MPa.
The mass ratio of the raw materials to the catalyst in the reaction kettle is 2-methyl-6-ethyl phenyl-imine: 1-S-diphenylphosphino-2-R-bis (3, 5-dimethylphenyl) phosphinotrien-ruthenium: iridium bromide 38000:10: 2; the reaction temperature is 50 +/-5 ℃, and the reaction time is 6 hours; after the reaction was completed, 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine was obtained by distillation.
4. Acylation reaction: preparation of s-metolachlor
The preparation process is as described above.
The above applications are only some embodiments of the present application. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept herein, and it is intended to cover all such modifications and variations as fall within the scope of the invention.
Claims (4)
1. A dropwise adding stirring acylation reaction method of metolachlor is characterized in that a reaction device comprises a reaction kettle, the reaction kettle is provided with a mechanical stirring device, the mechanical stirring device comprises an upper stirring motor, the stirring motor is connected with a transmission rotating shaft, a stirring paddle group is arranged on the rotating shaft, the stirring paddle group comprises a first stirring paddle positioned above and a second stirring paddle positioned below, wherein the second stirring paddle is smaller than the first stirring paddle, and the shape of the second stirring paddle follows the shape of an arc surface at the bottom of the reaction kettle;
a first feeding pipeline is arranged at one side of the reaction kettle, a first electromagnetic valve and a first flowmeter are arranged on the first feeding pipeline, a second feeding pipeline is arranged at the other side of the reaction kettle, a second electromagnetic valve and a second flowmeter are arranged above the second feeding pipeline,
a third feeding pipeline is arranged above the reaction kettle, a third electromagnetic valve and a third flow meter are arranged above the third feeding pipeline,
a rain dripping mechanism is arranged in the reaction kettle, is positioned above the reaction kettle and is a circular stainless steel plate, uniform holes are formed in the plate, and when reaction is carried out, liquid above enters the kettle through a third feeding pipeline and is dripped into reaction liquid below through the holes in the circular stainless steel plate in a rain mode;
a gas discharge pipeline is arranged above the reaction kettle;
during the acylation reaction, firstly, a preset amount of sodium carbonate is put into a reaction kettle, then the control cabinet controls the first electromagnetic valve to be opened, and 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine is fed into the reaction kettle through a first feeding pipeline; opening a second electromagnetic valve, and feeding benzene into a second feeding pipeline; then the motor drives pivot and paddle and begins to rotate to stir at first rotational speed, makes the liquid intensive mixing, and the third solenoid valve is opened afterwards, and the benzene solution of chloracetyl chloride is sent into the cauldron to the third conveying pipeline, drips into the reaction liquid of below through drenching dropwise add mechanism, and the paddle continues slowly to stir with the second rotational speed this moment, and the reaction is accomplished after 1 h.
2. The dropwise stirring acylation reaction method of s-metolachlor as claimed in claim 1, wherein the raw materials are used in the ratio of 1-methoxypropyl-2- (2-methyl-6-ethylphenyl) amine: sodium carbonate: benzene =40.5 Kg: 33.4 Kg: 220L.
3. The dropwise stirring acylation reaction method of s-metolachlor as claimed in claims 1-2, wherein the first rotation speed is 180 rpm.
4. The dropwise stirring acylation reaction method of s-metolachlor as claimed in claims 1 to 3, wherein the second rotation speed is 60 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011580053.7A CN112844281A (en) | 2020-12-28 | 2020-12-28 | Dropwise stirring and acylation reaction method of s-metolachlor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011580053.7A CN112844281A (en) | 2020-12-28 | 2020-12-28 | Dropwise stirring and acylation reaction method of s-metolachlor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112844281A true CN112844281A (en) | 2021-05-28 |
Family
ID=75997607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011580053.7A Pending CN112844281A (en) | 2020-12-28 | 2020-12-28 | Dropwise stirring and acylation reaction method of s-metolachlor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112844281A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114558517A (en) * | 2022-03-08 | 2022-05-31 | 上海亚孚化学有限公司 | Coupling agent preparation facilities with adjustable |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040251A1 (en) * | 2008-10-08 | 2010-04-15 | 湖南大学 | Process and apparatus for preparing terephthalic acid by air oxidation of para-xylene |
| CN204338162U (en) * | 2014-12-30 | 2015-05-20 | 山东易达利化工有限公司 | A kind of reactor with composite stirring oar |
| CN205925699U (en) * | 2016-08-16 | 2017-02-08 | 甘肃工业职业技术学院 | Chemical industry raw material mixing filter responses jar convenient to compounding |
-
2020
- 2020-12-28 CN CN202011580053.7A patent/CN112844281A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010040251A1 (en) * | 2008-10-08 | 2010-04-15 | 湖南大学 | Process and apparatus for preparing terephthalic acid by air oxidation of para-xylene |
| CN204338162U (en) * | 2014-12-30 | 2015-05-20 | 山东易达利化工有限公司 | A kind of reactor with composite stirring oar |
| CN205925699U (en) * | 2016-08-16 | 2017-02-08 | 甘肃工业职业技术学院 | Chemical industry raw material mixing filter responses jar convenient to compounding |
Non-Patent Citations (1)
| Title |
|---|
| 李倩: "《（S）-异丙甲草胺的不对称合成研究》", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114558517A (en) * | 2022-03-08 | 2022-05-31 | 上海亚孚化学有限公司 | Coupling agent preparation facilities with adjustable |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724028A (en) | Interlocking control hydrogenation reaction method for agricultural herbicide technical production | |
| CN102924285B (en) | Preparation method of dimethyldiallylammonium chloride | |
| CN112844281A (en) | Dropwise stirring and acylation reaction method of s-metolachlor | |
| CN112844248B (en) | Dehydrogenation interlocking control method for preparation of s-metolachlor raw pesticide | |
| CN204865828U (en) | Cinnamic acid gas -liquid mixture reation kettle | |
| CN109529748A (en) | A kind of chemical industry synthesis reaction kettle | |
| CN212167083U (en) | Weighing type feed additive agitating unit | |
| CN112844237A (en) | Feeding control method for dehydration reaction in preparation of agricultural herbicide technical | |
| CN216630748U (en) | Production device of high-purity phenylacetic acid ethyl ester | |
| CN105111100B (en) | The lab scale continuous process system of cyclohexanone oxime | |
| CN108727211B (en) | Method and device for continuous acylation synthesis of pretilachlor | |
| CN106732253A (en) | One kind filters integrated reactor of weighing | |
| CN110256204A (en) | A kind of preparation method of prenol | |
| CN111018907A (en) | Continuous kettle type industrial production method and system for crude acetal product | |
| CN208465874U (en) | A kind of external mixer for hydrogen fluoride | |
| CN220361183U (en) | Addition kettle for ethyl maltol production | |
| CN209352924U (en) | A kind of pyridine carboxylic acid biological enzyme reactor | |
| CN214681746U (en) | Zinc reagent preparation facilities and reaction system | |
| CN210994311U (en) | Production device for synthesizing imazethapyr by one-step method | |
| CN207391292U (en) | Amino acid Water soluble fertilizer process units | |
| CN208066350U (en) | A kind of novel ester reaction kettle | |
| CN107382738B (en) | A method of preparing alkyl ynamine | |
| CN206705702U (en) | A kind of aluminium polychloride production system | |
| CN219898170U (en) | Safe type reation kettle | |
| CN201141011Y (en) | Natural identical methyl acetyl carbinol dimer perfume reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210528 |
|
| RJ01 | Rejection of invention patent application after publication |