CN110938019B - Continuous synthesis method of isoproturon - Google Patents
Continuous synthesis method of isoproturon Download PDFInfo
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- CN110938019B CN110938019B CN201911257732.8A CN201911257732A CN110938019B CN 110938019 B CN110938019 B CN 110938019B CN 201911257732 A CN201911257732 A CN 201911257732A CN 110938019 B CN110938019 B CN 110938019B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
- C07C273/1827—X being H
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/189—Purification, separation, stabilisation, use of additives
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Abstract
The invention discloses a method for continuously synthesizing isoproturon, which takes p-isopropylaniline as a starting material, performs continuous kettle-type phosgenation reaction with phosgene, performs continuous thermal decomposition to prepare p-isopropylaniline isocyanate, and performs kettle-type continuous amination reaction with dimethylamine to prepare the product isoproturon. The invention realizes the continuous production of the p-isopropyl phenyl isocyanate, adopts continuous tower type thermal decomposition and light-dispelling to replace kettle type light-dispelling, saves nitrogen and reduces the time of an operating platform; unreacted phosgene is pumped into the photochemical kettle again for reaction after being cooled, separated and absorbed by toluene, so that the phosgene utilization rate is improved, and the phosgene tail gas treatment cost is reduced; realizing continuous automatic operation of isoproturon synthesis.
Description
Technical Field
The invention relates to a method for synthesizing isoproturon.
Background
Isoproturon, the chemical name is N- (4-isopropylphenyl) -N ', N' dimethyl urea, high-efficient low-toxicity substituted urea herbicide. The weeding composition has the characteristics of wide weed control spectrum, long applicable period and the like, can prevent and kill off annual weeds such as crab grass, goosefoots, bluegrass, alopecurus, and the like, is suitable for weeding in partial vegetable fields such as tomatoes, potatoes, seedling-raising Chinese chives, sweet (hot) peppers, eggplants, broad beans, peas, onion and the like, and can be used before and after germination. The herbicide is compounded with other herbicides, has a synergistic effect, and is one of ideal dry-land herbicides.
At present, several hundreds of patents about isoproturon synthesis and its compound are reported at home and abroad, wherein the patents of the invention for synthesizing the original medicine mainly comprise the following patents: 1. a phosgene synthesis route using p-isopropylaniline as a raw material. 2. A non-phosgene synthesis route which takes p-isopropylaniline as raw material. 3. The synthesis route of p-isopropyl nitrobenzene as raw material and carbon monoxide. However, at present, the domestic industrial production is carried out by a phosgene route taking p-isopropylaniline as a raw material, and the typical phosgene routes comprise two routes: one is that chlorine hydride gas is introduced into toluene solution of p-isopropylaniline to form salt, and then phosgene is introduced to react to generate p-isopropylphenyl isocyanate; the other is that a toluene solution of p-isopropylaniline is dripped into a toluene solution containing phosgene for luminescence reaction to generate carbamoyl chloride; then the temperature is raised to remove hydrogen chloride to generate toluene solution of p-isopropyl phenyl isocyanate. After nitrogen gas is used for dispelling light, gas dimethylamine is introduced for reaction to generate a crude isoproturon product, and the crude isoproturon product is obtained through layering, crystallization and drying after water washing. The process has the following defects in operation:
firstly, salifying by using hydrogen chloride and then reacting by using phosgene to protect amino groups, the conversion of p-isopropylaniline can be ensured, but hydrogen chloride gas is consumed more and the treatment cost of tail gas is increased.
② in the process of adding p-isopropylaniline toluene solution by cold crystallization, the dropwise adding on the liquid surface can cause the side reaction of the added p-isopropylaniline due to insufficient light contact amount, and in order to ensure the reaction to obtain better efficiency, the concentration of reactants and the reaction temperature are required to fluctuate only in a narrower range.
The photochemical reaction is completed, and phosgene and hydrogen chloride can not be completely removed by using nitrogen, so that dimethylamine consumption is high in the isoproturon synthesis process, the whole system efficiency is low, and the ammonia nitrogen in the wastewater is high and is difficult to treat.
The whole reaction process is an intermittent reaction mode, which is not beneficial to automatic control operation and has high labor cost.
In this regard, the present project technician has been conducting analytical studies in order to seek better solutions. The invention better solves the problems in the production process of isoproturon, and the product quality and the yield are improved. The production process is not reported.
Disclosure of Invention
The invention aims to provide a continuous synthesis method of isoproturon, which realizes the continuous production of p-isopropylphenyl isocyanate.
The technical solution of the invention is as follows:
a method for continuously synthesizing isoproturon is characterized in that: the preparation method comprises the steps of taking p-isopropylaniline as a starting material, carrying out continuous kettle type phosgenation reaction on the p-isopropylaniline and phosgene, then carrying out continuous thermal decomposition on the p-isopropylaniline to obtain p-isopropylaniline isocyanate, and carrying out kettle type continuous amination reaction on the p-isopropylaniline and dimethylamine to obtain the product isoproturon.
The reaction kettle is provided with a stirrer and a cooling system.
The material mol ratio of phosgene to p-isopropylaniline is 3-4: 1.
the continuous synthesis method of isoproturon comprises the following specific steps:
(1) synthesis of p-isopropyl isocyanate
Pumping 100L of liquid phosgene toluene solution into a 300L phosgenation kettle with a stirrer and a cooling system; controlling the temperature in the kettle at 0-20 ℃, optimally (5-8) DEG C, and spraying 20% of p-isopropylaniline toluene solution from the position below the liquid level at the speed of 1000L/h; and simultaneously, according to the molar ratio of phosgene to p-isopropylaniline of 3-4: 1, pumping 40-60% phosgene toluene solution at a speed of 800-1000L/h for phosgenation reaction; the average time of the materials staying in the kettle is about 10 minutes; sequentially feeding the materials into a first-stage thermal decomposition tower, a second-stage thermal decomposition tower and a third-stage thermal decomposition tower, wherein the retention time of the materials in each stage of tower is about 1-2.5 hours, the temperature of the first-stage thermal decomposition tower is controlled to be 10-40 ℃, the temperature of the second-stage thermal decomposition tower is controlled to be 40-80 ℃, and the temperature of the third-stage thermal decomposition tower is controlled to be 80-110 ℃; hydrogen chloride and unreacted phosgene generated in the thermal decomposition process are removed;
after the thermal decomposition is finished, the material enters an intermediate buffer storage tank; pumping into a gas removing tower to remove residual hydrogen chloride and phosgene in the material by using nitrogen; after the gas is removed to be qualified, cooling the gas, and putting the gas into a toluene solution storage tank of p-isopropylphenyl isocyanate for synthesizing isoproturon; cooling, separating and absorbing excessive phosgene and hydrogen chloride tail gas in the first, second and third thermal decomposition towers, pumping into the photochemical kettle again for reaction after the excessive phosgene and the hydrogen chloride tail gas are separated, the hydrogen chloride tail gas containing a small amount of phosgene and the phosgene tail gas driven out by the gas driving tower are removed from the phosgene tail gas treatment tower to be absorbed into industrial hydrochloric acid;
(2) synthesis of isoproturon
Adopting kettle type first and second stage continuous reaction:
continuously pumping the p-isopropylphenyl isocyanate toluene solution in a p-isopropylphenyl isocyanate toluene solution storage tank into a primary amination kettle at the speed of 1200-1800L/h, and simultaneously continuously introducing dimethylamine gas at the speed of 30-60 kg/h; controlling the reaction temperature in the primary amination kettle to be 0-10 ℃, entering a secondary amination pH value adjusting kettle when the pH value in the primary amination kettle reaches about 7, and simultaneously introducing dimethylamine gas at the speed of 3-10 kg/h; controlling the reaction temperature in the secondary amination kettle to be 10-15 ℃, and finishing amination when the pH value in the secondary amination kettle reaches 8-10;
after amination is finished, the materials are pumped into a washing kettle, hot water is added according to the volume ratio of 1:1, stirring and washing are carried out, the temperature of the washing kettle is controlled to be about 80 ℃, and the retention time of the materials is 20 minutes. Then enters a first-stage phase separator to separate an organic phase and a water phase. Wherein: the water phase enters a secondary phase separator again, an entrained organic phase is separated out and is pumped into a washing kettle for reuse; separating the organic phase in a continuous crystallization separator;
the temperature of the continuous crystallizer is controlled to be 0-5 ℃. Drying the separated product tide to obtain an isoproturon product.
The invention has the advantages that:
firstly, continuous kettle type phosgenation reaction is adopted, and continuous tower type thermal decomposition and light dispelling are carried out. Realizes the continuous production of the p-isopropyl phenyl isocyanate.
② in the phosgenation process, a continuous reaction mode of continuously spraying toluene solution of p-isopropylaniline under the liquid surface of the toluene solution continuously introduced with phosgene is adopted to replace the common intermittent reaction mode of dropping p-isopropylaniline toluene solution on the liquid surface.
And thirdly, continuous tower type thermal decomposition and light dispelling are adopted to replace kettle type light dispelling, nitrogen is saved, and the time of an operation table is reduced.
Fourthly, unreacted phosgene is pumped into the photochemical kettle again for reaction after being cooled, separated and absorbed by toluene, the phosgene utilization rate is improved, and the phosgene tail gas treatment cost is reduced.
And fifthly, adopting kettle type continuous amination reaction, co-feeding cumene group isocyanate toluene solution and dimethylamine for amination, washing and crystallization. Realizing continuous automatic operation of isoproturon synthesis.
The present invention will be further described with reference to the following examples.
Detailed Description
The continuous synthesis process of isoproturon includes the following steps:
(1) synthesis of p-isopropyl isocyanate
Pumping 100L of liquid phosgene toluene solution into a 300L phosgenation kettle with a stirrer and a cooling system; controlling the temperature in the kettle at 0-20 ℃ (e.g. 0 ℃, 5 ℃, 8 ℃ and 20 ℃), and spraying 20% p-isopropylaniline toluene solution from the position below the liquid level at the speed of 1000L/h; and simultaneously, according to the molar ratio of phosgene to p-isopropylaniline being 3-4: 1 (example 3:1, 4: 1), pumping 40-60% (40%, 50%, 60%) phosgene in toluene solution at a rate of 800-1000L/h (example 800L/h, 900L/h, 1000L/h) for phosgenation reaction; the average time of the materials staying in the kettle is about 10 minutes; sequentially entering a first-stage thermal decomposition tower, a second-stage thermal decomposition tower and a third-stage thermal decomposition tower, wherein the retention time of materials in each stage of tower is about 1-2.5 hours, the temperature of the first-stage thermal decomposition tower is controlled at 10-40 ℃ (10 ℃, 20 ℃ and 40 ℃), the temperature of the second-stage thermal decomposition tower is controlled at 40-80 ℃ (40 ℃, 60 ℃ and 80 ℃), and the temperature of the third-stage thermal decomposition tower is controlled at 80-110 ℃ (80 ℃, 90 ℃ and 110 ℃); hydrogen chloride and unreacted phosgene generated in the thermal decomposition process are removed;
after the thermal decomposition is finished, the material enters an intermediate buffer storage tank; pumping into a gas removing tower to remove residual hydrogen chloride and phosgene in the material by using nitrogen; after the gas is removed to be qualified, cooling the gas, and putting the gas into a toluene solution storage tank of p-isopropylphenyl isocyanate for synthesizing isoproturon; cooling and separating excessive phosgene and hydrogen chloride tail gas in the first, second and third thermal decomposition towers, pumping the excessive phosgene and hydrogen chloride tail gas into the photochemical kettle for reaction after the excessive phosgene and hydrogen chloride tail gas are absorbed by toluene, and removing the separated hydrogen chloride tail gas containing a small amount of phosgene and the phosgene tail gas removed from the gas removing tower into a phosgene tail gas treatment tower for absorption to obtain industrial hydrochloric acid;
(2) synthesis of isoproturon
Adopting kettle type first and second stage continuous reaction:
continuously pumping the p-isopropylphenyl isocyanate toluene solution in a p-isopropylphenyl isocyanate toluene solution storage tank into a primary amination kettle at the speed of 1200-1800L/h (for example, 1200L/h, 1500L/h and 1800L/h), and simultaneously continuously introducing dimethylamine gas at the speed of 30-60 kg/h (for example, 30 kg/h, 40 kg/h and 60 kg/h); controlling the reaction temperature in the primary amination kettle at 0-10 ℃ (e.g. 0 ℃, 5 ℃ and 10 ℃), entering a secondary amination pH value adjusting kettle when the pH value in the primary amination kettle reaches about 7, and simultaneously introducing dimethylamine gas at the speed of 3-10 kg/h (e.g. 3 kg/h, 6 kg/h and 10 kg/h); controlling the reaction temperature in the secondary amination kettle to be 10-15 ℃ (example 10 ℃, 12 ℃ and 15 ℃), and ending amination when the pH value in the secondary amination kettle reaches 8-10 (examples 8, 9 and 10);
after amination is finished, the materials are pumped into a washing kettle, hot water is added according to the volume ratio of 1:1, stirring and washing are carried out, the temperature of the washing kettle is controlled to be about 80 ℃, and the retention time of the materials is 20 minutes. Then enters a first-stage phase separator to separate an organic phase and a water phase. Wherein: the water phase enters a secondary phase separator again, an entrained organic phase is separated out and is pumped into a washing kettle for reuse; separating the organic phase in a continuous crystallization separator;
the temperature of the continuous crystallizer is controlled to be 0-5 ℃ (e.g. 0 ℃, 3 ℃, 5 ℃). Drying the separated product damp product to obtain the isoproturon product. The product quality is more than 98 percent, and the yield is more than 98 percent. Realizing the continuous production of the product device.
Claims (1)
1. A method for continuously synthesizing isoproturon is characterized in that: taking p-isopropylaniline as an initial raw material, carrying out continuous kettle type phosgenation reaction on the p-isopropylaniline and phosgene, then carrying out continuous thermal decomposition to prepare p-isopropylaniline, and carrying out kettle type continuous amination reaction on the p-isopropylaniline and dimethylamine to prepare the product isoproturon; the method comprises the following specific steps:
(1) synthesis of p-isopropyl isocyanate
Pumping 100L of liquid phosgene toluene solution into a 300L phosgenation kettle with a stirrer and a cooling system; controlling the temperature in the kettle at 0-20 ℃, and spraying 20% of p-isopropylaniline toluene solution from the position below the liquid level at the speed of 1000L/h; and simultaneously, according to the molar ratio of phosgene to p-isopropylaniline of 3-4: 1, pumping 40-60% phosgene toluene solution at a speed of 800-1000L/h for phosgenation reaction; the average time of the materials staying in the kettle is 10 minutes; sequentially entering a first-stage thermal decomposition tower, a second-stage thermal decomposition tower and a third-stage thermal decomposition tower, wherein the retention time of materials in each stage of tower is 1-2.5 hours, the temperature of the first-stage thermal decomposition tower is controlled to be 10-40 ℃, the temperature of the second-stage thermal decomposition tower is controlled to be 40-80 ℃, and the temperature of the third-stage thermal decomposition tower is controlled to be 80-110 ℃; hydrogen chloride and unreacted phosgene generated in the thermal decomposition process are removed; after the thermal decomposition is finished, the material enters an intermediate buffer storage tank; pumping into a gas removing tower to remove residual hydrogen chloride and phosgene in the material by using nitrogen; after the gas is removed to be qualified, cooling the gas, and putting the gas into a toluene solution storage tank of p-isopropylphenyl isocyanate for synthesizing isoproturon; cooling and separating excessive phosgene and hydrogen chloride tail gas in the first, second and third thermal decomposition towers, pumping the excessive phosgene and hydrogen chloride tail gas into the photochemical kettle for reaction after the excessive phosgene and hydrogen chloride tail gas are absorbed by toluene, and removing the separated hydrogen chloride tail gas containing a small amount of phosgene and the phosgene tail gas removed from the gas removing tower into a phosgene tail gas treatment tower for absorption to obtain industrial hydrochloric acid;
(2) synthesis of isoproturon
Adopting kettle type first and second stage continuous reaction: continuously pumping the p-isopropylphenyl isocyanate toluene solution in a p-isopropylphenyl isocyanate toluene solution storage tank into a primary amination kettle at the speed of 1200-1800L/h, and simultaneously continuously introducing dimethylamine gas at the speed of 30-60 kg/h; controlling the reaction temperature in the primary amination kettle to be 0-10 ℃, entering a secondary amination pH value adjusting kettle when the pH value in the primary amination kettle reaches 7, and simultaneously introducing dimethylamine gas at the speed of 3-10 kg/h; controlling the reaction temperature in the secondary amination kettle to be 10-15 ℃, and finishing amination when the pH value in the secondary amination kettle reaches 8-10; after amination is finished, pumping the material into a washing kettle, adding hot water according to the volume ratio of 1:1, stirring and washing, controlling the temperature of the washing kettle at 80 ℃, and keeping the material body for 20 minutes; then enters a first-stage phase separator to separate an organic phase and a water phase; wherein, the water phase enters a secondary phase separator again, an entrained organic phase is separated out and pumped into a water washing kettle for reuse; separating the organic phase in a continuous crystallization separator; the temperature of the continuous crystallizer is controlled to be 0-5 ℃, and the separated product damp is dried to obtain an isoproturon product, wherein the product quality is more than 98%, and the yield is more than 98%.
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